International Congress Engineering of Advanced Materials ICEAM2017 10 – 12 October 2017 · Erlangen · Germany International Congress Engineering of Advanced Materials ICEAM2017

www.iceam2017.fau.de www.iceam2017.fau.de

Content

1 – Welcome 1 2 – Information on EAM and FAU 2 3 – Confirmed Speakers (Plenary, EAM Talk, Keynote) 3 4 – Scientific Organizing Committee and Congress Office 4 5 – ICEAM2017 Program 5 6 – Plenary Talk Abstracts 10 7 – EAM Talk Abstracts 17 8 – Keynote Talk Abstracts 25 9 – Session Talk Abstracts 42 10 – Poster Presentation Abstracts 129 11 – List of Participants 230

Welcome to the International Congress Engineering of Advanced Materials ICEAM2017 10 – 12 October 2017 Erlangen, Germany

It is our pleasure to welcome you to Erlangen for the International Congress Engineering of Advanced Materials ICEAM2017, organized by the Cluster of Excellence – Engineering of Advanced Materials (EAM) at the Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU).

ICEAM2017 provides a showcase for 10 years of interdisciplinary research at EAM and places it in an international context for state-of-the-art science and engineering research. The congress addresses local, national and international researchers working in the fields where EAM is active. The program themes will focus on EAM’s four application fields: Nanoelectronic Materials, Photonic and Optical Materials, Catalytic Materials and Lightweight Materials. Furthermore, the key role played by our cross-sectional topics, namely Functional Particle Systems, Nanoanalysis and Microscopy, and Multiscale Modeling and Simulation will be emphasized throughout the congress.

With a mix of high profile external invited plenary, keynote and session talks, combined with excellent internal contributions and a high-quality poster session, we hope for a wide range of inspiring interactions and fruitful discussions.

We are looking forward to the next days, full of scientific expertise and exchange.

Prof. Wolfgang Peukert Prof. Peter Wasserscheid Cluster Coordinator Cluster Co-Coordinator

Institute of Particle Technology Institute of Chemical Reaction Engineering FAU Erlangen-Nürnberg FAU Erlangen-Nürnberg Cauerstr 4 Egerlandstr. 3 91058 Erlangen 91058 Erlangen Germany Germany

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Cluster of Excellence Engineering of Advanced Materials (EAM) www.eam.fau.de

In 2007, the Cluster of Excellence ‘Engineering of Advanced Materials––Hierarchical Structure Formation for Functional Devices’ (EAM) was established at FAU as part of the German federal and regional governments’ Excellence Initiative. It is the only interdisciplinary research collaboration of its type in Germany to focus on the investigation of functional materials and their processing at all length scales. Its research centers on the fundamental and applied aspects of designing and creating novel high-performance materials. At the Cluster 200 researchers from nine disciplines and three faculties collaborate in 90 projects in basic research as well as in many areas of application. More than 1,900 publications in peer-review journals in the past ten years and 14 ERC grants for EAM researchers are examples of its outstanding success in research.

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) www.fau.eu

Founded in 1743, FAU has a rich history. It is a strong research university with an international perspective and one of the largest universities in Germany, with 39,868 students, 263 degree programs, 4,000 academic staff (including over 576 professors), 177,6 million euros (2016) third-party funding, and 500 partnerships with universities all over the world. Teaching at the University is closely linked to research and focuses on training students in both theory and practice to enable them to think critically and work independently. The research itself also strikes the perfect balance between a theoretical approach and practical application. FAU’s outstanding research and teaching is reflected in top positions in both national and international rankings, as well as the high amount of DFG funding which its researchers are able to secure.

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Confirmed Speakers

Plenary Prof. Cynthia Friend Harvard University Prof. Paolo Samori Université de Strasbourg & CNRS Prof. Andreas Schreyer European Spallation Source ESS ERIC, Prof. Ole Sigmund Technical University of Denmark Prof. Andreas Stein University of Minnesota

EAM Talks – all Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Wolfgang Peukert Research Area A1 Functional Particle Systems Prof. Erdmann Spiecker Research Area A2 Nanoanalysis & Microscopy Prof. Günter Leugering Research Area A3 Multiscale Modeling & Simulation Prof. Andreas Hirsch Research Area B Nanoelectronic Materials Prof. Robin Klupp Taylor Research Area C Photonic & Optical Materials Prof. Peter Wasserscheid Research Area D Catalytic Materials Prof. Carolin Körner Research Area E Lightweight Materials

Keynote Prof. Alán Aspuru-Guzik Harvard University Prof. Irene Beyerlein University of California, Santa Barbara (UCSB) Prof. Helmut Cölfen Universität Konstanz Prof. William Curtin École polytechnique fédérale de Lausanne (EPFL) Prof. Michael Engel Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Hannsjörg Freund Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) PD Dr. Marco Haumann Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) PD Dr. Wolfgang Hieringer Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Norbert Koch Humboldt-Universität zu Berlin, Integrative Research Institute for the Sciences (IRIS) Dr. Ning Li Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Dr. Advenit Makaya European Space Agency (ESA) Prof. Bernd Meyer Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU)

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Prof. Regina Palkovits Rheinisch-Westfälische Technische Hochschule Aachen (RWTH) Dr. Stefanie Rechberger Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Markus Schmidt Leibniz-Institut für Photonische Technologien Jena (IPHT) Prof. Bala Subramaniam Center for Environmentally Beneficial Catalysis (CEBC), University of Kansas Prof. Tobias Unruh Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Nicolas Vogel Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Prof. Tanja Weil Max-Planck-Institut für Polymerforschung, Mainz Prof. Gregor Witte Philipps-Universität Marburg Prof. Jana Zaumseil Universität Heidelberg

Scientific Organization Committee Dr. Monica Distaso Prof. Dr.-Ing. Hannsjörg Freund Prof. Dr. Marcus Halik PD Dr. Heinz Werner Höppel Prof. Robin N. Klupp Taylor, MEng, DPhil (Oxon) Dr. Doris Segets Prof. Dr. Michael Stingl Prof. Dr. Tobias Unruh Prof. Dr. Nicolas Vogel Dr. Fabian Wein

ICEAM2017 Congress Office Marlene Scheuermeyer, Ina Viebach (Program coordination), Aline Looschen (Administration coordination), Michael Hartmann (Accounting) ICEAM2017 Congress Office Cluster of Excellence Engineering of Advanced Materials (EAM) Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Nägelsbachstraße 49b, 91052 Erlangen, Germany Phone: +49 9131 85-20846 E-Mail: [email protected] www.iceam2017.fau.de

4 9:00 – EAM Talk 1 > H 11 Tuesday 9:30 Introduction EAM · Research Area A1: Functional Particle Systems – Process, structure and property design Oct 10 2017 Prof. Wolfgang Peukert LFG, FAU Erlangen-Nürnberg 9:00 –— 13:30 9:30 – Plenary Talk 1 > H 11 10:00 Design of sustainable catalytic processes on nanoporous ­materials Prof. Cynthia Friend Harvard University

10:00 COFFEE BREAK > Tentoria

10:30 – KeyNote 1 > H 13 10:30 – KeyNote 2 >H 12 11:00 Interfaces in multiphase structural nanocomposites 11:00 Metal-incorporated silicates via evaporation- Prof. Irene Beyerlein University of California (UCSB) induced ­self-assembly as superior catalytic materials Prof. Bala Subramaniam University of Kansas

SESSION I > H 13 SESSION II > H4 SESSION III > H12 SESSION IV > H15 Photonic and optical materials – Architectured materials: proces- Characterization of catalytic Pharmaceutical- and bio- in situ characterization sing, interface design, structure materials and interfaces 1 materials (formation, formation and properties characterization, and simulation)

11:10 – TALK 1 > H 13 TALK 5 > H4 TALK 9 > H12 TALK 13 > H15 11:30 In situ determination of the Ultrafine-grained laminated metal Using fast pressure transients to connect In situ study of the growth crystallinity and temperature composites – a new promising mechanistic studies in ultrahigh vacuum of poorly water-soluble drug of nanoparticle aer­ osols class of materials for lightweight to catalytic reactor performance: nanoparticles prepared by raman spectroscopy applications oxygen assisted coupling of methanol by antisolvent precipitation Leo Alexander Bahr Frank Kümmel on nanoporous gold Dennis M. Noll LTT, FAU Erlangen-Nürnberg WW1, FAU Erlangen-Nürnberg Prof. Robert Madix Harvard University NC, FAU Erlangen-Nürnberg

11:30 – TALK 2 > H 13 TALK 6 > H4 TALK 10 > H12 TALK 14 > H15 11:50 Investigation of a flame spray Enhancement of the formability Model-catalytic studies of novel Formation of drug pyrolysis process using of multi-layered 6000 series liquid-organic-hydrogen-carriers: nanocrystals with several optical measurement aluminum alloys by functional indole, indoline and octahydro- improved dissolution techniques gradients indole on Pt(111) characteristics Bettina Münsterjohann Jürgen Herrmann Matthias Schwarz Christoph Konnerth LTT, FAU Erlangen-Nürnberg LFT, FAU Erlangen-Nürnberg PC, FAU Erlangen-Nürnberg LFG, FAU Erlangen-Nürnberg

11:50 – TALK 3 > H 13 TALK 7 > H4 TALK 11 > H12 TALK 15 > H 15 12 : 10 Stabilization of gold Nanocarbon reinforced Noble metal free photocatalytic H2 Hydrodynamic mixing of turbulent nanoparticles lightweight generation on black TiO2: on the influence miscible flows in a T-micromixer in micellar solutions metal composites of crystal facets vs. crystal damage under real operating conditions Tilo Schmutzler NC, FAU Erlangen-Nürnberg Dr. Qianqian Li Imperial College London Dr. Ning Liu WW4, FAU Erlangen-Nürnberg Tobias Schikarski LSTM, FAU Erlangen-Nürnberg

12 :10 – TALK 4 > H 13 TALK 8 > H4 TALK 12 > H12 TALK 16 > H15 12:30 Build up of colloidal interfaces: Fiber optic temperature sensing Real-time monitoring of products The effect of synthesis photoluminescence of functionalized with transparent glass-filled during aqueous electrochemical pathway on amorphous ZnO nanoparticle dispersions polymers reactions calcium carbonate Krisztina Kocsis Wolfgang Wildner Dr. Ioannis Katsounaros Martina Schüßler Universität Salzburg LKT, FAU Erlangen-Nürnberg Helmholtz-Institute Erlangen-Nürnberg WW3, FAU Erlangen-Nürnberg

12:30 Lunch break > Tentoria

5 13:30 – Plenary Talk 2 > H 11 Tuesday 14:00 New multiscale approaches in topology optimization Prof. Ole Sigmund Technical University of Denmark Oct 10 2017 14:00 – EAM Talk 2 > H 11 13:30 –— 20:30 14:30 Research Area A3: Multiscale modeling, simulation and optimization of advanced materials Prof. Günter Leugering AM2, FAU Erlangen-Nürnberg

14:40 KeyNote 3 > H 13 14:40 – KeyNote 4 > H 12 15:10 Additive manufacturing of tailor-made catalytic reactors 15:10 Insight into SILP catalyzed gas-phase reactions Prof. Carolin Körner WTM & ZMP · Prof. Hannsjörg Freund CRT, FAU Erlangen-Nürnberg via combined kinetic and DFT studies PD Dr. Wolfgang Hieringer TC, FAU Erlangen-Nürnberg 15:10 coffee break > Tentoria PD Dr. Marco Haumann CRT, FAU Erlangen-Nürnberg 15:40 – KeyNote 5 > H 13 16 :10 Materials and processes for space and in-space applications 15:40 – KeyNote 6 > H 12 Dr. Tommaso Ghidini European Space Agency (ESA) 16 : 10 Billions and billions of molecules Prof. Alan Aspuru-Guzik Harvard University

SESSION V > H 13 SESSION VI > H4 SESSION VII > H12 SESSION VIII > H15 Transport, Additive manufacturing Characterization of catalytic Photonic and optical materials flow, and jamming of functional components materials and interfaces 2 (simulation­ and numerical optimization)

16:20 – TALK 17 > H 13 TALK 21 > H4 TALK 25 > H12 TALK 29 > H15 16:40 Modelling and simulation Fabrication and characterisation of X-ray photoemission studies of a liquid Particle synthesis modeled by nonlocal of multiphase pulsed electric a fully auxetic 3D lattice structure model system for a Pd-Ga bimetallic balance laws – process simulation field (PEF) applications via selective electron beam melting dehydrogenation catalyst and optimization Dr. Tobias Horneber TU Berlin Torsten Wolf ZMP, FAU Erlangen-Nürnberg Mathias Grabau PC II, FAU Erlangen-Nürnberg Lukas Pflug AM2, FAU Erlangen-Nürnberg

16:40 – TALK 18 > H 13 TALK 22 > H4 TALK 26 > H12 TALK 30 > H15 17:00 Lattice Boltzmann simulations of Parametric shape optimization XPS investigation of the catalytically Systematic design of zero- the statics and dynamics of magneto- of lattice structures for phononic triggered energy release in the 2,3- index-materials using topology capillary swimmers band gaps dibromo-substituted norbornadiene/ optimization Dr. Alexander Sukhov Dr. Fabian Wein AM2, FAU Erlangen-Nürnberg quadricyclane storage system on Ni(111) Dr. Fengwen Wang Helmholtz-Institute Erlangen-Nürnberg Udo Bauer PC II, FAU Erlangen-Nürnberg Technical University of Denmark

17:00 – TALK 19 > H 13 TALK 23 > H4 TALK 27 > H12 TALK 31 > H 15 17:20 Model for lateral diffusion obstructed by Single phase phononic band gap Design rules for oxygen evolution catalysis Structural optimization for crowding and trapping on a 2D interface material produced by selective at porous iron oxide electrode surfaces: multi-criteria electromagnetic Mislav Cvitkovic PULS, FAU Erlangen-Nürnberg & electron beam melting thousand-fold performance improvement applications Institute Ruđer Bošković IRB, Croatia Maximilian Wormser ZMP, FAU Erlangen-Nürnberg Sandra Haschke ChTFM, FAU Erlangen-Nürnberg Prof. Michael Stingl AM2, FAU Erlangen-Nürnberg

17:20 – TALK 20 > H 13 TALK 24 > H4 TALK 28 > H12 TALK 32 > H15 17:40 Distinct disordered glassy states Tailoring the grain structure Titania nanotubes integrated with polymer Hierarchical low haze metal arrays of soft spheres in IN718 containing Prussian Blue centres as optimize transparency for transparent Dr. Moumita Maiti Martin Gotterbarm a hydrogen peroxide sensor conducting electrodes TP I, FAU Erlangen-Nürnberg ZMP, FAU Erlangen-Nürnberg Katarzyna Grochowska Dr. Karina Bley Polish Academy of Sciences LFG, FAU Erlangen-Nürnberg 17:50 – EAM Talk 3 > H 11 18:20 Research Area D: Catalytic Materials Prof. Peter Wasserscheid CRT, FAU Erlangen-Nürnberg

18:30 – poster session > Tentoria 6 20:30 9:00 – Plenary Talk 3 > H 11 WEDNESDAY 9:30 Designing functional porous and nanostructured materials at multiple length scales Prof. Andreas Stein University of Minnesota Oct 11 2017 9:30 – EAM Talk 4 > H 11 9:00 –— 14:00 10:00 Research Area C: Photonic & Optical Materials – Developments in particle-based optical materials Prof. Robin Klupp Taylor LFG, FAU Erlangen-Nürnberg

10:00 coffee break > Tentoria 10:30 – KeyNote 7 > H 13 10:30 – KeyNote 8 > H 12 11:00 Theory of strengthening in high entropy alloys 11:00 Optofluidics in fibers: a new base for nonlinear Prof. William Curtin École polytechnique fédérale de Lausanne (EPFL) optics and nanoobjects detection Prof. Markus Schmidt Universität Jena

11:00 – KeyNote 9 > H 13 11:00 – KeyNote 10 > H 12 11:30 Sorting und printing of semiconducting carbon nanotubes 11:30 Design of nanoporous polymers for catalysis for high-performance field-effect transistors and separation in biorefineries Prof. Jana Zaumseil Universität Heidelberg Prof. Regina Palkovits RWTH Aachen

SESSION IX > H 13 SESSION X > H4 SESSION XI > H12 SESSION XII > H15 From molecular layers 2D and 3D structural characteri- Catalytic materials Photonic and optical materials to thin films zation and nanomechanics of (processing and modeling) (structure formation and architectured and porous materials characterization)

11:40 – TALK 33 > H 13 TALK 37 > H4 TALK 41 > H12 TALK 45 > H15 12:00 Electronic structure of one- and two- Mechanical testing of copper Selective oxidation of lignocellulosic Exploiting optical forces dimensional polymers fabricated alloy micropillars containing biomass to formic acid and high- in hollow-core photonic in a hierarchical on-surface synthesis a single twin boundary grade cellulose with tailor-made poly- crystal fibre on Au(111) Dr. Benoit Merle oxometalate catalysts (SelOxPOM) Richard Zeltner Max Planck Intitute Prof. Sabine Maier SPM, FAU Erlangen-Nürnberg WW1, FAU Erlangen-Nürnberg Dr. Jakob Albert CRT, FAU Erlangen-Nürnberg for the Science of Light, Erlangen

12:00 – TALK 34 > H 13 TALK 38 > H4 TALK 42 > H12 TALK 46 > H15 12:20 Resonance of the depolarization ratio Base cells and interpretation Selective oxidation of water-soluble Functional superparamagnetic supra- in circularly polarized photoluminescence of 3D two-scale optimization results biomass to formic acid in a continuous particles: from magnetic nanoparticles of transition metal dichalcogenides for additive manufacturing process to lightweight powders and optically Hans Tornatzky Bich Ngoc Vu Anna Bukowski interactive dispersions TU Berlin AM2, FAU Erlangen-Nürnberg CRT, FAU Erlangen-Nürnberg Dr. Karl Mandel Fraunhofer ISC & Universität Würzburg

12:20 – TALK 35 > H 13 TALK 39 > H4 TALK 43 > H12 TALK 47 > H 15 12:40 Bridging the scales between nano- An unforeseen mechanism for the Atomic layer deposition of Pd and SnO2 Integrating plasmonic materials particles’ surface chemistry and generation of functionally graded onto TiO2 nanotubes: effect of the within core-shell nanowires: an colloidal stability lightweight biogenic ceramics support on the ethanol electrooxidation electrochemical approach Dr. Doris Segets by systematic lattice curvature Dr. Lionel Santinacci Dr. Gilles Bourret LFG, FAU Erlangen-Nürnberg Dr. Joe Harris WW3, FAU Erlangen-Nürnberg Aix-Marseille University CNRS Universität Salzburg

12:40 – TALK 36 > H 13 TALK 40 > H4 TALK 44 > H12 TALK 48 > H15 13:00 Synthesis and structural characteri- Microstructure design of porous Model based study on the precipitation Looking for synergies in molecular sation of nanoparticles of Holmium materials described by the biot model and ageing of Cu/Zn hydroxycarbonates plasmonics by hybrid functional Hafnate (Ho2Hf2O7) for SOFC in the homogenization framework by as methanol catalyst precursor phases nanostructures applications gradient-based shape optimization Andreas Güldenpfennig Dr. Tobias König Leibniz Institut für Polymer- Suneela Sardar University of Leeds Daniel Hübner AM2, FAU Erlangen-Nürnberg LFG, FAU Erlangen-Nürnberg forschung Dresden · Cluster of Excellence CFAED 7 13:00 Lunch break > Tentoria 14:00 – Plenary Talk 4 > H 11 14:30 The power of light: from fast photodetectors to photoswitchable WEDNESDAY transistors based flexible multilevel memories Oct 11 2017 Prof. Paolo Samori Université de Strasbourg & CNRS 14:00 –— 23:00 14:30 – EAM Talk 5 > H 11 15:00 Research Area B: Nanoelectronic Materials Prof. Andreas Hirsch OC II, FAU Erlangen-Nürnberg

15 :10 – KeyNote 11 > H 13 15:10 – KeyNote 12 > H 12 15:40 Controlling charge density at electronic material interfaces 15:40 Giant colloidal cluster from confined with molecular electron acceptors and donors self-assembly: structure and properties Prof. Norbert Koch HU Berlin Prof. Michael Engel MSS, FAU Erlangen-Nürnberg Prof. Nicolas Vogel LFG, FAU Erlangen-Nürnberg 15:40 coffee break > Tentoria

SESSION XIII > H 13 SESSION XIV > H4 SESSION XV > H12 SESSION XVI > H15 Chemistry at the solid / Materials’ interfaces (formation, Catalytic and porous materials Self-organization liquid interface characterization and simulation) (processing and modeling) and packing

16:10 – TALK 49 > H 13 TALK 53 > H4 TALK 57 > H12 TALK 61 > H15 16:30 Thin water films as reactive Towards hybrids: adsorption, Zeolitic materials with hierarchical Anisotropic self-assembly interfaces for nanomaterials ordering and metalation porosity: synthesis pathways from isotropic building blocks growth of porphyrins on MgO nano- and applications Marcel Rey Prof. Oliver Diwald cube surfaces Prof. Wilhelm Schwieger LFG, FAU Erlangen-Nürnberg Universität Salzburg Johannes Schneider Universität Salzburg CRT, FAU Erlangen-Nürnberg

16:30 – TALK 50 > H 13 TALK 54 > H4 TALK 58 > H12 TALK 62 > H15 16:50 Nonlinear optics Thin films and their interfaces Synthesis and characterization Phase field crystal model at interfaces seen by x-ray techniques of hierarchical micro/macroporous of colloidal quasicrystals Rebecca Dinkel Dr. Johannes Will MFI type zeolites Benedikt Decker LFG, FAU Erlangen-Nürnberg NC, FAU Erlangen-Nürnberg Tobias Weissenberger TP I, FAU Erlangen-Nürnberg CRT, FAU Erlangen-Nürnberg

16 :50 – TALK 51 > H 13 TALK 55 > H4 TALK 59 > H12 TALK 63 > H 15 17:10 Atomic layer deposition from STEM-EDS imaging of in situ cation Thermal dewetting of Pt on anodic Self-assembly and growth dissolved precursors exchange at solid state between TiO2 nanotubes shows dramatically of soft quasicrystals Dirk Döhler diverse nanoparticles populations: enhanced photocatalytic H2 generation Prof. Michael Schmiedeberg CTFM, FAU Erlangen-Nürnberg how it works with minimal co-catalyst amounts TP I, FAU Erlangen-Nürnberg Prof. Andrea Falqui King Abdullah University Nhat Truong Nguyen of Science and Technology (KAUST), Saudi Arabia WW4, FAU Erlangen Nürnberg

17:10 – TALK 52 > H 13 TALK 56 > H4 TALK 60 > H12 TALK 64 > H15 17:30 Supramolecular organic-inorganic Atom probe tomography of interfaces Design, processing and application Morphological properties hybrid materials in functional nanomaterials of metal oxides fabricated in meso- of the epithelial tissue Anja Krieger Prof. Peter Felfer crystalline habits Jakov Lovric MN, FAU Erlangen-Nürnberg WW1, FAU Erlangen-Nürnberg Dr. Monica Distaso LFG, FAU Erlangen-Nürnberg Institute Ruđer Bošković IRB, Croatia

17:40 – EAM Talk 6 > H 11 18 :10 Research Area E: Lightweight Materials – Designing materials properties by nano- and mesostructuring 19:00 Reception > Kreuz+Quer Prof. Carolin Körner WTM & ZMP, FAU Erlangen-Nürnberg 20:00 Congress Dinner > Kreuz+Quer 8 23:00 Night watchman guided tour 9:00 – Plenary Talk 5 > H 11 thursday 9:30 The European Spallation Source: New opportunities for materials science Prof. Andreas Schreyer European Spallation Source ESS ERIC Oct 12 2017 9:30 – EAM Talk 7 > H 11 9:00 –— 14:30 10:00 Research Area A2: Nanoanalysis & Microscopy – Advanced 3D analysis and nanocharacterization as key tools for development of new materials and devices Prof. Erdmann Spiecker IMN, FAU Erlangen-Nürnberg 10:00 coffee break > Tentoria 10:30 – KeyNote 13 > H 13 10:30 – KeyNote 14 > H 12 11:00 Diamond quantum materials for biomedicine applications 11:00 Mesocrystals Prof. Tanja Weil Max-Planck-Institut für Polymerforschung, Mainz Prof. Helmut Cölfen Universität Konstanz

11:00 – KeyNote 15 > H 13 11:00 – KeyNote 16 > H 12 11:30 Morphology of organic solar cells 11:30 Experimental and theoretical characterization of the structure and Dr. Ning Li i-MEET · Dr. Stefanie Rechberger IMN, FAU Erlangen-Nürnberg stability of phosphonic acid self-assembled monolayers on ZnO surfaces Prof. Tobias Unruh NC, FAU Erlangen-Nürnberg Prof. Gregor Witte Phillipps-Universität Marburg · Prof. Bernd Meyer CC, FAU Erlangen-Nürnberg

SESSION XVII > H 13 SESSION XVIII > H4 SESSION XIX > H12 SESSION XX > H15 New approaches Bio-interfaces Liquid film catalysis – New characterization methods, in solar harvesting SILP and SCILL new instruments or novel combination of methods

11:40 – TALK 65 > H 13 TALK 69 > H4 TALK 73 > H12 TALK 77 > H15 12:00 Capillary suspensions – a generic platform for Covalent immobilization of Water-gas shift reaction A new universal toolkit for robust paste formulation and its application for 3D glycopeptides and proteins onto in supported uncertainty quantification, data printed porous ceramics with high specific carbon nano-onions (CNOs) ionic liquid phase analytics and machine learning mechanical strength and highly conductive, via Maleimide-Sulfhydryl ligation Robert Stepic in material engineering printable silver pastes Viviana Maffeis PULS, FAU Erlangen-Nürnberg Prof. Wolfgang Stummer Prof. N. Willenbacher Karlsruhe Intitute of Technology KIT Istituto Italiano di Tecnologia M, FAU Erlangen-Nürnberg

12:00 – TALK 66 > H 13 TALK 70 > H4 TALK 74 > H12 TALK 78 > H15 12:20 Binary Indium-Zinc oxide based photo- Multiparameter flow cytometry as tool to simul­ Keeping an eye on equilibrium: identi- 3D analysis of soft-matter functional anodes for dye-sensitized solar cells taneously monitor cellular nanoparticle uptake fying [Ru(CO)xCly]z species in SILP materials using cryo-tomography Andreas Kunzmann and biocompatibility in nanosafety studies catalysts for the water gas shift reaction Dr. Chandra Macauley PC I, FAU Erlangen-Nürnberg Dr. Christina Janko Universitätsklinikum Erlangen Tanja Bauer PC, FAU Erlangen-Nürnberg WW1, FAU Erlangen-Nürnberg

12:20 – TALK 67 > H 13 TALK 71 > H4 TALK 75 > H12 TALK 79 > H 15 12:40 Functionalized black Si for water Development of a novel cancer-on-a-chip: Ionic liquid/support interactions Conceptual design and realization photooxidation design and performance of micro-featured in ultrathin layers on metal surfaces of a laboratory nano-CT based on a Maxime Dufond Aix-Marseille University CNRS scaffolds to study cell heterogeneity in vitro Matthias Lexow field emission electron microscope Dr. Aldo Leal-Egana PC II, FAU Erlangen-Nürnberg Dr. Jens Engel Fraunhofer-Entwicklungszentrum WW7, FAU Erlangen-Nürnberg Röntgentechnik EZRT, Fraunhofer IIS

12:40 – TALK 68 > H 13 TALK 72 > H4 TALK 76 > H12 TALK 80 > H15 13:00 The electronic dynamics in main-chain Role of dispersive interactions Thermal lattice Boltzmann Characterization of nanorods alternating fullerene and dye oligomers at biointerfaces method for catalytic flows dispersed in aerosol for organic photovoltaics Dr. Robert Blackwell through porous media and colloidal systems Bianka Puscher PC I, FAU Erlangen-Nürnberg PULS, FAU Erlangen-Nürnberg Dr. Daniel Berger Dr. Thaseem Thajudeen Helmholtz-Institute Erlangen-Nürnberg LFG, FAU Erlangen-Nürnberg 13:00 Lunch break > H 11 14:30 – 9 LAB Tours 14:00 Concluding Session · Poster Award > H 11 16:30

Plenary Talk Abstracts

Plenary Talk 1 – Prof. Cynthia Friend Plenary Talk 2 – Prof. Ole Sigmund Plenary Talk 3 – Prof. Andreas Stein Plenary Talk 4 – Prof. Paolo Samori Plenary Talk 5 – Prof. Andreas Schreyer

10 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Plenary Talk 1 Erlangen, Germany

Design of Sustainable Catalytic Processes on Nanoporous Materials

Friend, Cynthia M.1,2,* (1) Department of Chemistry, Harvard University, 12 Oxford St., Cambridge MA 02138 USA (2) School of Engineering and App*lied Sciences, Harvard University, 29 Oxford St., Cambridge, MA 02138 USA e-mail: [email protected]

Keywords: Heterogeneous catalysis, nanoporous, selective oxidation

Catalytic processes generally and reaction selectivity specifically are by their nature kinetically controlled. To fully understand the kinetics of catalytic processes, understanding the elementary reactive steps[1] and the state of the catalytic material under reaction conditions[2] is essential. The reactive elementary steps provide a means of modeling and predicting kinetics and reaction selectivity. At the same time, the state of material, including the composition, geometric and electronic structure of reactive sties must be defined under operating conditions because these are all factors in determining catalytic function of a material. Selected examples of Au-based nanoporous catalysts will be used to illustrate the combined use of fundamental studies to determine reaction mechanism and kinetics with in situ studies using ambient pressure XPS and environmental TEM to follow the evolution of catalytic material under reaction conditions.

Figure 1: Schematic illustrating approach. Reaction mechanisms are determined using surface science experiments under ultrahigh vacuum conditions and modeled at the molecular scale using density functional theory (top left). Based on understanding of the mechanism, nanoporous alloy materials are designed, synthesized and tested for catalytic activity (top right). In situ studies of catalyst evolution provide further understanding of how the composition and structure of the material varies with temperature and the composition of the reactant stream.

References [1] Personick, M.L.; Madix, R.J.; Friend, C.M. ACS Catal. 2017 7 965-985. [2] Zugic, B.; Wang, L.-C.; Heine, C.; Zahharov, D.N.; Lechner, B.A.J.; Stach, E.A.; Biener, J.; Salmeron, M.; Madix, R.J.; Friend, C.M. Nat. Mat. 2016 doi: 10:1038/nmat4824.

11 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Plenary Talk 2 Erlangen, Germany

New multiscale approaches in topology optimization

Sigmund, O. 1,* ; Groen, J. 1 ; Wu, J. 2 ; Dyring, S. 1 and Aage, N. 1

(1) Department of Mechanical Engineering, Technical University of Denmark (2) Technical University of Delft

*e-mail: [email protected]

Keywords: Structural optimization, topology optimization, multiscale methods

Fired by recent progresses in additive manufacturing techniques, multiscale topology optimization approaches have recently received intense interest and many efficient and interesting approaches have been presented. Common challenges of multiscale schemes include lack in separation of scales, tiling of locally optimized microstructures and manufacturability. This paper discusses various new approaches to overcome these challenges performed within the TopOpt group (www.topopt.dtu.dk) at the Technical University of Denmark. In one approach we revisit the original homogenization-based topology optimization schemes and suggest a simple graphical projection scheme that realizes fine-grained optimal structures from coarse-scale homogenization solutions [1]. The scheme includes length-scale constraints on solid and void features. Further, we demonstrate how the same scheme can be used to provide high quality starting guesses for truss and frame optimization with large numbers of elements. In another approach we introduce a local volume constraint to provide porous and optimized infill structures for closed-walled 2d and 3d structures realized by additive manufacturing technologies [2]. By adding advanced projection schemes we allow variable outer shape to be included in the design process as well. The structures provide two-scale designs without the requirement of separation of scales.

References [1] Groen, J. & Sigmund, O. Homogenization-based topology optimization for high-resolution manufacturable micro-structures, 2017, submitted.

[2] Wu, J.; Aage, N.; Westermann, R. & Sigmund, O. Infill Optimization for Additive Manufacturing - Approaching Bone-like Porous Structures, Transactions on Visualization and Computer Graphics, 2017, to appear.

12 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Plenary Talk 3 Erlangen, Germany

Designing Functional Porous and Nanostructured Materials at Multiple Length Scales

Stein, A. 1,*

(1) Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, U.S.A. *e-mail: [email protected]

Keywords: hard templating, soft templating, functional porous materials

Templating methods employing soft templates (e.g., surfactants, block co-polymers, emulsions), hard templates (e.g., colloidal particles, colloidal crystals), or both together, are powerful approaches for controlling structure of materials, in particular porous materials, on multiple length scales to effect specific functions. Many applications require materials with complexity in both structure and composition. During synthesis and processing of complex materials, multiple interactions between templates and precursors can provide a richness in structure, but can also be exploited to influence the arrangement and distribution of separate components in a complex material. This tutorial review will highlight methods of controlling parameters of importance for functional materials, including surface area; pore geometry and shape; pore hierarchy, interconnectivity and accessibility; transport path length; material composition and component distribution in multicomponent systems; surface functionality; site isolation; and stability. The impact of these parameters on functional materials for energy storage and conversion, catalysis, sensing, and optical/photonic materials will be discussed with specific examples from our research.

Figure 1: Interactions in the synthesis of complex porous materials.

13 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Plenary Talk 4 Erlangen, Germany

The power of light: from fast photodetectors to photoswitchable transistors based flexible multilevel memories

Paolo Samorì*

(1) ISIS – University of Strasbourg & CNRS, 8, allée Gaspard Monge, 67000 Strasbourg (France)

*e-mail: [email protected]

Keywords: keyword 1, keyword 2, keyword 3

One among the major challenges in organic electronics is the fabrication of multifunctional devices, i.e. that can respond to multiple and independent stimuli. Such a challenge can be accomplished by developing multicomponent materials in which each component imparts a well-defined function to the ensemble. The controlled combination of such components and their integration in real devices can be achieved by mastering the supramolecular approach. Inspired by nature, functional units can be located at all the device interfaces. In my lecture will review our recent works on the combination of carbon-based nanomaterials, an in particular organic semiconductors, with photochromic molecules (diarylethenes or azobenzenes) in order to realize smart, high-performing and light-sensitive (opto)electronic devices as well as flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels. I will also introduce a novel approach towards harvesting photocurrent which is based on the fabrication of a novel nanomesh scaffold that can wire-up simultaneously hundreds electroactive nanowires. Optimized PTCDI-C8 nanowire photovoltaic devices exhibit a signal-to-noise ratio approaching 107, a photoresponse time as fast as 10 ns and an external quantum efficiency >55%. This nanomesh scaffold can also be used to investigate the fundamental mechanism of photoelectrical conversion in other low-dimensional semiconducting nanostructures. References [1] For reviews see: (a) X. Zhang, L. Hou, P. Samorì, Nat. Commun. 2016, 7, 11118. (b) E. Orgiu, P. Samorì, Adv. Mater. 2014, 26, 1827-1845. [2] For modulating charge injection at metal-organic interface with a chemisorbed photochromic SAM see: (a) N. Crivillers, E. Orgiu, F. Reinders, M. Mayor, P. Samorì, Adv. Mater. 2011, 23, 1447-1452. (b) T. Mosciatti, M.G. del Rosso, M. Herder, J. Frisch, N. Koch, S. Hecht, E. Orgiu, P. Samorì, Adv. Mater. 2016, 28, 6606. [3] For hybrid structure combining organic semiconductors blended with Au nanoparticles coated with a photochromic SAM see: C. Raimondo, N. Crivillers, F. Reinders, F. Sander, M. Mayor, P. Samorì, Proc. Natl. Acad. Sci. U.S.A. 2012, 109, 12375-12380. [4] For blends energy level phototuning in a photochromic - organic semiconductor blend see: (a) E. Orgiu, N. Crivillers, M. Herder, L. Grubert, M. Pätzel, J. Frisch, E. Pavlica, G. Bratina, N.

14 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Plenary Talk 4 Erlangen, Germany

Koch, S. Hecht, and P. Samorì, Nat. Chem. 2012, 4, 675-679. (b) M. El Gemayel, K. Börjesson, M. Herder, D.T. Duong, J.A. Hutchison, C. Ruzié, G. Schweicher, A. Salleo, Y. Geerts, S. Hecht, E. Orgiu, P. Samorì, Nat. Commun. 2015, 6, 6330. [5] For the fabrication of memory devices: T. Leydecker, M. Herder, E. Pavlica, G. Bratina, S. Hecht, E. Orgiu, P. Samorì, Nat. Nanotech. 2016, 11, 769–775. [6] For the novel nanomesh scaffold based photodetector: L. Zhang, X. Zhong, E. Pavlica, S. Li, A. Klekachev, G. Bratina, T.W. Ebbesen, E. Orgiu, P. Samorì, Nat. Nanotech. 2016, 11, 900–906.

15 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 Plenary Talk 5 Erlangen, Germany

The European Spallation Source: New Opportunities for Materials Science

Schreyer, A. 1,*

(1) European Spallation Source ERIC, Tunavägen 24, 22100 Lund *e-mail: [email protected]

Keywords: Materials Science, Neutrons, Neutron Spallation Sources, Instrumentation

The European Spallation Source (ESS), which is currently under construction in Lund, Sweden, is designed to push the limits of research with neutrons to new horizons. ESS will open up new opportunities for materials research which are complementary to those at synchrotron sources. These will include unprecedented in-situ and in-operando experiments which are only possible with neutrons. After a short summary of the design and the specifications of the European Spallation Source an overview of the current status and schedule of the ESS construction project will be given with a strong focus on the instruments and the surrounding scientific infrastructure. The overall goal of ESS is to begin user operation with 8 instruments in 2023. The plan is to reach the full scope of 22 public instruments by 2028. Selected examples of new scientific opportunities will be discussed.

Figure 1: Artists view of the European Spallation Source in Lund, Sweden after completion

16

EAM Talk Abstracts

EAM Talk 1 – Prof. Wolfgang Peukert EAM Talk 2 – Prof. Günter Leugering EAM Talk 3 – Prof. Peter Wasserscheid EAM Talk 4 – Prof. Robin Klupp Taylor EAM Talk 5 – Prof. Andreas Hirsch EAM Talk 6 – Prof. Carolin Körner EAM Talk 7 – Prof. Erdmann Spiecker

17 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 EAM Talk 1 Erlangen, Germany

Research Area A1 Functional Particle Systems: Process, Structure and Property Design

Wolfgang Peukert1,2,*

(1) Institute of Particle Technology, Department of Chemical and Biological Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstr. 4, 91058 Erlangen, Germany (2) Interdisciplinary Center for Functional Particle Systems, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Haberstr. 9a, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Product design, particle technology, unifying principles

In recent years, chemical engineering and in particular particle science and technology have gone through major transitions. For most of the last century, process engineering was focused on unit operations. Today, product design is the second pillar of chemical engineering. It refers to a broad range of biological, chemical and physical products, their specific properties and the related industrial applications. Modern devices such as solar cells, displays, fuel cells, catalysts or pharmaceutical formulations inherently depend on the particulate properties of the building blocks. Our mission in research area A1 at the Interdisciplinary Center of Functional Particle Systems is to address grand challenges in particle science and technology. These are related to the formation, processing and application of particulate systems along the five dimensions of size, shape, surface, structure and composition. The following five unifying principles of particulate product design are proposed which are widely applicable to many different kinds of products including solid, liquid, and even gaseous particles: i) Particle formation by top-down and bottom-up approaches, ii) interactions between the building blocks, iii) structure formation by self-organization and by transport processes, iv) characterization along the process chain, v) multiscale modelling and simulation. The joint venture of chemical engineering with materials science in concert with the basic sciences opens new prospects for all involved disciplines. In particular, chemical and biochemical engineering contributes through particle technologies to physics related fields of technology such as printable electronics, particle-based photonics, or 3D printing. Rigorous mathematical optimization methods based on predictive models for structure-property and process-structure functions are the key for the design of products, structures, and processes and will catalyze new possibilities for true design of particulate products. We show how these principles are applied within EAM for the design of functional particles, functional materials and processes the produce them.

18 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 EAM Talk 2 Erlangen, Germany

Research Area A3 Multiscale Modeling & Simulation: Multiscale modeling, simulation and optimization of advanced materials

Leugering, G.1,*

(1) Lehrstuhl für Angewandte Mathematik, Cauerstr. 11, 91058 Erlangen

*e-mail: [email protected]

The cross-sectional Research Area A3 is concerned with modeling, simulating and optimizing macroscopic materials and structural properties based on their constituent components, such as particles, molecules and atoms. A guiding principle of A3 is that simulation is used as a new paradigm in gaining qualitative knowledge and quantitative data alongside theoretical and experimental facts. This necessitates multiscale modeling, simulation and optimization across all scales. On the qualitative side, molecules that have not yet been synthesized can be anticipated via modeling and simulation. Nucleation, growth, and interaction of cracks and dislocations with precipitates are modeled and simulated from the atomistic up to the continuum scale. Similarly, new materials, and in particular meta-materials and band-gap materials are designed in the context of mathematical optimization techniques, given their desired functionality. On the quantitative side, data-driven model-based simulation and optimization in the context of the application areas can be used directly in the process chain. In this talk we provide some exemplary highlights of the projects within A3 and focus particularly on material optimization, thereby taking up issues from the plenary lecture by Ole Sigmund.

19 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 EAM Talk 3 Erlangen, Germany

Research Area D Catalytic Materials

Peter Wasserscheid 1,*

(1) Friedrich-Alexander-University Erlangen-Nürnberg, Department of Chemical and Biological Engineering, Egerlandstrasse 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: hybride materials, hierarchical structures, supported liquids, operando spectroscopies

Research Area D of the EAM cluster deals with the development of more efficient catalytic materials that enable performing future chemical transformations in a more sustainable way. An ideal catalytic material combines highest selectivity, catalytic activity and robustness with synthetic availability and processibility. This requires the preparation of materials with structurally optimized, molecularly uniform sites, efficient ways of manufacturing these new materials in technical quantities, and optimized reactor systems for applying them.

Consequently, our research includes synthetic, analytic, process-related and theoretical aspects and covers a broad range of length- and timescales as shown in Figure 1. The interdisciplinary research is performed by a team of scientists from Chemistry, Chemical Engineering and Materials Science. In the frame of EAM we have focused our efforts on a) catalysts with supported, non-volatile liquids (SILP, SCILL and SCALMS technologies), b) microporous coatings on meso- and macroporous support systems, and c) catalytic particles in surface-confined systems. The presentation will give an overview of our research highlights and will elaborate in more detail on the knowledge-driven catalyst design for dehydrogenation reactions.

Figure 1: Multiscale approach in engineering catalytic materials

20 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 EAM Talk 4 Erlangen, Germany

Research Area C Photonic & Optical Materials: Developments in particle-based optical materials

Klupp Taylor, R.N. 1,2*

(1) Institute of Particle Technology, Friedrich-Alexander University of Erlangen-Nürnberg, Cauerstrasse 4, 91058 Erlangen (2) Interdisciplinary Center for Functional Particle Systems, Friedrich-Alexander University of Erlangen-Nürnberg, Haberstrasse 9a, 91058 Erlangen

*e-mail: [email protected]

Keywords: refractive index, plasmon resonance, surface anisotropic particles

In this talk I will outline some of the key challenges that have been tackled in Erlangen during the past decade with regard to the development of particle-based optical materials. These challenges, both theoretical and experimental have been addressed by a unique team of physicists, chemists, mathematicians, material scientists and particle technologists and have made great progress in establishing a new workflow for the design and fabrication of optical materials like pigments and transparent conductive films. Two different facets of this work will be presented in the talk. We have shown that theoretical models are indispensable for the design of optical materials with properties that exceed those resulting from empirical studies. However, without suitable materials properties i.e. complex refractive index data these models cannot meet their full potential. Since such properties generally have to be measured from a real material specimen and determined by model inversion a “chicken and egg” problem occurs. For the example of iron oxide I will demonstrate how we have tackled this problem, combining ellipsometric measurements on polished pigment pellets and reflectance measurements of paint samples containing model pigments in order to obtain materials data which improve on the very disparate set of data found in the literature. In the second part of the talk I will describe progress in nanostructured optical particle synthesis and characterization. A simple and highly scalable new route to produce particles that have both highly tunable plasmonic properties and surface anisotropy has been championed in Erlangen thanks to the identification of a previously overlooked materials chemistry “loophole”. It will be shown how the optical properties of such particles are not only highly relevant for applications but have assisted with process development from microgram up to gram scale.

21 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 EAM Talk 5 Erlangen, Germany

Research Area B Nanoelectronic Materials

Andreas Hirsch

(1) Friedrich-Alexander-University Erlangen-Nürnberg, Department of Chemistry and Pharmacy, Henkestraße 42, 91054 Erlangen

e-mail: [email protected]

Keywords: nanoelectronic materials, nanoparticles, organic inorganic hybrid materials

This research area of the EAM cluster is devoted to the design and property investigation of organic and inorganic hybrid materials as components for transistors and optoelectronic devices. The wide spread activities within this research area include a) the control of the dimensionality, (OD, 1D, 2D, 3D) at the fundamental level, b) interface engineering with organic ligands, c) charge transfer at and across multifunctional - advanced interfaces, c) low cost/temperature processing, d) device performance as a function of the defect states, e) solar cells, FETs and LEDs as demonstrators. The underlying multiscale approach is depicted in Figure 1. Examples of highlights stemming from these efforts are: a) supramolecular transistors based on self-assembled monolayers of organic semiconductors on inorganic surfaces, b) the chemical surface functionalization of nanoparticles and nanorods with unprecedented optical-, magnetic-, supramolecular-, and switchable dispersion properties, c) the quantum chemical simulating of supramolecular electronics of tailored hybrid materials, d) the development of new prototypes of printable dye sensitized solar cells and bulk heterojunctions, e) the design of new organic ligands and coupling motifs, f) the development of covalent- and non-covalent graphene chemistry, g) the transport of electrons through molecular wires.

MACROSCALE MESOSCALE NANOSCALE

Self-Assembly Layer and Interface Formation

Device Development Synthesis and Hierarchical Characterization Ordering 500 nm Functionalization Defect Characterization along the Process Chain FT2, FT3, JD2, JD3 Figure 1: Multiscale approach in engineering materials for nanoelectronics

22 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 EAM Talk 6 Erlangen, Germany

Research Area E Lightweight Materials: Designing materials properties by nano- and mesostructuring

Körner, C. 1*

(1) Department Material Science, University Erlangen-Nuremberg, Martensstr. 5, 91058 Erlangen

*e-mail: [email protected]

Keywords: lightweight material, meso- and nanostructure, architectured materials

The mechanical and physical properties of structural lightweight materials result from the composition and the particular microstructure. In addition, the mesostructure on the length scale much larger than the microstructure but much smaller than the dimensions of the component has strong influence on the materials properties. This mesostructure can be used to design architectured materials with enhanced and exceptional properties. This research area explores the production, characterization and modeling of advanced lightweight materials with exceptional properties resulting from nano- and mesostructuring of ceramics, metals and polymers. An overview of different approaches to realize particle reinforced, ultrafine grained, laminated or cellular materials with outstanding properties is given. The potential of mesostructuring for designing materials with extraordinary properties is highlighted on the basis of selected examples, e.g. laminated materials or cellular materials.

Figure 1: Mechanical metamaterial showing full phononic band gaps fabricated by selective electron be beam melting.

23 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 EAM Talk 7 Erlangen, Germany

Research Area A2 Nanoanalysis & Microscopy: Advanced 3D analysis and nano- characterization as key tools for development of new materials and devices Spiecker, E.1,*

(1) Lehrstuhl für Mikro- and Nanostrukturforschung & Center for Nanoanalysis and Electron Microscopy (CENEM), Friedrich-Alexander-Universität (FAU) Erlangen-Nürnberg, Cauerstr. 6, 91058 Erlangen, Germany *e-mail: [email protected]

Keywords: Nanoanalytics, Electron Microscopy, Scattering Techniques, Tomography, In situ Microscopy For the development of new materials and devices a decent understanding of the relationship between synthesis/fabrication, structure and properties is absolutely essential. This is particu- larly true for nanostructured materials which are controlled by interfaces and size effects giving rise to enhanced properties and new functionalities. In order to analyze such materials at the nanometer and atomic scale state-of-the-art characterization methods based on short-wave radi- ation (electrons, X-rays/ neutrons) and scanning probes are urgently needed. At FAU these tech- niques are represented by the Center for Nanoanalysis and Electron Microscopy (CENEM) which evolved from a cross-sectional research area of the Cluster of Excellence “Engineering of Advanced Materials”. Within the past 10 years the CENEM has been rapidly developed and cutting-edge instrumentation has been established, including a double-corrected monochromat- ed TEM/STEM, a highly versatile combined SAXS/GISAXS/GIXD laboratory instrument, a state-of-the-art atom probe tomography (APT) instrument and, most recently, a cutting-edge high-resolution X-ray microscope/NanoCT. The philosophy of CENEM’s research is the appli- cation of complementary characterization techniques. Moreover, CENEM provides a full chain of tomography techniques which provide 3D data which can be directly used as input for mate- rials modeling and simulation. Finally, within CENEM’s Research Training Group novel in situ methods are developed which enable unique insights into the structure formation, functionality and deformation behavior of nanomaterials. In the talk highlights of CENEM’s research carried out in close collaboration with the project partners in the Cluster will be presented.

Figure 1: ‘Stamping transfer’ technique as example for advanced 3D analysis of functional particles [1]

References [1] Przybilla, T; Apeleo Zubiri, B.; Beltrán, A.B.; Butz, B.; Machoke, A.G.F.; Inayat, A.; Distaso, M.; Peukert, W.; Schwieger, W.; Spiecker, E. Small Methods 2017, accepted.

24 Keynote Talk Abstracts

Keynote Talk 1 – Prof. Irene Beyerlein Keynote Talk 2 – Prof. Bala Subramaniam Keynote Talk 3 – Prof. Carolin Körner, Prof. Hannsjörg Freund Keynote Talk 4 – PD Dr. Marco Haumann, PD Dr. Wolfgang Hieringer Keynote Talk 5 – Dr. Advenit Makaya Keynote Talk 6 – Prof. Alán Aspuru-Guzik Keynote Talk 7 – Prof. William Curtin Keynote Talk 8 – Prof. Markus Schmidt Keynote Talk 9 – Prof. Jana Zaumseil Keynote Talk 10 – Prof. Regina Palkovits Keynote Talk 11 – Prof. Norbert Koch Keynote Talk 12 – Prof. Michael Engel, Prof. Nicolas Vogel Keynote Talk 13 – Prof. Tanja Weil Keynote Talk 14 – Prof. Helmut Cölfen Keynote Talk 15 – Dr. Ning Li, Dr. Stefanie Rechberger, Prof. Tobias Unruh Keynote Talk 16 – Prof. Gregor Witte, Prof. Bernd Meyer

25 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 1 Erlangen, Germany

Interfaces in multiphase structural nanocomposites

Beyerlein, I. J. *

Mechanical Engineering Department, Materials Department, University of California, Santa Barbara, 93106, USA

*e-mail: [email protected]

Keywords: defects, microstructure, modeling

Nanolayered multi-phase metal composites have been found to exhibit remarkable strength and in some cases, simultaneous ductility and formability. Their outstanding structural properties have been connected to the unusually high density of biphase interfaces they possess. As the spacing between adjacent bimetal interfaces shrinks to very fine nanoscales (<10~100 nm), the interfaces begin to control crystal structure and key deformation mechanisms, such as dislocation motion and deformation twinning. The important aspects of interfaces that should be targets in the design of nanolayered composites remain to be clarified. A better understanding of the material variables that control local defect-interface interactions, for instance, would greatly benefit the design of these exceptional materials. In this talk, we will show recent results from our combined synthesis, experimental, and multiscale modeling studies on bi-phase FCC/BCC and HCP/BCC (e.g., Cu/Nb or Zr/Nb or Mg/Nb) nanolaminates with layer thicknesses < 50 nm made via deposition techniques, as well as from severe plastic deformation techniques, which are needed for making bulk size specimens suitable for standard forms of testing. The various composite material combinations, crystal structures, and synthesis methods under investigation have helped to accelerate understanding of microstructure-property relationships. We first highlight that these nanolaminates show exceptionally high strength, and in some cases, large strains to failure and formability (under rolling). Next we describe the approaches used to closely integrate the microstructural characterization and 3D modeling efforts for the purposes of relating the interface morphology and crystallography, the phase textures, and the mechanisms activated during external deformation. We discuss the ways interfaces are found to control microstructural and texture evolution, and in turn, affect the macroscopic properties. Last, we will present the unique mechanisms afforded by the high density of biphase interfaces that enable a desirable combination of structural properties.

26 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 2 Erlangen, Germany

Metal-Incorporated Silicates Via Evaporation-Induced Self-Assembly As Superior Catalytic Materials

Ramanathan, A.; Wu, J-F.; Maiti, S.K. and Subramaniam, B.*

Center for Environmentally Beneficial Catalysis, The University of Kansas, Lawrence, KS 66047, USA

*e-mail: [email protected]

Keywords: Evaporation-Induced Self-Assembly, mesoporous silicate, epoxidation, metathesis

Abstract: We have developed novel catalytic materials by incorporating metals such as Zr, Nb, W and Mo [1-3] into mesoporous silicates by a relatively simple one-step Evaporation-Induced Self-Assembly (EISA) process. Remarkably, a high and tunable dispersion of the metal oxide species (either isolated or oligomeric) is achieved without any detectable formation of bulk M-oxide species even at metal loadings up to 15% (Figure 1, left). Consequently, the M-EISA materials display relatively low Brønsted acidity (Figure 1, middle) compared to those prepared by either impregnation or direct hydrothermal synthesis routes (Fig. 1, right).

Figure 1: (left) Elemental mapping showing dispersion of Si, O and W in W-EISA, (middle) Low Brønsted acidity of Nb-EISA at various loading and (right) enhanced propene yield over W-EISA catalyst compared to W catalysts prepared by impregnation and hydrothermal synthesis Applications of M-EISA materials as superior catalysts for a variety of chemical transformations will be presented. Examples include propylene epoxidation with H2O2, wherein Nb-EISA materials show exceptional overall performance yielding >99% PO selectivity with

>99% H2O2 utilization and ~1% Nb leaching. For the cross-metathesis reaction of ethylene and 2-butene, W-EISA [2] and Mo-EISA [3] catalysts show superior propene yields and TOFs. XPS characterization of W-EISA catalysts reveal that most of the active W species are present on the catalyst surface and are readily accessible [2]. Computational chemistry work that explains some of the structure/property-function relationships will also be presented. References [1] Zhu, H.; Maheswari, R.; Ramanathan, A.; Subramaniam, B. Micropor. Mesopor. Mater, 2016 223, 46-52. [2] Wu, J. F.; Ramanathan, A.; Subramaniam, B. J. Catal. 2017 10.1016/j.jcat.2017.02.014. [3] Ramanathan, A.; Wu, J. F.; Maheswari, R.; H u, Y. ; Subramaniam, B. Micropor. Mesopor. Mater, 2017 245, 118-125.

27 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 3 Erlangen, Germany

Additive Manufacturing of Tailor-Made Catalytic Reactors

Freund, H.1,*, Körner, C.2,*

(1) Institute of Chemical Reaction Engineering (2) Institute of Materials Science and Engineering for Metals Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU)

*e-mails: [email protected]; [email protected]

Keywords: Additive Manufacturing, Selective Electron Beam Melting, Catalytic Reactors, Structured Catalysts An intelligent matching of reaction and transport processes is key to the design of optimal catalytic reactors. For the realization of optimal reaction and process conditions, specific requirements regarding heat and mass transport characteristics demand for suitable catalyst support materials and structures. In this regard, additive manufacturing (AM) techniques have emerged as enabling technology which unlocks a new degree of freedom in the design. AM allows for the fabrication of open cellular structures of nearly arbitrary geometrical complexity in a well-defined and highly reproducible manner. In our work, we study periodic open cellular structures (POCS) that were manufactured by selective electron beam melting (SEBM). POCS are promising novel catalyst supports as they can eliminate the drawbacks of conventional randomly packed fixed-bed reactors, i.e., high pressure drop and hotspots. In fact, POCS combine the advantages of randomly packed beds (radial mixing, tortuosity of the flow) and honeycombs (high geometric specific surface area, low pressure drop) owing to their high porosities and their characteristic 3D cellular architecture. Based on extensive experimental investigations as well as modeling and simulation correlations for specific surface area, pressure drop and heat transport for POCS were established [1-5]. With these models, the design and optimization of POCS that are tailor-made according to the needs of the reaction system is possible. The tailor-made POCS were manufactured, functionalized by catalytic coating, and then applied in different catalytic reaction systems with focus on the optimization of heat transport (for a highly exothermic gas phase reaction) and gas-liquid distribution (in a trickle-bed reactor system), respectively. The tailor-made POCS were benchmarked against conventional randomly packed bed reactors, and a great potential for process intensification could clearly be demonstrated. References [1] Inayat, A.; Schwerdtfeger, J.; Freund, H.; Koerner, C.; Singer, R.F.; Schwieger, W.; Chem. Eng. Sci. 66(12) (2011) 2758-2763. [2] Klumpp, M.; Inayat, A.; Schwerdtfeger, J.; Koerner, C.; Singer, R.F.; Freund, H.; Schwieger, W.; Chem. Eng. J. 242 (2014) 364-378. [3] Inayat, A.; Klumpp, M.; Lämmermann, M.; Freund, H.; Schwieger, W.: Chem. Eng. J. 287 (2016) 704-719. [4] Lämmermann, M.; Schwieger, W.; Freund, H.: Catal. Today 273 (2016) 161-171. [5] Bianchi, E.; Schwieger, W.; Freund, H.; Adv. Eng. Mater. 18(4) (2016) 608-614.

28 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 4 Erlangen, Germany

Insight into SILP catalyzed gas-phase reactions via combined kinetic and DFT studies

Hieringer, W. 1*; Haumann, M. 2*

(1) Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Lehrstuhl für Theoretische Chemie, Egerlandstr. 3, 91058 Erlangen, Germany, corresponding author: [email protected] (2) Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Lehrstuhl für Chemische Reaktionstechnik (CRT), Egerlandstr. 3, 91058 Erlangen, Germany, corresponding author: [email protected]

Keywords: supported ionic liquid phase (SILP), kinetic modeling, density functional theory (DFT)

A detailed kinetic investigation of the gas-phase continuous hydroformylation of 1-butene has been carried out. The supported ionic liquid phase (SILP) catalyst was based on a

Rh-diphosphite, the ionic liquid [EMIM][NTf2] and silica support material. Based on the established Wilkinson mechanism, the hyperbolic rate expressions were used to fit the experimental results. While the hydroformylation could be modeled with high accuracy, the hydrogenation and isomerization trends could not be reproduced by the given rate expressions.

substrates Pore Ionic liquid

A + B C + D

+ - + - + - M + - M + - + - M + -

Rh*:Support 27.0 % 12.8 %

products

Figure 1: Schematic description of SILP catalysis using fixed-bed reactors.

An alternative reaction mechanism was developed and allowed an excellent fit of experimental data by the new reaction rate expressions. Important steps of the new mechanism were studied using DFT calculations. References [1] Walter, S.; Spohr, H.; Franke, R.; Hieringer, W.; Wasserscheid, P.; Haumann, M. ACS Catalysis, 2017, 7, 1035-1044.

29 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 5 Erlangen, Germany

Materials and Processes for Space and In-Space Applications

Ghidini, T.1,*

(1) Structures, Mechanisms and Materials Division, European Space Agency, ESA/ESTEC, Keplerlaan, 1, PO Box 299, 2200 AG Noordwijk (NL)

*e-mail: [email protected]

Keywords: In-Space Manufacturing, Advanced Manufacturing, Additive Manufacturing The majority of the materials used for the manufacturing of spacecraft structures and mechanical devices, propulsion systems and launchers are usually selected from known and well-proven aircraft applications. However, the advancement in space technology has been made possible by many specific breakthroughs in materials processing, facilitating the development of highly sophisticated spacecraft systems, launchers and components, operating in extremely aggressive environments. In the present paper, an overview will be given over the most challenging materials and manufacturing processes developments which have enabled highly demanding and innovative space missions of the European Space Agency (ESA). As an exemplary case, Additive Manufacturing (AM) has been identified as a key enabling technology for current and future space missions. AM technologies have been extensively exploited by the Agency on conventional and non-conventional metals, polymers, ceramics and geopolymers (e. g. Moon regolith), ranging from few grams up to few tons of material. Applications on satellites and launchers structures, radio frequency antennas and components, mechanisms, propulsion and thermal management systems have been developed, including on-orbit as well as on-planet manufacturing.

30 International Congress Engineering of Advanced Materials ICEAM2017 10 October 2017 10 - 12 October 2017 Keynote Talk 6 Erlangen, Germany

Billions and Billions of Molecules

Alán Aspuru-Guzik*

Department of Chemistry and Chemical Biology Harvard University

* http://aspuru.chem.harvard.edu

Many of the challenges of the twenty-first century are related to molecular processes such as the generation and storage of clean energy, water purification and desalination. These transformations require a next generation of more efficient, chemically stable, and non-toxic materials. Chemical space, the space of all possible synthesizable molecules, is practically infinite and promises to have relevant candidate functional molecules to address these challenges. One of the main goals of my research group is to develop understanding and tools for the exploration chemical space in order to accelerate the discovery of organic materials. Our design cycle is sped up by the constant interaction of theoreticians and experimentalists, the use of high-throughput computational techniques, machine learning, and the development of specialized big data tools. We have had recent successes in theoretically predicting and experimentally confirming in record times top performers in the areas of organic electronics, organic flow batteries and organic light-emitting diodes. In this talk, I will discuss what I consider are the key factors related with a successful high-performance screening approach as illustrated by these three different applications. I will end by discussing the future prospects and challenges associated with developing appropriate metrics for the cartography of chemical space.

31 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 7 Erlangen, Germany

Theory of Strengthening in High Entropy Alloys

W. A. Curtin*

Ecole Polytechnique Federale de Lausanne EPFL-STI-IGM-LAMMM, Station 9, 1015 Lausanne, Switzerland

*e-mail: [email protected]

High Entropy Alloys can be viewed as high-concentration, multicomponent solid-solution strengthened metals. A key concept is to envision each individual elemental component as a “solute” embedded in an “effective medium” matrix of the alloy itself [1]. This concept is demonstrated explicitly within the setting of atomistic simulations using Embedded Atom Potentials [2]. Within this framework, the computation of the interaction energy between each solute type and the average dislocation in the average matrix material can be obtained. These interaction energies are then the input to an analytic parameter free model of solute strengthening as a function of temperature and strain rate [3] that has been extended to arbitrary concentrations and number of components [1]. In the absence of true interaction energies, the theory can be reduced using elasticity and solute misfit volumes, leading to a simple analytic model for strengthening in terms of measurable material parameters [1]. We demonstrate the quantitative success of the simple model in applications to (i) the family of Ni-Co-Cr-Fe-Mn fcc Cantor alloys, including temperature dependence [1] and rate-sensitivity [4], (ii) the Al-doped

Cantor alloys NiCoCrFeMnAlx and NiCoCrFeAlx [5], and (iii) the Noble metal alloys Pd-Pt-Rh-Ir-Au-Ag-Cu-Ni [6]. Use of the theory to design new alloys, extensions to include twinning and short-range, and concepts for BCC HEA alloys are discussed.

[1] C. Varvenne et al., Acta Materialia 118, 164-176 (2016) [2] C. Varvenne et al., Phys. Rev. B 93, 104201 (2016). [3] G. P. M. Leyson et al., Nature Materials 9, 750-755 (2010) [4] G. Laplanche, et al., in preparation. [5] C. Varvenne and W. A. Curtin, Scripta Materialia (under revision). [6] C. Varvenne and W. A. Curtin, Scripta Materialia (submitted).

32 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 8 Erlangen, Germany

Optofluidics in fibers: a new base for nonlinear optics and nanoobjects detection

Schmidt, M. A.1,2,3,*

(1) Leibniz Institute of Photonic Technology, Albert-Einstein-Str. 9, 07745 Jena (2) Abbe Center of Photonic and Faculty of Physics, Friedrich-Schiller-University Jena, Jena 07743 (3) Otto Schott Institute of Material Research, Fraunhoferstr.6, 07743 Jena *[email protected]

Keywords: microstructured fibers, optofluidics Integrating sophisticated materials inside microstructured fibers represent a promising path to include more functionality into optical fibers. Beside solid materials such as gold or soft glasses particular interesting is the combination of liquids and fibers, which allows to access new regimes for fiber optics.

Figure 1: (a) Schematic of single virus detection inside optofluidic nanobore fibers via transversely recording the elastically scattered light. (b) Octave-spanning supercontinuum generation inside carbon-disulphide nonlinear optofluidic liquid core fiber, generated by pumping with a femtosecond laser.

In the first part of the talk I will focus on our recent results in the area of single virus detection in water-filled nanobore fiber, where we have shown that the Brownian motion of nanoparticles and single viruses can be recorded at high acquisition speed using elastic light scattering, thus allowing for the detection of deep subwavelength nanoobjects with low background signal and no labeling (Fig. 1a) [1]. The second part is related to ultrafast nonlinear light generation and the first indication of a new kind of optical soliton inside carbon-disulphide filled liquid core fibers (Fig. 1b), where we have observed octave-wide mid-IR supercontinuum generation spanning from 1.1 µm towards more than 2.6 µm [2].

References [1] Faez, S. et al. ACS Nano. 2015, 6, 12349. [2] Chemnitz M. et al., Nat. Commun. 2017, accepted.

33 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 9 Erlangen, Germany

Sorting und Printing of Semiconducting Carbon Nanotubes for High-Performance Field-effect Transistors

Zaumseil, J.*

Institute for Physical Chemistry, Universität Heidelberg, Heidelberg, D-69120, Germany

*e-mail: [email protected]

Keywords: carbon nanotubes, printing, charge transport

Dense networks of semiconducting single-walled carbon nanotubes (s-SWCNTs) are a promising material for future printed and flexible electronics due to their high charge carrier mobilities, stretchability and transparency [1-3]. Large volumes of highly purified dispersions of long (>1 µm) s-SWCNT for printing have recently become available through polymer-wrapping in combination with shear-force-mixing [4]. The resulting possibility of large area printing of s-SWCNTs raises the question of reproducibility and the influence of the printing process on the performance of the final field-effect transistors (FETs). Here, we present aerosol-jet printed FETs based on sparse and dense networks of sorted (6,5) s-SWCNTs with excellent ambipolar device characteristics, molecular p- and n-doping for complementary circuits and new concepts for low-voltage and high-frequency FETs. Finally, we will present a model to describe and understand charge transport in random networks of s-SWCNTs with different diameters and thus bandgaps.

Figure 1: Aerosol-jet printing of polymer-sorted (6,5) SWCNTs for field-effect transistors with ambipolar current-voltage characteristics.

References [1] Schießl et al., ACS Appl. Mater. Interfaces, 2015, 7, 682-689. [2] Rother et al., ACS Appl. Mater. Interfaces, 2016, 8, 5571- 5579. [3] Schießl et al., Adv. Interf. Mater., 2016, 3, 1600215. [4] Graf et al., Carbon, 2016, 105, 593-599.

34 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 10 Erlangen, Germany

Design of Nanoporous Polymers for Catalysis and Separation in Biorefineries

Regina Palkovits1*

(1) Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany

*e-mail: [email protected]

Keywords: nanoporous polymer, covalent organic framework, heterogeneous catalysis, biorefinery, immobilization

Renewable carbon feedstocks such as biomass and CO2 present an important element of future circular economy. Especially biomass as highly functionalized feedstock provides manifold opportunities for the transformation into attractive platform chemicals. However, this change of the resources requires a paradigm shift in refinery design. Fossil feedstocks are processed in gas-phase at elevated temperature. On the contrary, biorefineries are based on processes in polar solvents at moderate conditions to selectively deoxygenate the polar, often thermally instable and high-boiling molecules.[1] Nanoporous polymers are a versatile class of materials to address the challenges associated with novel biorefinery concepts.[2] Using hypercrosslinked polymers, a selective adsorption of 5-hydroxymethylfurfural (HMF) from aqueous fructose solution became possible.[3] Covalent triazine frameworks (CTF) formed via trimerization of dinitriles enabled molecular metal coordination on their nitrogen functionalities [4] as well as nitrogen-stabilization of supported metal nanoparticles. In this regard, an efficient oxidation of HMF over CTF supported Ru nanoparticles could be achieved.[5] Recently, also porous phosphor containing frameworks emerged. After Ru coordination, these materials facilitated an efficient base-free H2 production from formic acid as well as the reverse reaction.[6] In summary, nanoporous polymers present promising and versatile materials able to unify advantages of molecular and solid catalysts

References [1] Delidovich, I., Leonhard, K., Palkovits, R., Energy Environ. Sci. 2014, 7, 2803. [2] M. Rose, ChemCatChem. 2014, 6(5), 1166. [4] Detoni, C., Gierlich, C., Rose, M., and Palkovits, R., ACS Sustainable Chem. Eng. 2014, 2(10), 2407. [3] Palkovits, R. Antonietti, M., Kuhn, P.,Thomas, A. and Schüth, F. Angew. Chem. Int. Ed. 2009, 48(37), 6909. [5] (a) Artz, J., Mallmann, S. and Palkovits, R., ChemSusChem. 2015, 8(4), 672; (b) Artz, J. and Palkovits, R., ChemSusChem. 2015, 8(22), 3832. [6] Hausoul, P., Broicher, C., Vegliante, R., Göb, C. and Palkovits, R., Angew. Chem. Int. Ed. 2016, 55, 5597.

35 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 11 Erlangen, Germany

Controlling charge density at electronic material interfaces with molecular electron acceptors and donors

Koch, N. 1,2,*

(1) Institut für Physik & IRIS Adlershof, Humboldt-Universität zu Berlin, Newtonstrasse 15, 12489 Berlin, Germany (2) Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Strasse 15, 12489 Berlin, Germany

*e-mail: [email protected]

Keywords: semiconductors, electronic materials, electronic properties

The energy level alignment at interfaces with electronic materials is critically important for the function and efficiency of electronic and opto-electronic devices. To modify the level alignment at interfaces, the control of the local charge density distribution turns out to be a most versatile approach. This control enables optimizing charge carrier density in semiconductors and the energy level alignment at electrical contacts and at semiconductor heterojunctions. Molecular electron acceptors and donors are potent agents that enable tuning the charge density within and at interfaces of established and emerging electronic materials, such as inorganic and organic semiconductors, perovskites, and two-dimensional (2D) transition metal dichalcogenides. The first example to be discussed shows that work function values of electrodes can be extended to ultra-low and ultra-high values via charge transfer induced by the molecular agents. Next, it is shown how the energy level alignment at inorganic/organic semiconductor heterojunctions can be adjusted by varying the work function of the inorganic compound surface, e.g. ZnO and GaN, by the agents. Finally, the charge density re-distribution within exemplary 2D semiconductors upon adsorption of a molecular acceptors is investigated, and the electronic properties of a one-dimensional intrinsic/p-type junction are revealed.

36 International Congress Engineering of Advanced Materials ICEAM2017 11 October 2017 10 - 12 October 2017 Keynote Talk 12 Erlangen, Germany

Giant Colloidal Cluster from Confined Self-Assembly: Structure and Properties

Wang, J.W.1, Mbah, C.F.2, Przybilla, T.3, Spiecker, E.3, Engel, M.2,*, Vo ge l , N . 1,*

(1) Institute of Particle Technology, FAU, Cauerstr. 6, Erlangen (2) Institute for Multiscale Simulation, FAU, Nägelsbachstr. 49B, Erlangen (2) Institute of Micro- and Nanostructure Research, FAU, Cauerstr. 6, Erlangen

*e-mails: [email protected], [email protected]

Keywords: hierarchical self-assembly, confinement, suprastructures, structural color

Spherical colloidal particles are promising building blocks for the hierarchical self-assembly of photonic materials [1]. Complex structures have been achieved by varying composition, interaction, or shape of the constituent particles [2]. Another approach is to utilize interfacial effects from the introduction of confinement to achieve patterning on the micron-scale. Recently it has been shown that entropy favors icosahedral symmetry for colloids assembling in spherical confinement [3].

Here, we investigate polystyrene colloids that aggregate within water-in-oil emulsion droplets and gradually densify upon water evaporation until crystallization sets in, resulting in densely packed colloid clusters [4]. We utilize droplet-based microfluidics to synthesize near-monodisperse clusters of 100 to 10000 colloids. The clusters have a well-defined internal structure and correspond to a discrete series of multiply twinned crystals, as is confirmed by high-resolution electron microscopy and tomography. To explain the internal structure of the clusters, we propose a geometric model that is compared to Monte Carlo computer simulations and allows extracting extremal principles that govern the assembly process. We also study the angle-dependent photonic color arising from icosahedral arrangement of colloidal particles.

References [1] N. Vogel, M. Retsch, C.A. Fustin, A. del Campo, U. Jonas, Advances in colloidal assembly: the design of structure and hierarchy in two and three dimensions, Chemical Reviews 115, 6265 (2015). [2] M.A. Boles, M. Engel, D.V. Talapin, Self-assembly of colloidal nanocrystals: From intricate structures to functional materials, Chemical Reviews 116, 11220 (2016). [3] B. de Nijs, S. Dussi, F. Smallenburg, J.D. Meeldijk, D.J. Groenendijk, L. Filion, A. Imhof, A. van Blaaderen, M. Dijkstra, Entropy-driven formation of large icosahedral colloidal clusters by spherical confinement, Nature Materials 14, 56 (2015). [4] N. Vogel, S. Utech, G. England, T. Shirman, K.R. Phillips, N. Koay, I. Burgess, M. Kolle, D. A. Weitz and J. Aizenberg. Color from hierarchy: diverse optical properties of micron-sized spherical colloidal assemblies. Proc. Natl. Acad. Sci. USA 2015, 112, 10845 [4] N. Vogel, S. Utech, G. England, T. Shirman, K.R. Phillips, N. Koay, I. Burgess, M.

37 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 Keynote Talk 13 Erlangen, Germany

Diamond Quantum Materials for Biomedicine Applications

Tanja Weil*

Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany

*e-mail: [email protected]

Fluorescent nanodiamonds (FNDs) are emerging as highly promising quantum materials for biomedical applications and precision sensing due to their unique optical and magnetic properties.[1] They are obtained by implementing elemental defects into the carbon lattice, such as the nitrogen vacancy (N-V), giving unconditionally stable fluorescence without bleaching or blinking even after several months of continuous excitation. The emission wavelength of FNDs is not size-dependent and is tuneable from the visible to the near infrared region according to the elemental defects. In addition, the N-V center in FNDs serves as single-spin sensor[2] that locally detects various physical properties offering great potential for atomic resolution imaging under physiological conditions. The advent of diamond quantum sensing promises solving the longstanding goal of single molecule detection with atomic resolution under ambient conditions[1] There is currently no other nanomaterial that would offer such features. The preparation of high quality N-V diamonds and the chemistry of surface modification with i.e. biopolymers[3-4] and proteins[2] will be discussed that provide the basis for quantum sensing and drug delivery in living biological environments. In addition, functionalization of N-V diamonds with proteins or DNA provides access to precisely assembled diamonds on DNA origami to access sophisticated quantum devices[4].

[1] Y. Wu, F. Jelezko, M. Plenio, T. Weil. Diamond Quantum Sensing in Biology. Angew. Chem. Int. Ed. 55, 23, 6586-6598 (2016). [2] A. Ermakova, G. Pramanik, J.M. Cai, G. Algara-Siller, U. Kaiser, T. Weil , Y.K. Tzeng, H.-C. Chang, L.P. McGuinness, M.B. Plenio, B. Naydenov, F. Jelezko. Detection of a few metallo-protein molecules using color centers in nanodiamonds. Nano Lett. 13, 7, 3305-3309 (2013). [3] Y. Wu, A. Ermakova, W. Liu, G. Pramanik, M. Vu, A. Kurz, L. McGuinness, B. Naydenov, S. Hafner, R. Reuter, J. Wrachtrup, J. Isoya, T. Simmet, F. Jelezko, T. Weil*. Programmable Biopolymers for Advancing Biomedical Applications of Fluorescent Nanodiamonds. Adv. Funct. Mater. 25, 42, 6576–6585 (2015). [4] T. Zhang, A. Neumann, J. Lindlau, Y. Wu, G. Pramanik, B. Naydenov, F. Jelezko, F. Schüder, S. Huber, M. Huber, F. Stehr, A. Hoegele, T. Weil*, T. Liedl*. DNA-based self-assembly of fluorescent nanodiamonds. J. Am. Chem. Soc. 137, 31, 9776–9779 (2015). [5] W. Liu, B. Naydenov, S. Chakrabortty, B. Wuensch, K. Hübner, S. Ritz, H. Cölfen, H. Barth, K. Koynov, H. Qi, R. Leiter, R. Reuter, J. Wrachtrup, F. Boldt, J. Scheuer, U. Kaiser, M. Sison, T. Lasser, P. Tinnefeld, F. Jelezko, P. Walther, Y. Wu, T. Weil. Fluorescent Nanodiamond-Gold Hybrid Particles for Multimodal Optical and Electron Microscopy Cellular Imaging. Nano Lett. 16, 10, 6236-6244 (2016).

38 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 Keynote Talk 14 Erlangen, Germany

Mesocrystals

Julian Brunner1, Holger Reiner1, Elena Sturm1, Helmut Cölfen1,*

(1) Physikalische Chemie, Universität Konstanz, Universitätsstr. 10, D-78457 Konstanz *e-mail: [email protected]

Keywords: Mesocrystal, Non-Classical Crystallization

Mesocrystals are fascinating crystalline nanoparticle superstructures since they combine the properties of nanocrystals with those of microscopic or macroscopic bodies. However, their precise assembly and handles to control their structure are often unknown. In this presentation mesocrystals of Au nanocubooctahedra and magnetite truncated nanocubes are discussed. For both cases, ways to control their formation are presented. The Au nanoparticles in the mesocrystals can be fused upon solvent changes leading to large crystallographically connected structures demonstrating that mesocrystals are only metastable species. For the example of the magnetite mesocrystals, it is shown that different structures can be formed in the same 2D film and that in 3D, the packing arrangement of the self-assembled nanoparticles can be changed by a variety of factors like the solvent. It will be demonstrated, that mesocrystals have many parallels to classical crystals with the difference that their building units are much larger and always anisotropic. Finally, the possibility will be shown, that mesocrystals can also be assembled from chemically different nanoparticle species.

Figure 1: Mesocrystal from magnetite nanocrystals

39 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 Keynote Talk 15 Erlangen, Germany

Morphology of organic solar cells

Li, N.1,*, Brabec, C.1, Rechberger, S.2,*, Spiecker, E.2 and Unruh, T.3,*

(1) Institute of Materials for Electronics and Energy Technology, Friedrich-Alexander Universität Erlangen-Nürnberg, Martensstr. 7, 91058 Erlangen, Germany (2) Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), Friedrich-Alexander Universität Erlangen-Nürnberg, Cauerstr. 6, 91058 Erlangen, Germany (3) Institute for Crystallography and Structural Physics & Center for Nanoanalysis and Electron Microscopy (CENEM), Friedrich-Alexander Universität Erlangen-Nürnberg, Staudtstr. 3, 91058 Erlangen, Germany

*e-mail: [email protected], [email protected], [email protected]

Keywords: organic solar cells, morphology, electron microscopy, X-ray scattering techniques

The field of organic photovoltaics (OPV) has developed significantly in the last years due to novel materials and adapted device engineering. For further improvement the morphology is an indispensable parameter, especially the nanoscale morphology of organic bulk heterojunction (BHJ) solar cells. The performance of organic solar cells is determined by the delicate, optimized BHJ microstructure, where the organic donor and acceptor are fine-mixed in the nano-meter regime to facilitate exciton dissociation at the donor / acceptor interface. The morphology and microstructure can be analyzed using electron microscopy, especially energy-filtered transmission electron microscopy (EFTEM), and X-ray scattering techniques. Even complex geometries such as organic ternary solar cells can be elucidated as well as in situ characterization of the microstructure formation can be realized using these complementary techniques. Finally, the correlations of the morphology, the device performance and stability are discussed.

Figure 1: J-V characteristics of small molecule/fullerene BHJ solar cells after different annealing treatments and respective EFTEM analyses.[1] References [1] Min, J.; et al. Nano Energy 2016 28, 241-249.

40 International Congress Engineering of Advanced Materials ICEAM2017 12 October 2017 10 - 12 October 2017 Keynote Talk 16 Erlangen, Germany

Experimental and theoretical characterization of the structure and stability of phosphonic acid self-assembled monolayers on ZnO surfaces

Witte, G.1,*, Meyer, B.2,*

(1) Fachbereich Physik, Molekulare Festkörperphysik, Philipps-Universität Marburg (2) Interdisciplinary Center for Molecular Materials and Computer-Chemistry-Center, Friedrich-Alexander-Universität Erlangen-Nürnberg

*e-mail: [email protected], [email protected]

Keywords: Chemistry at the solid-liquid interface, surface science analysis, simulation Functionalization of metal oxides by covalently-bound self-assembled monolayers (SAMs) is utilized in molecular electronics, dye-sensitized solar cells or the tailoring of electronic properties of nanoparticles. ZnO is of special interest because of its transparency and high charge carrier mobility, which makes it a promising conductive oxide for use as transparent electrode in optoelectronic devices. Here, the influence of surface orientation and pretreatment on the formation and stability of SAMs has been studied for the case of phenylphosphonic acid (PPA) on ZnO single crystals. Using thermal desorption spectroscopy (TDS), near-edge X-ray adsorption fine structure spectroscopy (NEXAFS) and density-functional theory (DFT) calculations, the thermal stability and orientational ordering of PPA-SAMs on the polar and mixed-terminated ZnO surfaces were analyzed [1]. On all surfaces, PPA-SAMs remain remarkably stable up to 550 K, while at higher temperatures a C−P bond cleavage and dissociative desorption takes place yielding two distinct desorption peaks. Based on DFT calculations, these desorption channels are attributed to protonated and deprotonated chemisorbed PPA molecules, which can be related to tri- and bidentate species, hence allowing to determine their relative abundance from the intensity ratio. Beside immersion, an alternative monolayer preparation based on vacuum deposition in combination with controlled desorption of excess multilayers is demonstrated, allowing to study in detail the impact of residual water on the SAM formation by comparing to intentionally hydroxylated substrates. Corresponding TDS data indicate that initial hydroxylation favors the formation of tridentate and deprotonated bidentate, while the wet-chemical SAM preparation on bare surfaces yields a larger fraction of protonated bidentate species. Furthermore, we show that the formation of the phosphonic acid-anchored SAMs on ZnO competes with an unwanted chemical side reaction, leading to the formation of surface precipitates and severe surface damage [2]. Using X-ray diffraction such surface precipitates are identified as zinc phosponate. The energetics of the transformation pathway has been evaluated by DFT, showing that the PPA molecules can induce strong structural changes in the ZnO surfaces and that crystalline zinc phosphonate is thermodynamically more favorable than PPA-SAMs on ZnO. References [1] Ostapenko, A.; Klöffel, T.; Meyer, B.; Witte, G. Langmuir 2016, 32, 5029-5037. [2] Ostapenko, A.; Klöffel, T.; Eußner, J.; Harms, K.; Dehnen, S.; Meyer, B.; Witte G. ACS Appl. Mater. Interfaces 2016, 8, 13472-13483.

41

Session Talk Abstracts

Session 1 – Session 20

42 International Congress Engineering of Advanced Materials ICEAM2017 Session 1 10 - 12 October 2017 Talk 1 Erlangen, Germany

In situ determination of the crystallinity and temperature of nanoparticle aerosols by Raman spectroscopy

Bahr, L. 1,2*, and Braeuer, A. 1,2

(1) Lehrstuhl für Technische Thermodynamik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Am Weichselgarten 8, 91058 Erlangen, Germany (2) Erlangen Graduate School in Advanced Optical Technologies, Friedrich-Alexander-Universität Erlangen-Nürnberg, Paul-Gordan-Str. 6, 91052 Erlangen, Germany

*e-mail: [email protected]

Keywords: optical characterization, crystallinity, nanoparticles, Raman spectroscopy

As an internal structural parameter, the polymorphic modification is of great importance for the properties of crystalline nanoparticles and, therefore, their application potential. For production purposes, gas-phase synthesis is a widely used method, as it combines the advantages of high resource-efficiency, capability for continuous operation and good ability of controlling particle properties.

With our contribution we demonstrate how Raman spectroscopy can be applied to determine these polymorphic modifications online and in situ during the production process. Distinction of different crystal structures via Raman spectroscopy is based on the excitation of various phonon modes in the crystal lattice. As the crystallinity of nanoparticles strongly depend on the temperatures present in the synthesis process, our technique was, furthermore, developed to measure this parameter simultaneously with the same optical sensor.

In detail, our presentation describes the NIR-Raman measurement setup we built up as well as a measurement chamber, in which defined nanoparticles can be dispersed in various gases (air, N2,

CO2) and spectroscopically analyzed. As example particle systems we used TiO2, ZrO2 and

Fe2O3. The acquired spectra were compared to reference spectra taken from non-dispersed nanoparticle powder by our new setup as well as by a commercial Raman-microscope. Temperature determination was accomplished via spectral fitting of simulated rotational Raman spectra of the gas species present (N2, O2, CO2) to the measured spectra. In addition, we used shifted-excitation Raman difference spectroscopy (SERDS) to reduce the influence of background light (e.g. from flame luminosity or reactor chamber black body radiation at high temperatures) and, consequently, enhance the quality and stability of our results.

The gained expertise will then – in a second step – be transferred to evaluate the influence of varying process parameters on the crystallinity of particles generated in a production process.

Acknowledgements The authors gratefully acknowledge the funding of this work by the German Research Foundation (DFG), project BR 2766/15-1, within the AIF-DFG Cluster MPaC.

43 International Congress Engineering of Advanced Materials ICEAM2017 Session 1 10 - 12 October 2017 Talk 2 Erlangen, Germany

Investigation of a Flame Spray Pyrolysis Process Using Several Optical Measurement Techniques

Münsterjohann, B. 1,3,4*, Huber, F. J. T. 1,3,4 , Stanzel, M. 2, Peukert, W. 2,3 and Will, S. 1,3,4

Friedrich-Alexender-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany (1) Lehrstuhl für Technische Thermodynamik (LTT) (2) Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik (LFG) (3) Cluster of Excellence Engineering of Advanced Materials (EAM) (4) Erlangen Graduate School in Advanced Optical Technologies (SAOT)

*e-mail: [email protected]

Keywords: PDA, shadowgraphy, Mie-scattering, chemiluminescence, TLAF, WALS

The flame spray pyrolysis (FSP) process is one of the mostly used gas-phase techniques in industry and research to produce a broad spectrum of complex and functional nanoparticles on a commercial scale. Nanoparticulate oxides, including zinc oxide (ZnO), gallium(III)-oxide

(Ga2O3) or indium(III)-oxide (In2O3) are low cost and promising materials for electronic and optical devices. To cover the high demand of these interesting materials, FSP turned out to be an economic, energy- and cost-efficient syntheses method. In the flame droplet formation, evaporation, combustion, nanoparticle formation and finally particle growth, agglomeration and sintering takes place. For the production of nanoparticles with well-defined properties, a detailed understanding of the interplay between these different particle formation steps and the influence of varying process conditions on the resulting nanoparticles is essential. However, due to the highly turbulent and multiphase character of the spray flame it is still limited. As the droplet formation and evaporation is one of the first crucial steps in the FSP process, it was characterized by Mie-scattering, Phase-Doppler Anemometry (PDA) and shadowgraphy measurements under different process conditions. PDA allows for pointwise droplet velocity and droplet size measurements whereas the spray geometry with its spray angle and height was analyzed by shadowgraphy measurements and Mie-scattering. The ethanol spray was investigated at both conditions with and without a flame so that the influence of evaporation and combustion on the droplet formation can be analyzed. In order to localize the nucleation zone where particle formation takes place, chemiluminescence measurements were performed for different material systems like pure metal oxides (ZnO, TiO2, SnO, Ga2O3, In2O3) and mixed oxides (ITO, indium zinc oxide, gallium zinc oxide). Furthermore the influence of varying precursor flow rates (2.5 l/min to 10 l/min) and precursor concentrations (0.1 mol/l to 0.5 mol/l) on the size and location of the nucleation zone was investigated. As temperature is one of the most important factors influencing particle size, morphology and crystallinity initial tests for measurements of temperature fields by Two-Line Atomic Fluorescence (TLAF) were performed. Finally, the sizes of the aggregates formed were determined by wide-angle light scattering (WALS).

44 International Congress Engineering of Advanced Materials ICEAM2017 Session 1 10 - 12 October 2017 Talk 3 Erlangen, Germany

Stabilization of gold nanoparticles in micellar solutions

Schmutzler, Tilo1,*; Schindler, Torben¹; Spiecker, Erdmann²; Unruh, Tobias¹;

(1) Chair for crystallography and structural physics, Friedrich-Alexander-University Erlangen-Nürnberg, Staudtstraße 3, 91058 Erlangen, Germany (2) Institute of Micro- and Nanostructure Research, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstrasse 6, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: gold nanoparticles, gold nanorods, CTAB, micelles, stabilization, degradation

Gold nanoparticles (AuNPs) exhibit outstanding optical properties. The plasmonic behaviour of such particles is strongly dependent on their size and shape. The synthesis includes high amounts of the structure directing agent and micelle forming surfactant hexadecyltrimethylammonium bromide (CTAB).[1] By using a strong reducing agent like [2] NaBH4 very small diameters in the range of a few nanometers can be achieved. These particles can be used to synthesize gold nanorods in a further step.[1] These small AuNPs tend to age within a few hours to days, they must be prepared freshly before each gold nanorod synthesis. We found that the time stability of these nanoparticles can be tremendously extended by the addition of n-hexanol to the micellar solution. This alcohol also affects the structure of the CTAB micelles which was studied using small angle X-ray scattering (SAXS) and contrast variation small angle neutron scattering (SANS). We were able to correlate the AuNP stability with the micelle morphology. We found, that the incorporation of alcohol molecules (n-pentanol, n-hexanol) into the micelles leads to a enhancement of the micellar volume within the solution which increases the sterical stabilization of gold nanoparticles. The use of more stable gold seed particles to synthesize gold nanorods leads to products with a higher yield of rod-like morphologies. The combination of X-ray and neutron scattering with UV-Vis-NIR absorption spectroscopy and transmission electron microscopy enabled us to understand the stabilization mechanism of gold Figure 1: The combination of SAXS, contrast variation nanoparticles in micellar solutions. This st SANS (1 row) leads to a deep understanding of the knowledge might be applicable to many stabilization mechanism of gold seed particles (2nd row) and other collidal systems and fits perfectly the thereof prepared gold nanorods (3rd row) that were into the focus of the EAM cluster of characterized using UV-Vis-NIR absorption spectroscopy excellence. and TEM.

References [1] T.K. Sau, A.L. Rogach, Adv. Mater. 2010 22, 1781. [2] N.R. Jana, L. Gearheart, C.J. Murphy, Langmuir 2001 17, 6782.

45 International Congress Engineering of Advanced Materials ICEAM2017 Session 1 10 - 12 October 2017 Talk 4 Erlangen, Germany

Build up of colloidal interfaces: photoluminescence of functionalized ZnO nanoparticle dispersions

Kocsis K.1,*, Niedermaier M.1, Kasparek V. 2, Berger T.1, and Diwald O.1

(1) Department of Chemisty and Physics of Materials, University of Salzburg, Jakob-haringer-Str. 2a, 5020 Salzburg, Austria (2) Central European Institute of Technology, Brno University of Technology, Purkynova 123, 61200 Brno, Czech Republic

*e-mail: [email protected]

Keywords: ZnO, colloid, zeta potential, photoluminescence Surfaces and interfaces of highly dispersed ZnO nanoparticles are key to the material’s extraordinary optical and electronic properties [1]. Functionalization is performed by manipulation of particles’ properties both for stabilization of the colloid but also to achieve desired material features. As changes in surface composition can influence both, surface potential and optical properties, our work focuses on potential correlations between optical and electronic properties of colloidal ZnO. For our investigations, nanoparticles synthesized from the gas phase and dehydroxylated via vacuum annealing serve as model system for the investigation of aqueous colloidal systems. First, the electronic materials’ properties were modified by point defects such as excess electrons generated on the solid/gas interface (i). As a next step, ZnO dispersions and thus solid/liquid interfaces were prepared via controlled condensation of water. On these systems we have found that colloidal particle properties and photoluminescence emission do not show dependence on the presence of specific point defects as well as stoichiometry changes induced by vacuum annealing. In contrast to the negligible effect of excess electrons, which arise from vacuum annealing, accumulation of photogenerated electrons at the solid/liquid interface by UV exposure in the presence of methanol (ii) shows significant changes in both, zeta potential and light emitting properties. Related effects including the effect of photocorrosion, i.e. the light induced dissolution of the metal oxide, will be discussed. As the ZnO particles’ agglomeration and stability in acidic environments compromises the reproducible determination of the colloidal properties [2], we also adjusted the surface charge via the adsorption of acetate and citrate ions in colloidal dispersion (iii). The observed clear correlation of zeta potential and photoluminescence emission properties can be rationalized by adsorption induced generation of surface charges and provides important means for the knowledge-based design of ZnO particles dispersions as interface determined functional materials’.

References [1] Berger T., Diwald O.; Defects in Oxide Nanoparticles Systems, Springer Ser. Surf. Sci., 2015 58, 273-301. [2] Kocsis K. et al., Surf. Sci., 2016 652, 253-260.

46 International Congress Engineering of Advanced Materials ICEAM2017 Session 2 10 - 12 October 2017 Talk 5 Erlangen, Germany

Ultrafine-grained laminated metal composites – a new promising class of materials for lightweight applications

Kümmel, F. * ; Schunk, C. ; Höppel, H.W. and Göken, M.

Institute I: General Materials Properties, Department of Materials Science and Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Martensstr. 5, 91058 Erlangen

*e-mail: [email protected]

Keywords: Accumulative Roll Bonding (ARB), ultrafine-grained (UFG) laminated metal composites (LMCs), fatigue behavior

Laminated metal composites (LMCs) are a unique class of hybrid materials in which alternating metallic layers are bonded together with discrete interfaces. The accumulative roll bonding process enables the production of thin-layered laminated metal composites. Moreover, it is possible to generate an ultrafine-grained microstructure during this process. For an optimization of these new structures a fundamental understanding of the interactions and deformation processes at the internal interfaces is necessary. In this talk, special attention is paid to aluminum/steel and copper/steel composites as the positives aspects of the two constituent materials can be combined. The mechanical properties of LMCs were tested by monotonic- and dynamic experiments in tensile and three-point bending test. The influence of the meso- and microstructure on the deformation behavior was intensively studied by scanning electron microscope. In order to clarify effect of the layer architecture on the internal stress distribution, finite element simulation were performed. By a smart layer architecture, the monotonic and fatigue strength of ultrafine-grained LMCs can be drastically increased. Furthermore, it was shown that a new class of functional materials can be designed that are characterized by a combination of different material properties like high strength and conductivity.

47 International Congress Engineering of Advanced Materials ICEAM2017 Session 2 10 - 12 October 2017 Talk 6 Erlangen, Germany

Enhancement of the formability of multi-layered 6000 series aluminum alloys by functional gradients

Herrmann, J.1,*, Merklein, M.1

(1) Institute of Manufacturing Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 13, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Accumulative Roll Bonding, formability, Tailor Heat Treated Blank

Modern lightweight materials like high-strength aluminum alloys play a key role for the realization of weight-saving concepts in industrial applications. The Accumulative Roll Bonding (ARB) process, which was first presented by Saito et al. [1], enables the production of multi-layered sheet material with increased strength. This process belongs to the group of Severe Plastic Deformation (SPD) techniques. Very large strains are realized during ARB by repeated stacking and roll bonding of the sheets without changing the overall dimensions. The mechanical processing leads to the formation of an ultrafine-grained (ufg) microstructure. Applying this process on precipitation hardenable aluminum alloys of the 6000 series the strength of the material can be increased significantly while the ductility will be reduced [2]. However, for the application of multi-layered aluminum alloys in sheet metal forming operations like deep drawing and bending, a good formability is mandatory. In this context, the Tailor Heat Treated Blank (THTB) technology is a well-known method to enhance the forming limits of conventional aluminum alloys of the 6000 series [3]. Based on a local short term heat treatment the flow behavior of the material towards crack critical areas can be improved. Within this contribution the THTB method is applied on multi-layered aluminum sheet material in order to increase the formability. The material properties are characterized in dependency of the heat treatment temperature in order to investigate the influence on the strength as well as the ductility of the sheet material. In a next step forming experiments are carried out in combination with a local heat treatment of the blanks. The realization of functional gradients like the local softening can be used to influence the flow behavior. The resulting effect on the forming limits will be investigated.

References [1] Saito, Y.; Tsuji, N.; Utsunomiya, H.; Sakai, T.; Hong, R.G. Scr. Mater. 1998 39, 1221-1227. [2] Lee, S.; Saito, Y.; Sakai, T.; Utsunomiya, H. Mat. Sci. Eng. A. 2002 325, 228-235. [3] Vollertsen, F.; Lange, K. CIRP Ann. Manuf. Technol. 1998 47, 181-184.

48 International Congress Engineering of Advanced Materials ICEAM2017 Session 2 10 - 12 October 2017 Talk 7 Erlangen, Germany

Nanocarbon reinforced lightweight metal composites Li, Q1,*, Tam, N1, Nasiri S2 and Zaiser M2

(1) Department of Aeronautics, Imperial College London, UK, (2) Institute of Material Simulation (WW8), University of Erlangen-Nuremberg, Fuerth, Germany *e-mail: [email protected]

Keywords: carbon nanotubes (CNTs), lightweight metal composites, dispersion, reinforcing mechanisms The interest to use nanocarbon such as CNTs to reinforce light metals has increased in recent years. Our previous research showed by adding 0.1wt% CNTs, the mechanical properties of the Mg AZ91 composites could all be improved up to 40%. However, the results are still below the theoretically predicted value [1-2] due to the CNT re-agglomerates during the production . In this paper we present for the first time using metal coated CNTs prepared by layer by layer coating to produce such Mg AZ91 composites. In order to effectively disperse CNTs in the Mg melt, we have coated metals such as Pt on the surface of CNTs. TEM and EDX confirm that atomic Pt has been successfully deposited onto CNTs as shown in Figure 1. Different from coating metal layers on CNTs in literature [3], surface decoration of CNT with metals as in this study may provide further benefits. If, instead of a continuous coating layer, isolated metal nanoparticles as in Figure 1a are deposited on the CNT surface then these nanoparticles may serve a dual purpose that goes well beyond what can be achieved by a continuous coating. Discrete metal nanoclusters on the CNT surface can help to prevent agglomeration by the simple means of acting as geometrical ’spacers’. This effect is well known in the context of graphene where decoration of exfoliated graphene sheets with Pt nanoclusters was shown to prevent face-to-face aggregation of the sheets [4]. The dispersion ability and stability of CNTs have been improved by the Pt coating. The mechanical properties are all improved. Individual pulled out CNTs are observed on the fracture surface of the Pt-coated CNT/AZ91 composites under SEM. We attribute this to a better dispersion and a possible improved wettability of CNTs in Mg melt facilitated by the Pt coating. Simulation of the interactions between different metals e.g. Ni and Pt and CNTs has also been carried out and the results agree with the experimental data. Possible reinforcing mechanisms active in nanocarbon reinforced metal matrix will also be discussed.

References [1] Q. Li, A. Viereckl, C.A. Rottmair and R.F. Singer, Comp. Sci. Tech. 2009 69, 1933. [2] Q. Li and R.F. Singer, Euromat 2013. [3] N. Du, H. Zhang, P. Wu, J. Yu and D. Yang, J. Phys. Chem. C 2009 113, 17387. [4] N. Park, D. Sung, S. Lim, S. Moon and S. Hong, App. Phys. Lett. 2009 94, 073105.

49 International Congress Engineering of Advanced Materials ICEAM2017 Session 2 10 - 12 October 2017 Talk 8 Erlangen, Germany

Fiber optic temperature sensing with transparent glass-filled polymers

Wildner, W. 1,*, Drummer, D. 1 (presenting author specified with an asterisk *)

(1) First Affiliation: Department of mechanical engineering, Institute of Polymer Technology

*e-mail: [email protected]

Keywords: fiber optic temperature sensors, epoxy, glass particles, thermo-optic coefficient

This abstract describes the possibilities of fiber temperature sensing with a compound of epoxy and glass particles with a similar refractive index (RI). Because of the different thermo-optic coefficients of these materials, the compound exhibits a strong wavelength- and temperature-dependent optical transmission, with a maximum at a matching RI between glass and polymer [1]. The compound was integrated into a polymer optical fiber for the fiber optic temperature measurements, figure 1. The polymer’s RI strongly decreases with the temperature, figure 2 (left) which causes temperature dependent RI differences between glass and polymer at specific wavelength. In order to evaluate the temperature of the compound, the transmitted intensity of two different LEDs with wavelengths of 460 nm and 650 nm was analyzed by measuring the voltage at a photodiode. The investigations show that the temperature dependency of the voltage at the photodiode increases with smaller particles and with increasing sensor length, figure 2 (middle) and the voltage ratio decreases up to 60 % for a temperature change of 30 K, figure 2 (right). The described fiber-optic sensor is very compact in size and has the potential for low-cost production; potential applications are disposable sensors for temperature monitoring in particular surroundings, such as magnetic fields or microwaves.

Figure 1: Sensor element with attached fibers and scattering area (glass-filled polymer)

Figure 2: Temperature dependent RI of glass particles and epoxy (left); Temperature dependent voltage at

the photodiode for the two LEDs of sensors with a particle size of d50.3 = 43 and different lengths (middle); Percentage change in the voltage ratio (= U (650 nm)/ U (460 nm)) for different sensors during the heating between 10°C and 40°C with regard to the intensity at a temperature of 10°C (right);

[1] Wolfgang W.; Drummer, D. IEEE Sensors Journal. 2015 16, 688‒692. 50 International Congress Engineering of Advanced Materials ICEAM2017 Session 3 10 - 12 October 2017 Talk 9 Erlangen, Germany

Using fast pressure transients to connect mechanistic studies in ultrahigh vacuum to catalytic reactor performance: oxygen assisted coupling of methanol on nanoporous gold

Robert J. Madix 1,*, Christian Reece 1 and Evgeniy Redekop 2

(1) Harvard University, 29 Oxford Street, Cambridge, MA 02138 (2) Department of Chemistry, University of Oslo, Postboks 1126, Blindern, 0318 Oslo

*e-mail: [email protected]

Studies of oxygen-assisted coupling of methanol on single crystal gold reveal the catalytic cycle responsible for ester formation. These results correctly predict the selectivity observed under catalytic conditions over nanoporous gold at 1 atm and 100-150 C. Fast, metered pressure pulses of methanol were passed over a small amount of the catalyst at 100-150 C at prescribed oxygen coverages and the transient responses of the products determined. The relationship between these kinetic studies and the mechanistic determinations from the modes studies will be discussed.

51 International Congress Engineering of Advanced Materials ICEAM2017 Session 3 10 - 12 October 2017 Talk 10 Erlangen, Germany

Model-Catalytic Studies of Novel Liquid-Organic-Hydrogen-Carriers: Indole, Indoline and Octahydroindole on Pt(111)

Schwarz, M.1*; Bachmann, P. 1; Nascimento Silva, T.1; Mohr, S.1; Scheuermeyer, M.2; Späth, F. 1; Bauer, U.1; Düll, F. 1; Steinhauer, J.1; Hohner, C.1; Döpper, T.3; Noei, H. 4; Stierle, A.4; Papp, C.1; Steinrück, H.-P. 1,5,6; Wasserscheid, P. 2,6; Görling, A.3,5,6; Libuda, J.1,5,6

(1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany (2) Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany (3) Lehrstuhl für Theoretische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany (4) Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg, Germany (5) Erlangen Catalysis Resource Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany (6) Interdisciplinary Center Interface Controlled Processes, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany

*[email protected]

Keywords: liquid-organic-hydrogen-carrier, octahydroindole, platinum, infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, density functional theory.

Liquid organic hydrogen carriers (LOHCs) are molecular compounds which allow storing hydrogen at room temperature and pressure by reversible hydrogenation. Indole (2,3-Benzopyrrole) is a potential LOHC, which may also serve as a building block for larger aromatic systems for hydrogen storage. Here, indole is the hydrogen- and energy-lean carrier compound which is hydrogenated to form the energy-rich octahydroindole. Indoline (2,3-Dihydroindole) would be a partly hydrogenated intermediate in this process. To explore the dehydrogenation mechanism of the above compounds, we follow a model catalytic approach. We exposed atomically clean Pt(111) to indole, indoline, and octahydroindole under UHV conditions, following adsorption and surface reactions by time-resolved and temperature-programmed infrared reflection-absorption spectroscopy (TR-IRAS, TP-IRAS). The multilayer desorption temperatures of the three compounds are 220, 200, and 180 K, respectively. In the monolayer both, indole and indoline, lie flat on the surface at 210 K. Upon annealing, a flat-lying di-σ-indolide is formed as common intermediate via deprotonation for indole or deprotonation and dehydrogenation for indoline, respectively. Also for octahydoindole deprotonation takes place around room temperature. In difference to indole and indoline, however, the reaction starts at the six-membered ring, leading to surface intermediates which are different from the hydrogen-lean compounds. At temperatures above 390 K all three molecules form the same non-saturated and partly decomposed surface species.

52 International Congress Engineering of Advanced Materials ICEAM2017 Session 3 10 - 12 October 2017 Talk 11 Erlangen, Germany

Noble metal free photocatalytic H2 generation on black TiO2: On the influence of crystal facets vs. crystal damage

Ning Liu1, *, Hans-Georg Steinrück2, Andres Osvet3, Patrik Schmuki1 (1) Department of Materials Science WW-4, LKO, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen, Germany; (2) SSRL Materials Science Division, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States; (3) Department of Materials Sciences 6, iMEET, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen, Germany. *e-mail: [email protected]

Keywords: black TiO2, single crystal, noble-metal free photocatalyst

Recently, we found that black TiO2 nanotubes treated by high pressure hydrogenation and hydrogen ion-implantation show an intrinsic co-catalytic active center for H2 evolution – similar in its effect to co-catalytic activation using noble metal decoration [1, 2]. In this study, we investigate noble metal free photocatalytic water splitting on TiO2 single crystal facets and on wafer slices. We measure H2 production before and after these surfaces have been modified by high pressure hydrogenation and hydrogen ion-implantation [3]. We find that on the natural, intact low index planes photocatalytic H2 evolution (in absence of noble metal co-catalyst) can only be achieved when the hydrogenation treatment is accompanied by the introduction of crystal damage, such as simple scratching, miscut in the crystal or by implantation damage. X-ray reflectivity, Raman, and optical reflection measurements show that plain hydrogenation leads to a ≈1 nm thick black titania surface layer without catalytic activity, while a colorless, density modified and ≈7 nm thick layer with broken crystal symmetry is present in the ion implanted surface. These results demonstrate that i) the H-treatment of an intact anatase surface needs to be combined with defect formation for catalytic activation, and ii) activation does not necessarily coincide with the presence of black color.

Figure 1: Photocatalytic hydrogen evolution rate under a He-Cd laser (λ=325 nm) illumination for natural anatase crystals with different treatments and optical image of natural intact anatase single crystal.

53 International Congress Engineering of Advanced Materials ICEAM2017 Session 3 10 - 12 October 2017 Talk 11 Erlangen, Germany

References [1] Liu N., Schneider C., Freitag D., Hartmann M., Venkatesan U., Müller J., Spiecker E., Schmuki P., Nano Lett., 2014, 14, 3309. [2] Liu, N., Haublein V., Zhou X., Venkatesan U., Hartmann M., Mackovic M., Nakajima T., Spiecker E., Osvet A., Frey L., Schmuki P., Nano Lett., 2015, 15, 6815. [3] Liu N., Steinrueck H., Osvet A., Yang Y., Schmuki P., Appl Phys Lett, 2017, 110, 072102. Author, S.; Author, T. Journal Abbrev. Year Volume, Pages.

54 International Congress Engineering of Advanced Materials ICEAM2017 Session 3 10 - 12 October 2017 Talk 12 Erlangen, Germany

Real-time monitoring of products during aqueous electrochemical reactions

Khanipour, P.; Reichert, A.; Löffler, M.; Spörler, S.; Mayrhofer, K.J.J. and Katsounaros, I.*

Forschungszentrum Jülich GmbH, Helmholtz-Institut Erlangen-Nürnberg für Erneuerbare Energien (IEK-11), Egerlandstraße 3, 91058 Erlangen, Deutschland

* Presenting author: [email protected]

Keywords: electrochemical synthesis, product determination, material libraries

Electrochemistry deals by definition with conversions between electrical and chemical energy, therefore it offers the most promising solution for the storage of renewable energy in the form of chemical bonds. In particular, the electrical energy from renewables can be used to drive electrochemical reactions and produce fuels or value-added chemicals. In either case, it is essential to steer the selectivity of the reaction towards a desired product. Some approaches have been successfully employed so far to monitor the products of aqueous electrochemical reactions. In long-term electrolysis (constant potential/current), dissolved or gaseous products can be determined at given times with classical analytical techniques (liquid or gas chromatography, nuclear magnetic resonance spectroscopy, etc) [1,2]. Under dynamic conditions, e.g. during cyclic voltammetry, volatile products can be detected after separation from the aqueous phase depending on their vapour pressure [3,4], while dissolved species can be determined offline after collection of liquid samples near the electrode vicinity [5]. However, the above do not allow the real-time detection of all products in gaseous and liquid phase. Here, we will present a novel methodology for the determination of reaction products in aqueous solutions in real-time, without the need of any separation techniques, thus allowing sufficient time/potential resolution together with excellent sensitivity. The methodology can be coupled with a home-made electrochemical cell, the scanning flow cell, which allows the rapid investigation of material libraries. Therefore, this new methodology offers a new excellent tool for the high-throughput screening of materials relevant for electrochemical synthesis.

Acknowledgements This work was supported by the Federal Ministry for Education and Research (BMBF) under the project grants 03SFK2Z0 (Power-to-X) and 033RC004C (eEthylen).

References [1] Hori, Y.; Murata, A.; Takahashi, R. J. Chem. Soc. Faraday Trans. 1989, 85, 2309–2326. [2] Kuhl, K. P.; Cave, E. R.; Abram, D. N.; Jaramillo, T. F. Energy Environ. Sci. 2012, 5, 7050–7059. [3] Baltruschat, H. J. Am. Soc. Mass Spec. 2004, 15, 1693–1706. [4] Wonders, A. H.; Housmans, T. H. M.; Rosca, V.; Koper, M. T. M. J. Appl. Electrochem. 2006, 36, 1215–1221. [5] Kwon, Y.; Koper, M. T. M. Anal. Chem. 2010, 82, 5420–5424.

55 International Congress Engineering of Advanced Materials ICEAM2017 Session 4 10 - 12 October 2017 Talk 13 Erlangen, Germany

In situ study of the growth of poorly water-soluble drug nanoparticles prepared by antisolvent precipitation

Noll, D. M.;1,* Schindler, T;1 Schuldes, I.;1 Unruh, T.1

(1) Friedrich-Alexander-Universität Erlangen-Nürnberg, Chair for Crystallography and Structural Physics, Staudtstraße 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: nanoparticles, organic, precipitation, growth, SAXS, SANS Antisolvent precipitation is an established and widely used bottom-up approach for the production of nanoparticles of poorly water-soluble active pharmaceutical ingredients (APIs). The bioavailability of these APIs can be enhanced by producing smaller particles but therefore the precipitation process has to be optimized and the influence of stabilizers on the nucleation kinetics, which is almost unknown in the field of organic nanoparticles, has to be studied. It has been shown that the nucleation of perylene as a model for organic nanoparticles is finished after the first tens of milliseconds.[1] Combined SAXS and SANS experiments demonstrate that the combination of both methods is highly suitable to study the stabilizer layer of organic nanoparticles on the example of triglyceride particles.[2-4] Combining the stopped-flow technique and SAXS and SANS enables to study the structure and the stabilizer layer of organic nanoparticles during the precipitation process and especially during the first milliseconds after the mixing process for the first time. First experiments at the D22 beamline (ILL, Grenoble) show the reliability of the combination of the stopped-flow technique with SANS to study the growth of fenofibrate nanoparticles (cf. fig. 1).

Figure 1: Left: First in situ SANS data show the growth of fenofibrate nanoparticles during antisolvent precipitation. For each mixing process fenofibrate solved in ethanol was mixed with the stabilizer solved in

D2O with a ratio of 1 : 9. The temporal resolution of 50 ms was achieved by 10 mixing processes. Right: Assuming spherical particles preliminary analyses show the growth of fenofibrate nanoparticles over a range of 300 s and that the smallest average diameters of over 20 nm during the first 50 ms. References [1] J. Mori et al., J. Cryst. Growth 2009 311, 553 [2] M. Schmiele et al., Phys. Rev. E 2013 87, 062316 [3] M. Schmiele et al., J. Phys. Chem. B 2014 118, 8808 [4] M. Schmiele et al., PCCP 2015 17, 17939

56 International Congress Engineering of Advanced Materials ICEAM2017 Session 4 10 - 12 October 2017 Talk 14 Erlangen, Germany

Formation of drug nanocrystals with improved dissolution characteristics Christoph Konnerth1,3,*, Veronika Braig2,3, Jochen Schmidt1, Geoffrey Lee2,3, Wolfgang Peukert1,3

(1) Institute of Particle Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany (2) Division of Pharmaceutics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany (3) Cluster of Excellence − Engineering of Advanced Material (EAM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstraße 4, Nägelsbachstraße 49b, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: active pharmaceutical ingredient, nanosuspension, media milling, spray-drying, formulation

A large number of new drug entities exhibit unfavourable physicochemical and biopharmaceutical properties. Especially poor aqueous solubility is a leading hurdle in formulation science, because it is often associated with an insufficient bioavailability after oral administration. Hence, a wide variety of formulation strategies such as particle size reduction techniques became more important for product engineering of problematic drug compounds to improve biopharmaceutical characteristics [1,2]. An industrially feasible formulation approach combining media milling and spray-drying has been applied to improve dissolution properties of structurally different BCS class II drug compounds to improve its in vitro dissolution characteristics. Besides commonly investigated key parameters stress energy (SE), stress number (SN) and mass specific energy input (Em), the influence of formulation variables (i.e. polymorphic form of the feed material, type and concentration of the applied stabiliser molecule) on product formation during wet comminution and its transformation into solid products has been studied in detail. It can be shown that low SE and high SN are advantageous with respect to process kinetics and minimum energy consumption. Moreover, drug characteristics are rather determined by liquid phase mediated dissolution and ripening phenomena (i.e. the (temperature-, solvent- and formulation dependent) solid-liquid equilibrium) than by pure mechanical fracture events or colloidal stability issues [3-5]. Furthermore, tablets prepared by direct compression which contain nanocrystalline drug particles exhibit a significant improvement of in vitro drug dissolution rate as compared to the dosage form containing drug particles in the micronised state, elucidating the great potential of this formulation approach for a systematic delivery of problematic BCS class II compounds. References [1] F. Kesisoglou, S. Panmai, Y. Wu, Adv. Drug Delivery Rev. 2007 7, 631-644. [2] G.G. Liversidge, K.C. Cundy, Int. J. Pharm. 1995 1, 91-97. [3] C. Konnerth, C. Damm, J. Schmidt, W. Peukert, Adv. Powder Technol. 2014 6, 1808-1816. [4] A. Ito, C. Konnerth, J. Schmidt, W. Peukert, Eur. J. Pharm. Biopharm. 2016 98, 98-107. [5] C. Konnerth, F. Flach, S. Breitung-Faes, C. Damm, J. Schmidt, A. Kwade, W. Peukert, Powder Tech. 2016 294, 71–79.

57 International Congress Engineering of Advanced Materials ICEAM2017 Session 4 10 - 12 October 2017 Talk 15 Erlangen, Germany

Hydrodynamic mixing of turbulent miscible flows in a T-micromixer under real operating conditions

Tobias Schikarski1,*, Wolfgang Peukert 2 and Marc Avila 1,3 (1) Institute of Fluid Mechanics, Friedrich-Alexander-University Erlangen Nuremberg, Erlangen, Germany (2) Institute of Particle Technology, Friedrich-Alexander-University Erlangen Nuremberg, Erlangen, Germany (3) Center of Applied Science Technology and Microgravity, University Bremen, Bremen, Germany

*e-mail: [email protected]

Keywords: Turbulent mixing, Direct numerical simulation, T-micromixer

Liquid antisolvent precipitation (LAP) is a basic and promising, but not well understood, pharmaceutical manufacturing process of drugs. The drug is initially dissolved in an alcohol like ethanol, which is then mixed with an antisolvent like water. In the mixing region a thermodynamic imbalance (supersaturation) arises and the drug precipitates forming nanoparticles. The bioavailability of the drug in the human body is determined by the size of the nanoparticles, and hence the aim of the pharmaceutical industry is to produce monodisperse particle distributions of the smallest possible sizes. The size of the nanoparticles is determined by the supersaturation, which in turn depends strongly on the mixing efficiency. Thus a detailed understanding of the flow phenomena is required to control and improve the particle formation. A promising approach to understand the fundamentals of the mixing of water-ethanol flows is DNS. This approach entails several challenges of different nature. First, the operating conditions of the manufacturing process involve highly turbulent flow (typically Re=(103,104)) so that the mixing is fast and homogeneous. Second, the diffusion of ethanol in water is naturally very slow, which results in very high Peclet numbers. Third, density and viscosity change nonlinearly with the fluid composition. This strongly couples the Navier-Stokes equations with the convection-diffusion equation. We here investigate turbulent mixing up to real operating conditions Re<= 4000 of water-ethanol flow in a simple T-micromixer, Fig. 1. The approach of analyzing the hydrodynamic mixing is three-way. On the one hand turbulent quantities such as scalar and momentum energy dissipation, anisotropy of the flow and Reynolds stresses are evaluated with respect to the local and global mixing behavior. Additionally, those parameters may serve as a benchmark of industrial accessible tools such as LES and RANS. On the other hand process and industrial relevant parameters such as pressure loss and overall degree of mixing are presented, which is linked to experimental results accentuating the possible prediction and valuable support by simulations.

We acknowledge funding from the Deutsche Forschungsgemeinschaft (DFG) through the Cluster of Excellence Engineering of Advanced Materials (EAM).

58 International Congress Engineering of Advanced Materials ICEAM2017 Session 4 10 - 12 October 2017 Talk 15 Erlangen, Germany

Figure 1: We here show instantaneous snapshots of an active scalar representing the mixing of water with ethanol. A horizontal cut through the T-mixers outlet channel gives the engineer/reader the opportunity to conceive easily the enhanced mixing effciency by the increased energy input (Reynolds number). Decreasing turbulent scales enlarge the interface between the mixture components, which improves substantially the reaction rate or particle kinetics.

59 International Congress Engineering of Advanced Materials ICEAM2017 Session 4 10 - 12 October 2017 Talk 16 Erlangen, Germany

The effect of synthesis pathway on amorphous calcium carbonate

Schüssler, M.1,* and Wolf, S. E.1,2

(1) Department of Materials Science and Engineering, Institute of Glass and Ceramics (WW3), Friedrich-Alexander-University Erlangen-Nuremberg, Martensstrasse 5, 91058 Erlangen, Germany. (2) Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander University Erlangen-Nürnberg (FAU), Haberstrasse 9a, 91058 Erlangen, Germany.

*e-mail: [email protected]

Keywords: amorphous calcium carbonate, nonclassical crystallization, spinodal decomposition

Amorphous calcium carbonate (ACC) is the thermodynamically most unstable form of calcium carbonate and plays an important role as a transitional or stabilized phase in the formation of biominerals. Variation of the synthesis of ACC causes different morphologies, particle sizes and short-range orders, which affect the transformation to crystalline polymorphs. Liquid-liquid phase separation of a supersaturated solution was proposed as a nonclassical route to a solid phase formation. We investigate the effect of different syntheses pathways, pH, and concentration on the ACC formation.

Figure 1: Phase diagram illustrating the binodal demixing and spinodal decomposition of calcium carbonate.

References [1] Addadi, L.; Raz, S.; Weiner, S. Adv. Mater.. 2003 15, 959-970. [2] Zou, Z.; Bertinetti, L.; Politi, Y.; Jensen, A. C. S.; Weiner, S.; Addadi, L.; Fratzl, P.; Habraken, W. J. E. M. Chem. Mater. 2015 27, 4237-4246. [3] Tobler, D. J.; Blanco, J. D. R.; Sorensen, H. O.; Stipp, S. L. S.; Dideriksen, K. Cryst. Growth Des. 2016 16, 4500-4508. [4] Zou, Z; Habraken, W. J. E.; Bertinetti, L.; Politi, Y.; Gal, A.; Weiner, S.; Addadi, L.; Fratzl, P. Adv. Mater. Interfaces 2017 4, 1600076.

60 International Congress Engineering of Advanced Materials ICEAM2017 Session 5 10 - 12 October 2017 Talk 17 Erlangen, Germany

Modelling and Simulation of Multiphase Pulsed Electric Field (PEF) Applications

Sailer, J.1 ; Horneber, T.1,* and Rauh, C.1,2

(1): Department of Food Biotechnology and Food Process Engineering, Technische Universität Berlin, Königin-Luise-Straße 22, 14195 Berlin, Germany (2): Institute of Fluid Mechanics, FAU Erlangen/Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: pulsed electric field, multiphase modelling, computational fluid dynamics

For several years, the technology of pulsed electric fields (PEF) is used in the food industry for tasks of product-friendly disinfection, as well as disruption of intact biological cells and tissues for ingredient release. Depending on the field of application (treatment of fruit juice, mash, or whole fruits like apples or tomatoes) various flow treatment chambers have to be optimised from lab scale up to industrial scale (mass flows up to 4 t per h). Amongst other things the flow profile, a homogeneous distribution of the electric field, total energy intake, and inactivation of microorganisms are optimisation criteria. Based on previous work [1,2] the C++ open source framework OpenFOAM was used and modified for the coupling and solving for the balancing equations of thermo-fluid dynamic (mass, momentum, energy) and electrostatic (charge conservation) by a finite volume technique. All material parameters (density, viscosity, thermal and electrical conductivity,…) are temperature dependent. Different treatment chambers are compared and characterised (collinear, coaxial, plate-plate). Additionally, for the case of the treatment of whole fruits (e.g. tomatoes, apples) a multi-physics solver (solid and fluid) was implemented which enables the detailed analysis of local effects regarding electric field strength and temperature. This multiphase solver was coupled with a fluid-structure interaction approach to model the movement of a whole fruit through the treatment chamber. Finally a transport equation for the survival rate of e.g. cell stability or enzymes is coupled to the solver [3] predicting the effect of the pulsed electric field on the product.

References [1] Krauss, J.; Ertunç, Ö; Rauh, C.; Delgado, A.: Innovative Food Processing Technologies: Advances in Multiphysics Simulation 2011, First Edition, Wiley. [2] Meneses, N.; Jaeger, H.; Knorr, D.: Innovative Food Processing Technologies: Advances in Multiphysics Simulation 2011, First Edition, Wiley. [3] Wölken, T.; Sailer, J.; Maldonado-Parra, F.; Horneber, T.; Rauh, C.: Handbook of Electroporation 2017, Springer.

61 International Congress Engineering of Advanced Materials ICEAM2017 Session 5 10 - 12 October 2017 Talk 18 Erlangen, Germany

Lattice Boltzmann simulations of the statics and dynamics of magnetocapillary swimmers

Sukhov, A. 1,*, Xie, Q. 2, Pande, J. 3, Smith, A. 3 and Harting, J. 1,2

(1) Dynamics of Complex Fluids and Interfaces, Forschungszentrum Jülich GmbH, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IEK-11), 90429 Nürnberg, Germany (2) Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 56000MB Eindhoven, The Netherlands (3) Institute for Theoretical Physics, Friedrich-Alexander University Erlangen-Nürnberg, 91054 Erlangen, Germany

*e-mail: [email protected]

Keywords: magnetocapillary microswimmers, self-assembly, magnetic particles When three or more identical ferromagnetic beads (diameters ~ 100 μm) are placed at a fluid-gas interface, they deform the fluid surface inducing thus attractive capillary interactions. An external static magnetic field applied perpendicularly to the interface (Fig. 1) results in repulsive dipole-dipole interactions, which, if balanced by the capillary interaction, lead to a stable particle arrangement. When, in addition, a small modulating time-dependent magnetic field distorts the static one, such system, also called a magnetocapillary swimmer, starts to self-propel. In recent experiments [1] it was shown that such microswimmers reach speeds of some 100 μm/s and can be well manipulated by external magnetic fields, which makes them potentially interesting for multiple applications like a controlled cleaning of liquid interfaces or even a drug delivery. We use a hybrid lattice Boltzmann and discrete element method to show the self-assembly of the swimmer as well as a sharp dependence of the average speed of the swimmer on the frequency of the time-dependent magnetic field, demonstrate the control of the direction of the swimmer motion using B-fields and perform analysis of the obtained results based on the bead-spring model [2, 3].

Figure 1: Schematics of the simulated system in 3D (a) and in the plane of the interface (b)

References [1] Grosjean G.; Lagubeau G.; Darras A.; Hubert M.; Lumay G.; Vandewalle N. Sci. Rep. 2015 5, 16035. [2] Pande J.; Merchant L.; Krüger T.; Harting J.; Smith A.-S. New J. Phys. 2017 in press. [3] Pande J.; Merchant L.; Krüger T.; Harting J.; Smith A.-S. arXiv:1611.1795.

62 International Congress Engineering of Advanced Materials ICEAM2017 Session 5 10 - 12 October 2017 Talk 19 Erlangen, Germany

Model for the obstructed lateral diffusion on a 2D interface

Cvitković, M.; 1,2,*, Smith, A.-S.; 2

(1) CLS Group, Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička 54, Zagreb, Croatia (2) PULS Group, Cluster of Excellence: EAM, FAU Erlangen-Nürnberg, Nägelsbachstr. 49b, Erlangen, Germany

*e-mail: [email protected]

Keywords: diffusion, trapping, crowding

Diffusion on two-dimensional interfaces is often obstructed due to interactions of diffusing particles with the environment. In general, interactions can appear between the particle and the interface, and between the particle and other particles. Interactions with the interface can be local, in which case the particle is trapped in a particular point (trap) for a segment of time. Such traps slow down normal diffusion and induce a regime of anomalous diffusion. The interaction with other particles can be either attractive or repulsive. In both cases diffusion is also slowed down, by forming larger complexes or by crowding the space for movement, respectively. To model the effect of both crowding and trapping on diffusion, we study a two–dimensional lattice gas in the field of randomly distributed traps, as a function of concentration of traps and the tracers. Tracers mutually interact with a hard wall potential, while the interaction of tracers and traps is modelled by binding and unbinding rates. We find that after the anomalous regime, the linear, but rescaled diffusion is recovered in the bulk of the parameter space. We determine several regimes in which scaling of the long–time MSD can be achieved, and derive the analytical expression for the effective diffusion coefficient in equilibrium. Interestingly, we discover a part of the parameter space in which an increase of the concentration of tracers effectively speeds up diffusion.

63 International Congress Engineering of Advanced Materials ICEAM2017 Session 5 10 - 12 October 2017 Talk 20 Erlangen, Germany

Distinct disordered glassy states of soft spheres

Maiti, Moumita* and Schmiedeberg, Michael University of Erlangen-Nuremberg, Staudtstrasse 7, 91058 Erlangen, Germany

*email: [email protected]

Approaching zero temperature a repulsive soft sphere system explores hard-sphere like behavior. We consider repulsive harmonic potential and explore densities below athermal jamming density and temperature regime close to zero. At early time we observe a disordered state of larger contact number. Then the system transits to another disordered state of lower contact number. There is no issue with crystallization for the bidisperse system, and for monodisperse packing we discard the states with crystallites and then analyze. From the analysis of the mean squared displacement, we observe a broader plateau for the second disordered state. The late time behavior like diffusivity also changes from one disordered state to the other. The disordered state with larger contact number can be interpreted as the behavior of soft spheres which later transits to hard-sphere like behavior. From the extrapolation to higher densities, this might imply that a soft sphere glass is different from the hard sphere glass.

64 International Congress Engineering of Advanced Materials ICEAM2017 Session 6 10 - 12 October 2017 Talk 21 Erlangen, Germany

Fabrication and characterisation of a fully auxetic 3D lattice structure via selective electron beam melting

Franziska Warmuth 1, Torsten Wolf 1,*, Fuad Osmanlic 1, Lucas Adler 1, 2, Matthias A. Lodes 1 and Carolin Körner 2

(1) Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-University Erlangen- Nürnberg, Dr.-Mack-Str. 81, D-90762 Fürth, Germany (2) Materials Science and Engineering for Metals (WTM), Friedrich-Alexander-University Erlangen- Nürnberg, Martensstr. 5, D-91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: auxetic, additive manufacturing, selective electron beam melting

Periodic cellular structures were first considered in the field of lightweight construction due to their high specific stiffness, damping and energy absorbing properties [1]. Usually, the mechanical properties and the deformation behaviour can be controlled by appropriate choice of the underlying unit cell [2, 3] and by adjusting the relative density [4]. A three-dimensional fully auxetic cellular structure with negative Poisson’s ratio is presented. Samples are fabricated from Ti6Al4V powder via selective electron beam melting. The influence of the strut thickness and the amplitude of the strut on the mechanical properties and the deformation behaviour of cellular structures is studied.

Figure 1: Cubic chiral unit cell. References [1] Gibson, L. J.; Ashby, M. F., Cambridge University Press 1999, Cellular Solids [2] Woesz, A.; Stampfl, J.; Fratzl, P., Adv. Eng. Mater. 2004, vol.6, 134–8 [3] Ashby, M. F., Phil. Trans. R. Soc. 2006, A 364, 15-30

65 International Congress Engineering of Advanced Materials ICEAM2017 Session 6 10 - 12 October 2017 Talk 22 Erlangen, Germany

Parametric Shape Optimization of Lattice Structures for Phononic Band Gaps

Wein, F. 1,*, Stingl, M.1

(1) Professur Mathematische Optimierung, FAU, Erlangen, Germany

*e-mail: [email protected]

Keywords: topology optimization, phononic band gaps

Topology optimization of phononic band gap structures (Sigmund & Jensen; 2003) yields periodic designs which suppress transmission of vibrations for a wide frequency range. However, the standard solutions are composed by solid material embedded within a weaker matrix material and are therefore bi-material designs. It is inherently difficult to find connected solid/void band gap designs exhibiting a certain stiffness. Not only are the standard maximal band gap and maximal stiffness designs mutual exclusive, the band gap optimization is also known for non-smoothness issues caused by multiple and switching eigenvalues. Nevertheless, in (Bilal & Hussein; 2012) an in-plane design with a normalized band gap of 0.77 is presented as the best known design of its kind. Here we propose a method, where a lattice is subject to parametric shape optimization and mapped onto a ersatz material model as used in topology optimization. From the parametric shape optimization, we have the assured connectivity of the structure and absolute control on the black and white contrast. We obtain square symmetric designs with normalized band gaps up to 1.6, however porosity and stiffness significantly differs from Bilal & Hussein's design.

Figure 1: A periodic strucuture with a normalized gap of 1.2 and a relative gap of 3.2 exibiting a Young’s modulus of 31% of solid material

66 International Congress Engineering of Advanced Materials ICEAM2017 Session 6 10 - 12 October 2017 Talk 23 Erlangen, Germany

Single phase phononic band gap material produced by selective electron beam melting

Wormser, M. 1,*, Warmuth, F. 1 and Körner C.2

(1) First Affiliation: Friedrich-Alexander Universität Erlangen-Nürnberg, Zentralinstitut für neue Materialien und Prozesstechnik (ZMP) Fürth, Dr.-Mack-Straße 81, 90762 Fürth (2) Second Affiliation: Friedrich-Alexander Universität Erlangen-Nürnberg, Lehrstuhl für Werkstoffe und Technologie der Metalle (WTM), Martensstraße 5, 91054 Erlangen

*e-mail: [email protected]

Keywords: additive manufacturing, phononic band gaps, metamaterials A phononic band gap is a frequency range where mechanical wave propagation is suppressed in a material. Such materials usually consist of two phases - a matrix with a regular array of inclusions - with a large mismatch of elastic constants. We have developed a single phase phononic band gap material using selective electron beam melting, a powder-based additive manufacturing method. By using only one material instead of two, the mechanism is different to the most descriptions in literature. The open cellular geometry (see Figure 1) was designed by FEM eigenmode analysis of a cubic strut-based unit cell [1]. Additionally, numerical dispersion relations were calculated to determine the band gap position. In a sound transmission experiment using additively manufactured Ti-6Al-4V samples the numerical results were verified. The influence of geometrical parameters on the band gap position was analyzed. It is shown that a combination of different types of unit cells can lead to wider band gaps. Therefore it is possible to design structures with low relative densities that absorb certain sound frequency ranges, e.g. for an application as insulators against vibration or noise.

Figure 1: Open cellular structure produced by selective electron beam melting. References [1] Körner, C., Liebold-Ribeiro, Y. Smart Mater. Struct. 2015 24, 025013.

67 International Congress Engineering of Advanced Materials ICEAM2017 Session 6 10 - 12 October 2017 Talk 24 Erlangen, Germany

Tailoring the grain structure in IN718

Martin R. Gotterbarm 1*, Johannes Köpf 2, Fuad Osmanlic 1, Matthias Markl 2 and Carolin Körner 2

(1) Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-University Erlangen- Nürnberg, Dr.-Mack-Str. 81, D-90762 Fürth, Germany (2) Chair of Materials Science and Engineering for Metals (WTM), Friedrich-Alexander-University Erlangen-Nürnberg, Martensstr. 5, D-91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: grain structure tailoring, additive manufacturing, selective electron beam melting, 3D grain growth model, cellular automata

The grain morphology typically found in parts manufactured by beam based additive manufacturing techniques for metals like selective electron beam melting (SEBM) are columnar grains elongated in the build direction [1,2]. For metals or alloys with a cubic crystal system like IN718 a strong <001> fiber texture parallel to the building direction can be observed, which results in an anisotropic mechanical behavior [3–5]. We present a method of altering the grain structure of SEBM-IN718 by adapting the scan strategy. The result are columnar grains deviating significantly from the build direction, as shown in Fig. 1. A deeper understanding of this effect is provided by exploitation of a recently developed 3D simulation of the solidification conditions during the SEBM process.

Figure 1: Tailored grain structures produced via SEBM. Left: IPF-Z Map of a tailored grain structure produced by SEBM by using an adapted scan strategy. Right: Corresponding 3D simulation.

68 International Congress Engineering of Advanced Materials ICEAM2017 Session 6 10 - 12 October 2017 Talk 24 Erlangen, Germany

References [1] H.E. Helmer, C. Körner, R.F. Singer, Additive manufacturing of nickel-based superalloy Inconel 718 by selective electron beam melting: Processing window and microstructure, J. Mater. Res. 29 (2014) 1987–1996. [2] A. Strondl, M. Palm, J. Gnauk, G. Frommeyer, Microstructure and mechanical properties of nickel based superalloy IN718 produced by rapid prototyping with electron beam melting (EBM), Mats. Sci. Tech. 27 (2009) 876–883. [3] C. Körner, Additive manufacturing of metallic components by selective electron beam melting — a review, International Materials Reviews 61 (2016) 361–377. [4] H.E. Helmer, N. Hartmann, C. Körner, R.F. Singer, Relation Between Processing Strategy, Grain Structure and Mechanical Properties in Superalloy Inconel 718 Processed by Selective Electron Beam Melting, in: DDMC 2014: Fraunhofer Direct Digital Manufacturing Conference proceedings, 2014. [5] A.A. Antonysamy, J. Meyer, P.B. Prangnell, Effect of build geometry on the β-grain structure and texture in additive manufacture of Ti6Al4V by selective electron beam melting, Materials Characterization 84 (2013) 153–168.

69 International Congress Engineering of Advanced Materials ICEAM2017 Session 7 10 - 12 October 2017 Talk 25 Erlangen, Germany

X-ray photoemission studies of a liquid model system for a Pd-Ga bimetallic dehydrogenation catalyst

Grabau, M. 1,*; Erhard, J. 3; Taccardi, N. 2; Krick Calderon, S. 1; Wasserscheid, P. 2; Neiss, C. 3; Görling, A. 3; Steinrück, H. P. 1, Papp, C. 1

(1) Physikalische Chemie 2, FAU Erlangen, Egerlandstraße 1-3, 91058 Erlangen (2) Chemische Reaktionstechnik, FAU Erlangen, Egerlandstraße 1-3, 91058 Erlangen (3) Theoretische Chemie, FAU Erlangen, Egerlandstraße 1-3, 91058 Erlangen

*[email protected]

Keywords: XPS, alloy, Pd, Ga

Using binary alloys in a well-functioning catalysts, in particular in applied industrial catalysis, is not a new concept. During the last decades, however, multi-metallic model systems have also attracted more and more the interest of surface scientists, seeking to understand the reasons for activity, selectivity and stability of certain catalyst systems on an atomic level [1,2,3]. In this study, we addressed model systems consisting of Pd-Ga alloys with a Pd content of up to 1.8 at.% in the liquid phase. These investigations help to characterize and understand a silica- supported Pd-Ga bimetallic catalyst, which has been shown to outperform commercial catalysts in the dehydrogenation of light alkanes [4]. For the liquid phase, an inhomogeneous Pd distribution along the surface normal was derived from a quantitative evaluation of ARXPS data collected in 0 and 80° emission. From these data, in combination with molecular dynamics simulations, a depletion of Pd at the interface was achieved, which goes along with an enrichment in the surface-near region below the interface. We also followed the oxidation of liquid Ga and Pd-Ga alloys at pressures up to 1 mbar of oxygen in situ at different temperatures.

Upon oxidation, a Pd-lean Ga2O3 film forms that covers the liquid-vacuum interface. This results in a redistribution of Pd towards the sample bulk. This Pd redistribution is independent of pressure, although, as is expected, the growth of Ga2O3 films strongly depends on temperature and pressure. Further, XPS and online mass spectrometry studies on the reactivity of supported Pd-Ga alloys will be discussed.

References [1] Clarke, J. K. A. Chem. Rev. 1975 75, 291- 305. [2] Ponec, V. Appl. Cat. A 2001 222, 31-45. [3] Zafeiratos, S.; Piccinin, S.; Teschner, D. Catal. Sci. Technol. 2012 2, 1787-1801. [4] Taccardi, N. et al. 2017, submitted for publication.

70 International Congress Engineering of Advanced Materials ICEAM2017 Session 7 10 - 12 October 2017 Talk 26 Erlangen, Germany

XPS Investigation of the Catalytically Triggered Energy Release in the 2,3-dibromo-substituted Norbornadiene/Quadricyclane Storage System on Ni(111)

Bauer U. 1,*, Späth F. 1, Weiß C. 2, Hirsch A. 2, Steinrück H.-P. 1 and Papp C. 1

(1) Department of Chemistry and Pharmacy, Physical Chemistry II, Egerlandstraße 3, 91058 Erlangen (2) Department of Chemistry and Pharmacy, Organic Chemistry II, Henkestraße 42, 91054 Erlangen *e-mail: [email protected]

Keywords: solar energy conversion, norbornadiene, high-resolution X-ray photoelectron spectroscopy

Dwindling fossil fuels force humanity to search for new energy production routes. Besides energy generation, the storage is also a crucial aspect. One promising new approach is to store energy from the sun chemically in strained organic molecules that can release this energy in a catalytic process. However, parameters such as quantum yields, absorption spectra, energy storage densities and half times of the parent and the strained compound need to be adjusted alongside the search for active catalysts and photosensitizers. A prototype example for such a molecular solar thermal system is the norbornadiene/quadricyclane molecule pair.1,2 We recently investigated the energy release and the surface chemistry of NBD and QC on a Pt(111) surface where we found an immediate conversion from QC to NBD ≤ 120 K. On Ni(111) we observed a lower catalytic activity and conversion occurs around 170 K.3,4 Herein, we now introduced bromine atoms at the 2,3 position of both compounds to study the influence towards adsorption behavior, energy release and their surface chemistry on Ni(111). With XPS we were able to observe the conversion of Br2-QC to Br2-NBD in-situ at elevated temperatures.

Figure 1: Figure 2: Illustration of the catalytic cycle in the Br2-NBD/Br2-QC molecular solar thermal energy system. During irradiation of the parent compound Br2-NBD by sun light, the energy rich Br2-QC isomer is produced. After adsorption at a catalyst surface, the stored energy is released and Br2-NBD is regained.

References [1] Dubonosov, A.; Bren, V.; Chemoivanov, V. Russ. Chem. Rev. 2002 71, 917-927. [2] Quant, M.; Lennartson, A.; Dreos A.; Kuisma M.; Erhart P.; Börjesson K.; Moth-Poulsen K. Chem. Eur. J. 2016 22, 13265-13274. [3] Bauer, U.; Mohr, S.; Döpper T.; Bachmann P.; Späth F.; Düll F.; Schwarz M.; Brummel O.; Fromm L.; Pinkert U.; Görling A.; Hirsch A.; Bachmann J.; Steinrück H.-P.; Libuda J.; Papp C. Chem. Eur. J. 2017 23, 1613-1622. [4] Bauer, U.; Fromm L.; Späth F.; Görling A.; Steinrück H.-P.; Papp C. unpublished 2017

71 International Congress Engineering of Advanced Materials ICEAM2017 Session 7 10 - 12 October 2017 Talk 27 Erlangen, Germany

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrode Surfaces: Thousand-Fold Performance Improvement

Haschke S.1,*, Pankin D.2, P e t r o v Y. 3, Manshina A.4 and Bachmann J. 1

(1) Department Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany (2) Center for Optical and Laser Materials Research, Saint-Petersburg State University, Uljanovskaya 5, 198504 St. Petersburg, Russia (3) Interdisciplinary Resource Center for Nanotechnology, Saint-Petersburg State University, Uljanovskaya 1, 198504 St. Petersburg, Russia (4) Institute of Chemistry, Saint-Petersburg State University, Universitetskii pr. 26, 198504 St. Petersburg; Russia

*e-mail: [email protected]

Keywords: iron oxide, nanostructured, oxygen evolution catalysis

The ability to electrolyze water into its elements in benign conditions at low cost will imply the exclusive use of cheap, abundantly available materials, instead of most advanced catalysts. Here, we demonstrate that iron oxide, the most abundant and least expensive transition metal compound, can be used as a catalytically active surface for the four-electron water oxidation to [1] O2 at neutral pH which represents the kinetic bottleneck of the overall reaction. Nanostructured iron(III) oxide electrodes, prepared from anodic alumina templates coated with

Fe2O3 by atomic layer deposition, are optimized for catalytic proficiency in the water oxidation reaction. Scanning helium ion microscopy, X-ray diffraction and Raman spectroscopy characterize the morphology and phase of samples submitted to various treatments. These methods document the contrasting effects of thermal annealing, on the one hand, and of electrochemical treatment, on the other hand. The electrochemical performance of the corresponding electrodes is quantified by steady-state electrolyses and electrochemical impedance spectroscopy. A rough and amorphous Fe2O3 with phosphate incorporation proves to be optimal in the water oxidation reaction. The combination of electrochemical treatments with the “anodic” pore geometry delivered an effective turnover increase by a factor of ≈1000 with respect to an as-deposited, planar Fe2O3 surface.

Figure 1: Nanostructured Fe2O3 electrode in top view (left), in cross section (middle) and the corresponding water oxidation performance at pH 7 at 0.49 V applied overpotential η. References [1] Kanan M.W., Nocera D.G., Science 2008 321, 1072-1075.

72 International Congress Engineering of Advanced Materials ICEAM2017 Session 7 10 - 12 October 2017 Talk 28 Erlangen, Germany

Titania nanotubes integrated with polymer containing Prussian Blue centres as a hydrogen peroxide sensor

Grochowska K.*1, Szkoda M.2, Nowaczyk G.3, Lisowska-Oleksiak A.2, Siuzdak K.1

(1) Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery Polish Academy of Sciences, Fiszera 14, 80-231 Gdańsk, Poland (2) Department of Chemistry and Technology of Functional Materials, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, 80-233 Gdańsk, Poland (3) Nanobiomedical Centre, Adam Mickiewicz University in Poznań, Umultowska 85, 61-614 Poznań, Poland

*e-mail: [email protected]

Keywords: titania nanotubes, conducting polymer, Prussian Blue, electrochemical sensor, hydrogen peroxide

Although hydrogen peroxide is a very simple molecule in nature, it is of particular significance in biological systems and finds practical applications in pharmaceutical, clinical and environmental fields. Thus, many works have focused on the development of electrochemical sensing of H2O2 [1] including enzyme anchored substrates, which operating is unfortunately limited due to the limited lifetimes, high costs, low stability and denaturation of enzymes. As an promising alternative to enzyme based sensors, the different non-enzymatic electrode materials dedicated to H2O2 detection have been developed. They contain transition metals and metal oxides, polypyrrole, MoS2, carbon nanotubes and Prussian Blue (PB), that is characterized by enzyme-like activity. PB was widely used as electron transfer mediator for the construction of oxidase-based electrochemical biosensor due to its redox and catalytic properties. In order to improve stability in wider pH-range or enhance the registered response towards H2O2, introduction of PB into the polymer matrix, addition of Au nanoparticles or carbon nanotubes have been proposed. Here, we present the highly ordered titania nanotubes (TiO2NTs) infiltrated with poly(3,4-ethylenedioxythiphene) as a matrix for Prussian Blue species incorporation [2] that can be used as a sensing material to hydrogen peroxide. The TiO2NTs were produced via two-step anodization procedure, followed by calcination at 450°C resulting in anatase phase formation and hydrogenation allowing for their surface activation. In the next step, electrochemical polymerization and subsequent multicyclic polarization took place resulting in the formation of hybrid organic-inorganic material pEDOT:PB uniformly deposited onto the ordered scaffold as revealed by TEM and SIMS inspection. The verification of the material activity in the presence of various H2O2 concentration and interfering species (dopamine, ascorbic acid, uric acid) was carried out by means of chronoamperometry, cyclic and differential pulsed voltammetry techniques. This work received financial support from the Polish National Science Centre: Grant No. 2012/07/D/ST5/02269 and the Foundation for Polish Science (FNP). References [1] Chen W., Cai S., Ren Q., Wen W., Zhao Y., Analyst 2012 137, 49-58. [2] Siuzdak K., Szkoda M., Karczewski J., Ryl J., Lisowska-Oleksiak A., RSC Adv. 2016 6, 76246-76250.

73 International Congress Engineering of Advanced Materials ICEAM2017 Session 8 10 - 12 October 2017 Talk 29 Erlangen, Germany

Particle synthesis modeled by nonlocal balance laws, process simulation and optimization

Alex, K.1 , Pflug, L.2,*, Spinola, M.2 , Stingl, M.3, and Leugering, G. 2

(1) UC Berkeley, ITS, 94720 Berkeley, USA (2) Lehrstuhl für Angewandte Mathematik 2, Cauerstr. 11, 91058 Erlangen (3) Mathematische Optimierung, Nägelsbachstr. 49B, 91052 Erlangen

*e-mail: [email protected]

Keywords: particle ripening process, nonlocal balance law, process optimization

Particle ripening processes can be described in a continuous way as the evolution of a particle-size density [1,2]. For this evolution, it is crucial to consider dynamical models depending nonlocally on the particle-size density, which leads - together with the conservation of the number of particles - to the necessity of modeling with so-called nonlocal balance laws. Thereby, a mathematical theory for this class of equations is developed, strongly relying on the analysis of fixed-point equations together with the concept of characteristics. Furthermore, these results are used to derive schemes for solving nonlocal balance laws numerically. The accuracy of the numerical scheme is studied in detail for a wide range of non-smooth initial data as well as ripening functions. Depending on the p-norm - measuring the error to the analytical solution - and the regularity of the initial data the convergence order of the presented scheme is in the range of 1/p to 3 with respect to the space-time discretization. Finally, computing sensitivities of the model with respect to process conditions make it possible to deduce necessary first order optimality conditions for optimal control problems relying on nonlocal balance laws. These conditions are used to compute gradient information of a given objective functional depending on the final particle size distribution with respect to process conditions.

References [1] Haderlein M., Segets D., Gröschel M., Pflug L., Leugering G.,Peukert W., Ch.E.J., 2015 260, 706-715 [2] Peukert W., Segets D., Pflug L., Leugering G.,In Adv. in Chem. Eng., 2015 46, 1-81 [3] Keimer A., Leugering G., Gröschel M., Wang Z., SIAM J. on C. and O., 2014, 52(4), 2141-2163

74 International Congress Engineering of Advanced Materials ICEAM2017 Session 8 10 - 12 October 2017 Talk 30 Erlangen, Germany

Systematic design of zero-index-materials using topology optimization

Wang F. * and Sigmund O.

Department of Mechanical Engineering, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark

*e-mail: [email protected]

Keywords: Topology optimization, zero-index-material, Dirac cone

Materials with zero refractive index, in which light experiences no phase change because of the infinite phase velocity in the materials, have many potential applications, such as optical cloaking and directional emission [1]. Zero-index-materials (ZIMs) were firstly realized by using metallic metamaterial structures with large loss and impedance mismatch. Recently, ZIMs were experimentally demonstrated via Mie resonance in dielectric photonic crystals [2, 3]. The zero index behavior was demonstrated to be related to a Dirac cone at the Brillouin zone (BZ) center [2, 3], where two linear dispersion bands intersect at a Dirac point. Previously, Dirac cones were designed via a tedious trial-and-error approach. More recently, topology optimization was employed to design Dirac points by excitating photonic crystals using prescribed model profiles [4]. However, it is very difficult to enforce linear dispersion around the target Dirac point using the approach presented in [4], and thus difficult to ensure a Dirac cone. In this work, we present an approach to design ZIMs using topology optimization in a systematic way based on band structure calculation of photonic crystals. The design of ZIMs is formulated as an optimization problem to design photonic crystals with Dirac cones, i.e. to tune low order dispersion bands to form a Dirac cone at the BZ center by distributing dielectric material in crystals. Moreover, manufacturability of the optimized ZIMs is ensured by considering different design realizations in the optimization procedure [5]. The optimized ZIMs are numerically evaluated using a prism presented in [3], composed of the optimized materials. References [1] Engheta, N. Science 2013 340(6130), 286-287. [2] Huang, X.; Yun, L.; Hang, Z. H.; Zheng, H.; Chan, C. T. Nat. Mater. 2011 10(8), 582-586. [3] Li, Y.; Kita, S.; Muñoz, P.; Reshef, O.; Vulis, D. I.; Yin, M.; Mazur, E. Nat. Photon. 2015 9(11), 738-742. [4] Lin, Z.; Pick, A.; Lončar, M.; Rodriguez, A. W. Phys. Rev. Lett. 2016 117(10), 107402. [5] Wang, F.; Lazarov, B. S.; Sigmund, O.; Struct. Multidiscip. O. 2011 43(6), 767-784.

75 International Congress Engineering of Advanced Materials ICEAM2017 Session 8 10 - 12 October 2017 Talk 31 Erlangen, Germany

Structural Optimization for multi-criteria electromagnetic applications

Semmler, Johannes; Stingl, Michael1,* (1) Professur für Mathematische Optimierung und ZISC - Zentralinstitut Scientific Computing,

Friedrich-Alexander-Universität Erlangen-Nürnberg, D-91052 Erlangen, Nägelsbachstr. 49b

*e-mail: [email protected]

The presentation is concerned with the numerical simulation and optimization of optical properties of mono layered nano-particle films. The optical properties of interest are the transmission through the film and its haze factor. While the transmission can modeled in a straight forward way based on Maxwell’s equation, for the haze factor a model close to an experimental setup is derived. The numerical solution gets involved due to the resulting size of computational domain, which renders the direct application of the FEM method infeasible. As a remedy a hybrid method is suggested, in the core of which analytical solutions for the far field are combined with FEM-based near filed solutions in a consistent way. Based on this, structural optimization problems are formulated by the help of which the influence of different particle arrangements can be studied. For the solution of the latter, a specialized material optimization solver is applied. Finally, the results of numerical studies are discussed and related to experimental results presented by Karina Bley in the same session.

76 International Congress Engineering of Advanced Materials ICEAM2017 Session 8 10 - 12 October 2017 Talk 32 Erlangen, Germany

Hierarchical low haze metal arrays optimize transparency for transparent conducting electrodes

Bley, K. 1,*, Semmler, J. 2 Rey, M. 1, Zhao, C. 1, Klupp Taylor, R. 1, Stingl, M. 2 and Vo ge l , N . 1

(1) Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Haberstraße 9a, 91058 Erlangen (2) Mathematik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstraße 11, 91058 Erlangen

*e-mail: [email protected]

Keywords: transparent conductive electrodes, metal nanohole arrays, haze factor Transparent conductive electrodes are key components in optoelectronic devices such as solar cells and touch displays. The combination of high transparency and high conductivity normally leads to a tread-off, as the presence of a high amount of conducting material means simultaneously a reduced optical transmission. Metal nanohole arrays are interesting model structures to combine both criteria and can be easily fabricated for instance via colloidal lithography. [1] This method enables the fabrication of metal nanohole structures with high precision, tunable sizes in nanoscale resolution and long-range order. To maximize transparency, the metallized area must be minimized, while retaining a percolated metal pathway to ensure conductivity. However, the percolation threshold fundamentally limits the achievable transparency. [2] An important third property to characterize the electrode performance is the amount of scattered light, the so-called haze factor. Depending on the application, either a low or a high haze value can be preferential. Here, we present a systematic study of structural parameters of metal nanohole arrays and their influence on the haze factor. We find the haze factor to be very sensitive to hole periodicity and diameter. Therefore, transmission and haze cannot be controlled individually, they are strongly related. Further, we develop a process to design hierarchical metal micro/nanohole arrays that maximize transparency and enable the creation of extremely low haze values by combination of holes with different length scale (Figure 1).

Figure 1: Characterization of 15 nm gold hierarchical micro/nanohole array (a) SEM image, (b) transmission spectra, and (c) photograph of reference and hierarchical micro/nanohole arrays. References [1] Stelling, C. et al. Sci. Rep. 2017 7, 42530. [2] Peng, Y. Applied Physics Letters. 2010 94, 041901.

77 International Congress Engineering of Advanced Materials ICEAM2017 Session 9 10 - 12 October 2017 Talk 33 Erlangen, Germany

Electronic structure of one- and two-dimensional polymers fabricated in a hierarchical on-surface synthesis on Au(111)

Christian Steiner1, Julian Gebhardt2, Maximilian Ammon1, Zechao Yang1, Alexander Heidenreich3, Natalie Hammer3, Andreas Görling2, Milan Kivala3, and Sabine Maier1*

(1) Department of Physics, University of Erlangen-Nürnberg, Erlangen (2) Chair of Theoretical Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Erlangen (3) Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Erlangen

*e-mail: [email protected]

On-surface synthesis, 2D polymers

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free 2D covalent networks remains a challenge and makes it difficult to unveil their electronic structure. Here, we report on the hierarchical on-surface synthesis of nearly defect-free 1D and 2D covalent architectures on Au(111), which were investigated by low-temperature scanning tunneling microscopy in combination with density-functional theory.[1] The carbonyl-bridged triphenylamine precursors formed six-membered macrocycles and 1D chains as intermediates in an Ullmann-type coupling reaction that were subsequently interlinked to 2D networks. We observed a reduction of the electronic band gap from the monomer to the 1D and 2D structures. The significant drop of the gap from the monomer to the polymer confirms an effective conjugation along the building blocks.

References [1] C. Steiner, et al. Nature Communications, 8, 14765 (2017)

78 International Congress Engineering of Advanced Materials ICEAM2017 Session 9 10 - 12 October 2017 Talk 34 Erlangen, Germany

Resonance of the depolarization ratio in circularly polarized photoluminescence of transition metal dichalcogenides

Tornatzky, H.*1;Gillen, R.1,2;Maultzsch, J.1,2

(1) Institut für Festkörperphysik, TU Berlin, Hardenbergstr. 36, 10623 Berlin, Germany (2) Institut für Physik der Kondensierten Materie, FAU, Erwin-Rommel-Str. 1, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: TMDs, PL, circular polarization

Transition metal dichalcogenides (TMDs) attract a lot of interest due to their unique properties. Especially the strong photoluminescence from the direct gap in few layered samples has been repeatedly investigated. Furthermore, TMDs have recently become promising materials for spin- and valleytronics as circular polarized excitation leads to the generation of electron-hole-pairs with distinct spin at either K or K’ points in the Brillouin zone. However, questions remain unanswered about the mechanisms of the scattering processes, especially on phonons. We have performed circular polarization resolved Raman and photoluminescence spectroscopy with different excitation energies. We observe a lower threshold for depolarization than what was predicted by Kioseoglou et al. for the scattering on two LA-phonons [1-3]. We will present the observed resonance of the conservation of the circular polarization and discuss different possible depolarization processes.

References [1] Kioseoglou, et al., Appl. Phys. Lett. 101, 221907 (2012). [2] Kioseoglou, et al., Phys. Status Solidi RRL 10, No. 1, 111–119 (2016). [3] Kioseoglou, et al., Scientific Reports, 6:25041 (2016).

79 International Congress Engineering of Advanced Materials ICEAM2017 Session 9 10 - 12 October 2017 Talk 35 Erlangen, Germany

Bridging the scales between nanoparticles’ surface chemistry and colloidal stability

Lin, W.;1,2 Süß, S.;1,2 Sobisch, T.;4 Burger, A.;3 Maid, H.;3 Hirsch,A.;2,3 Lerche, D.;4 Peukert, W;1,2 and Segets, D.1,2

(1) Institute of Particle Technology (LFG), FAU; (2) Interdisciplinary Center for Functional Particle Systems (FPS), FAU; (3) Institute of Organic Chemistry, FAU; (4) LUM GmbH, Berlin *e-mail: [email protected] Keywords: Functionalization, ligand binding, Hansen dispersibility parameter, formulation The performance of small nanoparticles in optoelectronic devices like solar cells or light emitting diodes (LEDs) largely depends on their surface chemistry and how well these particles can be embedded in an appropriate continuous phase. However, to date no holistic approach to formulation of nanoparticles does exist which includes thermodynamics and kinetics of ligand binding on the molecular level, dispersibility and colloidal stability on the mesoscale, as well as product properties like optoelectronic device performance on the macroscopic level. Herein, we use ZnO semiconductor nanoparticles (NPs) that can be modified with catechol derivatives of varying functionality to demonstrate how surface chemistry can be linked to NPs dispersibility and colloidal stability against agglomeration. For the molecular characterization, a well-validated toolbox of different methods that has been established by our group is applied [1, 2]. Thereby gained information on binding energy and in particular on surface coverage is then linked to the particle level by solubility, or better dispersibility parameters. The applied concept of Hansen Solubility Parameters (HSP) is based on the Hildebrand-Parameter (HP), which is directly connected to the chemical potential and thus to the activity coefficient. To account for the origin of the interactions, C. Hansen subdivided HP into disperse, polar and H-Bond contribution. Herein, a standardized and non-subjective procedure using analytical centrifugation (AC, LUMiSizer) was developed to transfer HSP to colloids and thus to determine Hansen Dispersibility Parameters (HDP) of NPs. AC is a powerful method to characterize in situ the stability as agglomeration can be directly made accessible by sedimentation in a well-defined sedimentation run [3]. If this procedure is repeated for a defined set of liquids with known HSP, based on experimentally determined sedimentation times, good and poor liquids for NP dispersion are identified. Finally, HDP of the NPs are derived via a recently developed ranking procedure and colloidal surface properties become accessible. These in turn can be correlated with the aforementioned molecular findings on surface chemistry to systematically analyze effects of particle size, ligand concentration, functionalities of different tail groups, as well as binding strength. In conclusion, our hierarchical concept allowed establishing structure-property relationships between molecular features of individual ligand molecules, ligand binding to colloidal particles at the molecular level and ink properties in terms of dispersibility at the macroscopic level. This paves the way towards knowledge-based formulation.

References 1. Lin, W., et al., Angew. Chem. Int. Ed., 2016. 55: p. 932-935. 2. Lin, W., et al., Chem. Mater., 2015. 27: p. 358-369. 3. Lerche, D., S. Horvat, and T. Sobisch, Dispersion Letters, 2015. 6: p. 13-18.

80 International Congress Engineering of Advanced Materials ICEAM2017 Session 9 10 - 12 October 2017 Talk 36 Erlangen, Germany

Synthesis and Structural Characterisation of Nanoparticles of Holmium Hafnate (Ho2Hf2O7) for SOFC Applications

Sardar, S.*, Kale, G., Ghadiri, M. School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, U.K.

*E-mail: [email protected]

Keywords: Nanoparticles, Pyrochlore, Alginate synthesis, Electrolytes, Holmium hafnate

Solid Oxide Fuel Cells (SOFCs) are an efficient and cost effective system for direct conversion of a variety of fuels to electricity. Morphology and microstructure of cell components are very important for durability and performance of SOFC. Sol gel processes are used to fabricate the SOFC components with preferred properties or functionalities, as they are capable of providing [1] good control of structure, composition, microstructure and morphology . A2B2O7 oxides with pyrochlore or defected fluorite structure are one of the most favourable candidates of SOFC electrolyte material. This study reports current work on the synthesis of Holmium Hafnate nanoparticles through the sol gel method using nitrates of holmium and hafnium as starting materials. Ion exchange with sodium alginate and its subsequent thermal decomposition are used to prepare the powder. Beads of gel are produced by ionic gelation between solutions of nitrates and sodium alginate and were subsequently washed and dried for 24 h in convection oven. Thermal decomposition of precursor is carried out at 700˚C for 2 h to obtain the nanoparticles of Ho2Hf2O7. This calcination temperature was decided after carrying out simultaneous thermogravimetric analysis and diffraction scanning calorimetry (TGA/DSC). Fine crystalline material is obtained on calcination at relatively low temperature (700˚C). Structural and morphological characterisation of the nanoparticles was carried out using X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Raman spectroscopy and Scanning electron microscopy (SEM). Crystal size is determined using SEM pictures by measuring individual crystal size. The local structure of Holmium Hafnate has been analysed by combined X-ray diffraction and spectroscopy. Raman Spectroscopy reveals the existence of defects in nanoparticles structure.

References: [1] Lu, Z., Zhou, X., Fisher, D., Templeton, J., Electrochemistry Communications, Vol. 12, No. 2, 2010, pp. 179-182.

81 International Congress Engineering of Advanced Materials ICEAM2017 Session 10 10 - 12 October 2017 Talk 37 Erlangen, Germany

Mechanical Testing of Copper Alloy Micropillars Containing a Single Twin Boundary

B. Merle, J. Liebig, S. Krauß, M. Göken

Materials Science & Engineering 1, Friedrich-Alexander-University Erlangen-Nürnberg (FAU) [email protected]

Nanotwinned metals are a promising class of modern materials combining a very high strength with a high ductility and excellent electrical properties. This remarkable strength is believed to be connected to the good efficiency of twin boundaries as obstacles to dislocation motion. The present study aims at identifying and characterizing the possible interaction modes between dislocations and coherent twin boundaries. This is achieved by compressing micropillars containing a single twin boundary of a controlled orientation. The influence of the stacking fault energy on the intrinsic strength of the twin boundary is also investigated by varying the investigated material.

In detail, the micropillars are fabricated from recrystallized polycrystalline samples of copper and α-brass, which is a low stacking-fault energy alloy exhibiting a high density of recrystallization twins. Coherent twin boundaries are selected from an EBSD orientation mapping of the sample and oriented by means of a custom 3D-printed sample holder. FIB- milling at these interfaces yields micropillar specimens containing a single twin boundary. Single crystalline reference samples are obtained from the bulk of the grains located on both sides of the twin boundary. The microcompression tests allow quantifying the influence of the twin boundary barrier on the strength of the sample as a function of the stacking fault energy of the material. The activated glide systems are subsequently identified from slip trace analysis and STEM mapping of lamellas obtained by lift-off from the bulk of the tested micropillars. This allows identifying the different deformation modes, which will be discussed in the presentation.

82 International Congress Engineering of Advanced Materials ICEAM2017 Session 10 10 - 12 October 2017 Talk 38 Erlangen, Germany

Base Cells and Interpretation of 3D Two-Scale Optimization Results for Additive Manufacturing

Vu, Bich Ngoc1,* ; Guess, Thomas1; Wein, Fabian1 and Stingl, Michael1

(1)Friedrich-Alexander-Universität Erlangen-Nürnberg, Zentrales Institut für Scientific Computing (ZISC), Germany

*e-mail: [email protected]

Keywords: structural optimization, base cells, additive manufacturing

Consider a two-scale material optimization approach in linear elasticity using homogenized base cells as introduced in [1]. We aim to realize the full workflow from optimization towards printing by additive manufacturing technologies. This encompasses the classification, selection and design of a suitable three-dimensional base cell with respect to manufacturing constraints, where the design variables control the local orthogonal stiffnesses of the base cell. In particular, we suggest structures with strong differences in these orthogonal stiffnesses and elaborate reasons for this choice. In order to obtain a continuously connected and manufacturable lattice structure, we interpret the two-scale optimization result in a post-processing step and generate a ready-to-print surface description of the lattice structure. This result then provides the base for a numerical validation of the obtained macroscopic design.

Figure 1: A microstructure consisting of local elements based on parametrized base cells.

References [1] Bendsøe, M. P.; Kikuchi, N.; Generating Optimal Topologies in Structural Design using a Homogenization Method, Comput. Methods in Appl. Mech. Eng 1998 Vol. 71, 197-224

83 International Congress Engineering of Advanced Materials ICEAM2017 Session 10 10 - 12 October 2017 Talk 39 Erlangen, Germany

An Unforeseen Mechanism for the Generation of Functionally Graded Lightweight Biogenic Ceramics by Systematic Lattice Curvature

Harris, J. 1*; Wallis, D.2; Böhm, C1; Hansen, L. 2; Feldner, P. 3; Merle, B. 3; and Wolf, S.1;

(1) Institute of Glass and Ceramics, Friedrich-Alexander-University (FAU), Martensstrasse 5, Erlangen (2) Department of Earth Sciences, University of Oxford, Oxford, Oxfordshire, OX1 3AN, UK (3) Institute I, FAU, Martenstrasse 5, Erlangen

*e-mail: [email protected]

Keywords: Lightweight materials, Functionally Graded Materials, Biomineralization

Biomineralizing organisms generate lightweight materials with task-optimized structures from earth-abundant elements in ambient conditions. Typical materials design motifs in Nature incorporate combinations of crystalline inorganic architectures and biopolymers, which yield functional materials with mechanical property gradients that increase damage tolerance and prevent catastrophic failure1. As a consequence, the strategies used by biomineralizing organisms can serve as an extensive source of inspiration for the emerging field of functionally graded materials. Here, we present an unforeseen mechanism for the generation of functionally graded materials by systematic crystallite-to-crystallite lattice rotation2. The model bivalve exploits the anisotropic mechanical properties of its crystalline component to generate a materials gradient by regulating crystallite orientation. Control over lattice orientation gradients, and orientation-related constraints on crystal growth, gives rise to a gradual disorder-to-order transition during microstructure formation, yielding a bioceramic with a gradient of mechanical properties. The microstructure is optimized for purpose with maximum resistance to both blunt and sharp contact damage at the exterior of the shell. These observations reveal a new mechanism, systematic crystal lattice curvature, for the generation of crystallographically co-aligned materials, and demonstrate a hitherto unforeseen method for the design of functionally graded solid-state materials.

Figure 1: EBSD map of a prism displaying orientation gradient, and wear resistance of the microstructure References [1] Weaver, JC.; Millieron, GE; Miserez, A et al. Science. 2012 336, 1275-1280. [2] Harris, J; Wallis, D; Böhm, C; Hansen, L; Feldner, P; Merle, B; Marin, F; Wolf, S.E. Submitted

84 International Congress Engineering of Advanced Materials ICEAM2017 Session 10 10 - 12 October 2017 Talk 40 Erlangen, Germany

Microstructure design of porous materials described by the Biot model in the homogenization framework by gradient-based shape optimization

Hübner, D.1,*, Lu ke š, V. 2, Rohan, E.2 and Stingl, M.1

(1) Department Mathematik, Friedrich-Alexander University Erlangen-Nürnberg (2) Department of Mechanics, NTIS, Faculty of Applied Sciences, University of West Bohemia in Pilsen

*e-mail: [email protected]

Keywords: Biot model, poroelastic material, homogenization, shape optimization, sensitivity analysis

Gradient-based shape optimization of microstructures generating locally periodic porous materials saturated by viscous fluid is discussed. The porous medium is described as the Biot continuum [2] obtained via the homogenization method, see e.g. [3]. The effective material properties are given by the drained skeleton elasticity, the Biot stress coupling, the Biot compressibility coefficients and the hydraulic permeability of the Darcy flow model. Using the domain method of the design velocity approach the sensitivity analysis for all homogenized material coefficients is presented. For the shape optimization the design of the microstructure is parametrized by control points of a B-spline tensor product volume which embeds the whole representative volume element. The objective of the optimization is to maximize stiffness while permitting sufficient permeability and vice versa. Issues of the spline box parametrization and the channel shape regularity are addressed. In conclusion numerical examples motivated by material design as well as two-scale optimization are presented.

References [1] Allaire, G.; Shape optimization by the homogenization method Springer Science & Business Media 2012 146. [2] Biot, M. A.; Theory of elasticity and consolidation for a porous anisotropic solid J. Appl. Phys.. 1955 26.2, 182-185. [3] Rohan, E.; Naili, S.; Lemaire, T.; Double porosity in fluid-saturated elastic media: deriving effective parameters by hierarchical homogenization of static problem Continuum Mech. Thermodyn. 2016 28, 1263-1293.

85 International Congress Engineering of Advanced Materials ICEAM2017 Session 11 10 - 12 October 2017 Talk 41 Erlangen, Germany

Selective oxidation of lignocellulosic biomass to formic acid and high-grade cellulose with tailor-made polyoxometalate catalysts (SelOxPOM)

Albert, J. 1*, Voß, D. 1, Bukowski, A. 1, Pickel, H. 1, Lakhe, K. 1, Modvig, A. 2, Riisager, A.2, Maerten, S. 3, Liauw, M. 3

(1) Institute of Chemical Reaction Engineering, FAU Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany (2) Department of Chemistry, Technical University of Denmark, Kemitorvet Building 206, 2800 Kgs. Lyngby, Denmark (3) Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany

*e-mail: [email protected]

Keywords: Biomass, Polyoxometalate, Oxidation The main goal of this EAM Starting Grant project was to design and to optimize tailor-made polyoxometalate catalysts for the stepwise oxidation of lignocellulosic biomass to produce formic acid and high-grade cellulose. The results of the research project will open new horizons for the sustainable use of biogenic raw materials with regard to chemical compounds. Regarding suitable biogenic substrates, lignocellulose seems to be a promising carbon source for the production of liquid fuels and platform chemicals.1 Polyoxometalates (POMs) are organo-metallic complexes of light transition metals at their highest oxidation state in combination with oxygen. They have attracted much attention in recent years because of their fascinating architectures and excellent physico-chemical properties. 2 A fractionated conversion of the main components of lignocellulose was reached by a variation of several transition metals and heteroatoms in the polyoxometalate cage in combination with process optimization. This groundbreaking scientific approach relies on our recent, very interesting observation that some homogeneous polyoxometalates firstly catalyze the selective decomposition of the amorphous hemicellulose followed by the oxidation of the phenolic lignin.3 In contrast to previously known wood pulping and paper manufacturing processes, the goal to achieve was to isolate high-grade cellulose as the only solid residue of the oxidation process instead of lignin which has only its caloric value. By the help of optimized, task-specific polyoxometalate catalyst materials and highly integrated processes new and attractive technologies for the valorization of complex biomasses should be implemented.

Figure 1: Schematic illustration of SelOxPOM-project goal.

86 International Congress Engineering of Advanced Materials ICEAM2017 Session 11 10 - 12 October 2017 Talk 41 Erlangen, Germany

References [1] Albert, J., Wasserscheid, P., Green Chem., 2015, 17 (12), 5164. [2] Albert, J., Mehler, J., Tucher, J., Kastner, K., Streb, C, Chemistry Select, 2016, 1, 2889. [3] Albert, J., Farad. Discuss, 2017, DOI: 10.1039/C7FD00047B.

87 International Congress Engineering of Advanced Materials ICEAM2017 Session 11 10 - 12 October 2017 Talk 42 Erlangen, Germany

Selective oxidation of water-soluble biomass to formic acid in a continuous process

Voß, D.; 1,*, Albert, J.; 1 and Wasserscheid, P.; 1

(1) Department of Chemical Engineering, Friedrich-Alexander-University Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: biomass oxidation, polyoxometalates, continuous process

The selective catalytic oxidation of biogenic feedstock in the OxFA process (Oxidation of Biomass to Formic Acid) is a promising way to use the energy stored in the primary energy carrier biomass to produce a secondary energy carrier such as formic acid. By the use of a homogeneous catalyst from the substance class of polyoxometalates, this conversion can be performed under mild reaction conditions in aqueous solution with very high selectivities. [1] In order to establish an integrated continuous biomass conversion process at laboratory scale, an upscaling was performed and a continuous operating plant was built. With this laboratory plant, it is possible to oxidize water-soluble biomass in a continuous process including an in situ extraction of the produced formic acid with a second, organic phase and an efficient recycle of the used catalyst and non-converted substrate into the reaction vessel. By variation of several process parameters, a sensitivity analysis of the process was performed in order to find the optimum process parameters for the subsequent pilot scale. The investigated parameters are, for instance, reaction temperature, oxygen pressure, gas entrainment, residence time and the ratio of catalyst and substrate as well as the ratio between substrate and extracting agent. Furthermore, investigations on the long-term stability and activity of the polyoxometalate catalyst HPA-5 (H8PV5Mo7O40) were performed. For the economical evaluation of the catalytic process and the efficiency of the catalyst, the turnover number (TON) and the turnover frequency (TOF) were estimated.

References [1] Wölfel, R.; Taccardi, N.; Bösmann, A.; Wasserscheid, P.; Green Chem. 2011, 13, 2759-2763

88 International Congress Engineering of Advanced Materials ICEAM2017 Session 11 10 - 12 October 2017 Talk 43 Erlangen, Germany

Atomic Layer Deposition of Pd and SnO2 onto TiO2 Nanotubes: effect of the support on the ethanol electrooxidation

Barr, M. K. S.;1 Assaud, L;1 Brazeau, N.;2 Hanbücken, M.;1 Ntais, S.;2 Santinacci, L1,* and Baranova, E. A.2

(1) Aix Marseille Univ, CNRS, CINaM UMR 7325, 13288, Marseille, France. (2) Department of Chemical and Biological Engineering, Centre for Catalysis Research and Innovation, University of Ottawa, 161 Louis-Pasteur St., Ottawa, ON, K1N 6N5, Canada

*e-mail: [email protected]

Keywords: electrooxidation, ALD, Palladium

Due to their low environmental impact and high power generation, fuel cells are promising alternative in automobile industry. The manufacturing of direct oxidation fuel cells by degradation of organic molecules, such as ethanol or methanol, using electrocatalysis is an attractive way to produce green energy. Direct Ethanol Fuel Cells (DEFCs) offer significant advantages due to ethanol non-toxicity and renewability and its high power density.

Development of efficient catalysts for ethanol oxidation that break C–C bond and produce CO2 has attracted great attention and represents one of the major challenges in electrocatalysis. The use of metal oxides such as CeO2, SnO2 and TiO2 are interesting alternative to the usual C-based supports because they exhibit a longer stability [1]. In comparison to acid media, the kinetics of ethanol oxidation is higher in alkaline solution. Although Pd can replace successfully Pt the electrooxidation is not complete leading to acetate and acetaldehyde instead of CO2. It is therefore necessary to improve the catalyst to break the C–C bond at low overpotentials. Thus novel approaches to promote Pd activity towards complete ethanol oxidation are needed. In a previous work [2], we have investigated the electrocatalytic properties of Pd particles grown by Atomic Layer Deposition (ALD) onto anodic TiO2 nanotubes (TiO2-nt). Such Pd/TiO2-nt systems have exhibited a high and stable electro-activity in alkaline medium. The influence of the TiO2-nt crystalline structure on the catalyst activity demonstrated the strong metal-support interaction. Since SnO2 is also known to promote ethanol oxidation over Pd in alkaline media, ALD has been used to uniformly coat the

TiO2-nt with SnO2. The comparison of the Pd/TiO2-nt and Pd/SnO2/TiO2-nt systems has been performed to assess the influence of the chemical nature of the support on the metallic catalysts without any morphological modifications. The influence of the deposition parameters on the morphology, the crystalline structure and the chemical composition has been investigated by various analytical techniques. It is observed that the catalytic activity of Pd/SnO2/TiO2-nt is stable and significantly higher than Pd/TiO2-nt. It demonstrates, again, the strong influence of the substrate on the activity of metallic nanoparticles and shows that ALD is a powerful tool to synthetize tailored catalytic systems on nanostructured substrates. References [1] Monyoncho, E. A.; Ntais, S.; Brazeau, N. et al., ChemElectroChem 2016, 3, 175 [2] Assaud, L.; Brazeau, N.; Barr, M. K. S.et al., ACS Appl. Mater. Interface, 2015, 7, 24533

89 International Congress Engineering of Advanced Materials ICEAM2017 Session 11 10 - 12 October 2017 Talk 44 Erlangen, Germany

Model based study on the precipitation and ageing of Cu/Zn hydroxycarbonates as methanol catalyst precursor phases

Güldenpfennig A.1,*, M. Hartig1, M. Haderlein1, M. Distaso1 and Peukert W. 1

(1) Institute of Particle Technology (LFG), Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: In situ FTIR, Crystallization kinetics, Avrami equation

Cu/ZnO catalysts for methanol synthesis from syngas are typically prepared by co precipitation of Cu/Zn-hydroxycarbonates with consecutive ageing and calcination of the solid phases. The first preparation steps and phase composition of precursor phases are known to have a crucial influence on the final catalyst properties and performances. In particular, the complex physico-chemical processes occurring during the aging of the solid after precipitation are not understood. Thus, in order to gain knowledge about the ageing kinetics, the reaction suspension was monitored by in situ FTIR spectroscopy and pH measurements using suitable immersible probes. In a first reaction step aqueous solutions of Cu/Zn nitrates were mixed with a sodium carbonate solution inside a T-mixer resulting in an amorphous Cu/Zn-hydroxycabonate precipitate. Upon ageing at elevated temperatures this precursor transforms into crystalline Rosasite

(CuZn)2CO3(OH)2. The evolution of IR-active absorption bands caused by newly formed bonds between the carbonate ion and metal ions was analyzed for different temperatures, carbonate concentrations and pH. In order to obtain kinetic parameters of the phase transformation, the intensity evolution of the characteristic Infrared bands over time was fitted with an extended version of the Avrami equation. It could be shown how both the liquid phase composition and the Cu to Zn ratio in the solid phase influence the ageing kinetics as well as the morphology and crystallinity of the product. An increase of the carbonate concentration accelerates the transformations and results in smaller crystallite sizes. The rate parameter of the Avrami equation obtained at different reaction temperatures was plotted in an Arrhenius plot in order to estimate the activation energy of the reaction. Based on these results the effects of different reaction parameters on Cu/ZnO catalyst precursor phases can be rationalized and help to optimize the synthesis towards a more active catalyst.

Acknowledgments: The authors acknowledge funding from the Deutsche Forschungsgemeinschaft (DFG) through the Cluster of Excellence Engineering of Advanced Materials and Clariant for fruitful discussions and financial support.

90 International Congress Engineering of Advanced Materials ICEAM2017 Session 12 10 - 12 October 2017 Talk 45 Erlangen, Germany

Exploiting optical forces in hollow-core photonic crystal fibre

Zeltner, R. 1,2 *, Xie, S.1, Pennetta, R.1, Bykov, D. 1, Euser, T. G. 3, and Russell, P. St.J. 1,2

(1) Max Planck Institute for the Science of Light, Staudtst.2, Erlangen, Germany (2) Cluster of Excellence Engineering of Advanced Materials, University of Erlangen-Nuremberg, Staudtst.2, Erlangen, Germany (3) University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom

*e-mail: [email protected]

Keywords: waveguides, irradiation sensing, optical forces Hollow-core photonic crystal fibre (HC-PCF) confine light over long path lengths inside a hollow-core by means of a photonic cladding. The possibility to infiltrate the core with a liquid specimen makes them a potent platform for photochemistry, spectroscopy [1] and long range optical manipulation [2] in liquid environments. Here, we demonstrate an irradiation sensor which is based on a fluorescent microparticle optically trapped and propelled inside the core of a HC-PCF [3]. Furthermore, we present a new way of light delivery to HC-PCF [4]. It is based on a fused silica “nanospike” inserted into the core of the HC-PCF and offers the unique feature of optomechanical self-aligning. A strong trapping laser can be used to align the coupling of a weak broadband signal, making the system perfectly suited for spectroscopic sensing applications inside HC-PCF.

Figure 1: (a) A fluorescent microparticle optically trapped inside the core of a HC-PCF can be used as an irradiation sensor. Emitted fluorescence couples to the fibre modes and is read out at the fibre end. (b) A nanospike optically trapped inside the core of a HC-PCF enables broadband coupling to HC-PCF. The nanospike is fabricated by tapering a single-mode fibre down to a final tip diameter of ~ 350 nm.

References [1] Cubillas, A., et al., Chem. Soc. Rev., 2013, 42, 8629-8648. [2] Garbos, M.K., et al., Opt. Express, 2011, 19 (20), 19643-19652 [3] Zeltner, R., et al., Appl. Phys. Lett., 2016, 108. [4] Zeltner, R., et al., ACS Photonic, 2017, 4 (2), 378-383.

91 International Congress Engineering of Advanced Materials ICEAM2017 Session 12 10 - 12 October 2017 Talk 46 Erlangen, Germany

Functional superparamagnetic supraparticles: From magnetic nanoparticles to lightweight powders and optically interactive dispersions

Karl Mandel1,2,*

(1) Fraunhofer Institute for Silicate Research ISC, Neunerplatz 2, 97082 Wuerzburg, Germany. (2) Department of Chemical Technology of Materials Synthesis, University of Wuerzburg, Roentgenring 11, 97070 Wuerzburg, Germany.

*e-mail: [email protected]

Keywords: supraparticles, magnetic particles, superparamagnetism

In the recent years, the art of synthesising and tailoring nanoparticles with distinct properties has attracted tremendous interest and has been explored very well. The next step further is to consider these particles as nano-building blocks which shall be combined bottom-up, to form again particles, but now complex, nanostructured particles, so called supraparticles. The aim is to achieve novel functional particles with interactive properties that can only be obtained from the smart assembly of nano-building blocks to combined entities. In this talk, two examples of such complex particle entities using nano iron oxides with superparamagnetic properties as building blocks will be shown. The first example is about the formation of hollow microballoons derived from superparamagnetic iron oxide nanoparticles with silica patches. Using patchy iron oxide nanoparticles is the key towards being able to create hollow micron sized entities which evolve from a lifelike Pickering-emulsion process. Ultimately, it is possible to obtain a magnetically steerable particle system with a density of less than 0.2 g·cm-3.[1] The second example is about a smart optical composite material with isotropic and anisotropic optical properties by combination of luminescence and high reflectivity which enables switching between both depending on an applied wavelength of light. The composite is formed as anisotropic core/shell particles by coating superparamagnetic iron oxide-silica microrods with a layer of the luminescent metal-organic framework and can be rotated by an external magnet. The integration and control of light emission modes within a homogeneous particle dispersion marks a new type of smart optical material, addressing fundamentally new directions for research on switchable multifunctional materials.[2]

References [1] Tim Granath, Angela Sanchez-Sanchez, Aleksey Shemliov, Valeria Nicolosi, Vanessa Fierro, Alain Celzard, Karl Mandel, ACS Nano 2016 10, 10347−10356 [2] Karl Mandel, Tim Granath, Tobias Wehner, Marcel Rey, Werner Stracke, Nicolas Vogel, Gerhard Sextl, Klaus Müller-Buschbaum, ACS Nano 2017 11, 779-787

92 International Congress Engineering of Advanced Materials ICEAM2017 Session 12 10 - 12 October 2017 Talk 47 Erlangen, Germany

Integrating plasmonic materials within core-shell nanowires: an electrochemical approach

Bourret, G.;1,* Ozel, T.;2 and Mirkin, C.

(1) Department of Chemistry and Physics of Materials, Paris-Lodron University of Salzburg, Jakob Haringer Strasse 2A, 5020 Salzburg, Austria (2) Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, USA

*e-mail: [email protected]

Keywords: nanowires, plasmonics, templated synthesis The optical and electrical properties of heterogeneous nanowires are profoundly related to their composition and nanoscale architecture. However, the intrinsic constraints of conventional synthetic and lithographic techniques have limited the types of multi-compositional nanowires that can be created and studied in the laboratory. Our recent progress in templated syntheses based on electrodeposition within porous membranes will be briefly discussed in the context of plasmonics.[1-4] In particular, we report a high-throughput technique that can be used to prepare coaxial nanowires with sub-10 nm control over the architectural parameters in both axial and radial dimensions. The method, which is termed coaxial lithography (COAL),[4] relies on templated electrochemical synthesis and can be used to create coaxial nanowires composed of combinations of metals, metal oxides, metal chalcogenides, and conjugated polymers. The optoelectronic properties of a plasmonic nanoring embedded hybrid core-shell semiconductor nanowire were studied. This demonstrates the potential of this new synthetic technique to radically change nanowire fabrication.

Figure 1: Coaxial lithography.[4] References [1] G. R. Bourret, T. Ozel, M. Blaber, C. Shade, G. C. Schatz and C. A. Mirkin Nano Lett. 2013, 13, 2270 [2] K. D. Osberg, M. Rycenga, G. R. Bourret, K. Brown and C. A. Mirkin Adv. Mater. 2012, 24, 6065 [3] T. Ozel, G. R. Bourret, A. Schmucker, K. Brown and C. A. Mirkin Adv. Mater. 2013, 25, 4515 [4] T. Ozel, G. R. Bourret and C. A. Mirkin Nature Nanotech. 2015, 10, 319

93 International Congress Engineering of Advanced Materials ICEAM2017 Session 12 10 - 12 October 2017 Talk 48 Erlangen, Germany

Looking for Synergies in Molecular Plasmonics by Hybrid Functional Nanostructures

1,2,* Tobias A.F. König

(1) Leibniz-Institut für Polymerforschung Dresden e.V., Institute of Physical Chemistry and Polymer Physics, Hohe Str. 6, 01069 Dresden (2) Cluster of Excellence Centre for Advancing Electronics Dresden (CFAED), Technische Universität Dresden, 01062 Dresden, Germany

*e-mail: [email protected]

Keywords: plasmonics, self-assembly, macroscopic

For the next generation of optical devices, the possibility of cost-efficient manufacturing requires both tailored control of the nanoparticle building blocks as well as an up-scaleable self-assembly method for macroscopic areas. We address these demands using bottom-up directed self-assembly of plasmonic nanoparticles to achieve collective plasmonic resonances in high quality plasmonic modes.[1] A first step toward these tailored modes are the controlled synthesis of the plasmonic building blocks with specific mintage materials (gold or silver), subwavelength dimensions and morphologies with less symmetry axis (cubic shape). For instance, we have recently been able to fabricate core shell nanoparticles with a specific dielectric spacer for controlled electric field enhancement.[2] As a second step, we use a directed self-assembly technique to align these building blocks to achieve collective plasmonic excitations such as constructive interference between plasmonic and diffraction modes (Fano resonance). Finally, we go one step further and use our directed self-assembly approach to discuss a magnetic metasurface. This magnetic mode could be excited using a plasmonic film coupled nanoparticle system.[3] This extraordinary electric field enhancement opens up new possibilities in ultra-sensitive sensing applications, plasmon-induced charge separations and the tailored control of the electric as well as magnetic field is important for energy conversion, super-absorber and metamaterial applications.

References [1] Nano Lett. 2014, 14, 6863. [2] J. Phys. Chem. C 2015, 119, 9513; Nanoscale 2017, accepted [3] Faraday Discuss., 2016, 191, 159.

94 International Congress Engineering of Advanced Materials ICEAM2017 Session 13 10 - 12 October 2017 Talk 49 Erlangen, Germany

Thin water films as reactive interfaces for nanomaterials growth

Diwald, O.1,*, Gheisi, A. R.2, Thomele, D.1, and Bernardi, J.3

(1) Department of Chemistry and Physics of Materials, University of Salzburg, Jakob-Haringer-Strasse 2a, A-5020 Salzburg (2) Department of Chemical and Bioengineering, Friedrich-Alexander Universität Erlangen-Nürnberg, Cauerstrasse 4, D-91058, Erlangen (3) University Service Center for Transmission Electron Microscopy, Vienna University of Technology, Wiedner Hauptstrasse 8-10, A-1040, Vienna

*e-mail: [email protected]

Keywords: oxide nanomaterials, non-equilibrium solids, ambient conditions, dissolution, recrystallization

Thin films of water covering metal oxide nanoparticles can give rise to the spontaneous and spatially controllable growth of hydroxide fibers in the ambient. Knowledge about the nature of the reactive interfaces and the underlying formation mechanisms is key to the rational development of metal oxide nanomaterials and associated microstructures. We used silicon tetrachloride as a water free chlorine ion source for the surface functionalization of MgO nanocubes and explored their subsequent transformation into magnesium oxychloride fibers upon contact with water. Specifically, we report on the reactivity of MgO nanocubes and cubes towards water inside the colloidal dispersion or from the gas phase [1] and show how the functionalization process and material dispersion determine the reaction pathway that can lead to very different types of hydroxides.[2] Lessons to be learned from this unique route to utilize reactive interfaces of oxide nanomaterials under ambient conditions can be applied to a variety of microstructural evolution processes[3] that involve high surface area materials and superficial and condensed water acting both as a reactant and as a reaction medium.

References [1] Baumann S.-O. et al. Langmuir, 2015, 31, 2770-2776. [2] Gheisi A. et al. RSC Adv., 2015, 5, 82564-82569 [3] Thomele D. et al. Angew. Chem. Int. Ed., 2017, 56, 1407-1410.

95 International Congress Engineering of Advanced Materials ICEAM2017 Session 13 10 - 12 October 2017 Talk 50 Erlangen, Germany

Nonlinear optics at interfaces

Dinkel, R.;1,* Meltzer, C.; 1 Engelhardt, K.; 1 Braunschweig, B.;2 Peukert, W. 1,3

(1) Institute of Particle Technology (LFG), Friedrich-Alexander University Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany (2) Institute of Physical Chemistry, Westfälische Wilhelms-Universität Münster, Correnstraße 28/30, 48149 Münster, Germany (3) Cluster of Excellence – Engineering of Advanced Material (EAM), Friedrich-Alexander University Erlangen-Nürnberg (FAU), Nägelsbachstraße 49b, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: nonlinear optics, interfaces, nanoparticles, ligand exchange, self-assembled monolayers

The in situ characterization of interfaces is of vital importance in order to understand and control processes and properties that arise at and from the interface. Nonlinear optical methods such as second-harmonic scattering (SHS) and sum-frequency generation (SFG) have been shown to be powerful tools for studying buried interfaces in situ and in real-time as both methods are inherently sensitive to the surface. Nonlinear optical techniques were applied for molecular layers at solid/liquid and air/liquid interfaces. For self-assembled monolayers (SAM), SFG is able to provide information about surface coverage and conformational order of the SAM. In combination with molecular dynamics (MD) simulations it was shown that the initial SAM is of low order due to inverted adsorption of molecules. However, these defects were found to be healed upon dewetting as a quasi-Langmuir Blodgett transfer took place which led to a significant increase in order and quality of the SAM.1 Moreover, SFG studies of proteins at the air/water interface gave insights into the molecular structure of the protein which determines the stability of the protein foam. The molecular protein structure has also been shown to depend on pH and added salt which in turn suggests how more stable foams can be achieved.2 Our group used SHS to study molecular effects at colloidal interfaces including polyelectrolyte brushes, titanate nanowires, gold nanoshells and amphoteric particles. Recently, we used SHS to study ligand exchange at the surface of colloidal gold and silver nanoparticles in situ.3,4 Upon adsorption of an optically transparent thiol the SHS intensity decreased as surface electrons were localized and the second-order polarization was reduced. The SHS intensity decrease was then correlated with the surface coverage of thiol which allowed for the determination of the Gibbs free energy of adsorption and the surface coverage. Furthermore, a two-step adsorption model was proposed on the basis of the kinetics of the ligand exchange reaction. This talk aims to give an overview of the possibilities of nonlinear optics at interfaces and go into detail about ligand exchange studies at nanoparticles. References [1] Meltzer, C.; Dietrich, H.; Zahn, D.; Peukert, W.; Braunschweig. B. Langmuir 2015 31, 4678−4685. [2] Engelhardt, K.; Lexis, M.; Gochev, G.; Konnerth, C.; Miller, R.; Willenbacher, N.; Peukert, W.; Braunschweig, B. Langmuir 2013 29, 11646−11655. [3] Dinkel, R.; Braunschweig, B.; Peukert, W. J. Phys. Chem. C 2016 120, 1673−1682. [4] Dinkel, R.; Braunschweig, B.; Peukert, W. J. Phys.: Condens. Matter 2017 29, 133002.

96 International Congress Engineering of Advanced Materials ICEAM2017 Session 13 10 - 12 October 2017 Talk 51 Erlangen, Germany

Atomic Layer Deposition from Dissolved Precursors Döhler, D.1*; Wu, Y. 1; Liu, X.1; Barr, M.2; Fichtner, J.1; Santinacci, L.2 and Bachmann, J.1

(1) Department of Chemistry and Pharmacy, Friedrich-Alexander University of Erlangen-Nürnberg, Egerlandstrasse 1, D−91058 Erlangen, Germany (2) CNRS, CINaM UMR 7325, Aix Marseille Université, F−13288 Marseille, France

*e-mail: [email protected]

Keywords: Atomic layer deposition, LBL, SILAR, thin films, magnesium oxide, microfluidic

We establish a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD) known with gaseous precursors toward precursors dissolved in a liquid. We prove the self-limiting growth of various solid thin films by novel “solution ALD” (sALD) reactions. sALD allows us to use new precursors, such as Grignard reagents, which are not accessible in “gas ALD” process, due to stability issues or a very low vapor pressure. We now focusing on new reactions to deposit films of organic or ionic nature, which could be used for photovoltaic devices. The films deposited are characterized by spectroscopic ellipsometry, diffuse optical absorption spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and infrared spectroscopy. sALD paves the way to new thin film chemistry with non-volatile or thermally unstable precursors.

Figure 1: Principle view of the sALD setup.

References [1] Wu, Y.; Döhler, D.; Barr, M.; Oks, E.; Wolf, M.; Santinacci, L.; Bachmann, J. Nano Lett. 2015 15 (10) pp 6379–6385

97 International Congress Engineering of Advanced Materials ICEAM2017 Session 13 10 - 12 October 2017 Talk 52 Erlangen, Germany

Supramolecular Organic-Inorganic Hybrid Materials

Krieger, A.1, Bernhardt, S.1 and Gröhn, F.1,*

(1) Department Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3

*[email protected]

Keywords: self-assembly, hybrid nanomaterial, solar energy conversion

Inspired by nature, self-assembly is used as a bottom up approach to design new well-defined nanomaterials in solution. Organic molecules like surfactants or macromolecules are combined with inorganic precursor molecules. Organic and inorganic materials interact by non-covalent forces like electrostatic interaction, π-π or hydrophobic and hydrophilic interactions and form supramolecular structures. By taking advantage of different chemical properties and geometric effects the shape and size of the organic-inorganic hybrid materials can be controlled in the synthesis. Structures with improved and tunable photocatalytic properties result due to complementary effects of the organic and the inorganic components in terms of morphology control and light absorbance. Novel self-assembled structures promising as photoactive and stable materials for solar energy conversion will be presented. The structure of the organic-inorganic materials is studied by light scattering, spectroscopy and microscopic techniques including AFM, SEM and TEM. Perovskite capped with surfactants and zinc oxide wrapped with functional molecules are shown, which demonstrate the possibilities to tailor the properties by self-assembly. Upon irradiation with visible light these assemblies can be used as photocatalysts without adding any further photosensitizer.

Figure 1: Morphology control through self-assembly formation of organic-inorganic hybrid materials.

98 International Congress Engineering of Advanced Materials ICEAM2017 Session 14 10 - 12 October 2017 Talk 53 Erlangen, Germany

Towards hybrids: adsorption, ordering and metalation of porphyrins on MgO nanocube surfaces Schneider J.1,*, Kollhoff F.2, Schindler T.3, Bichlmaier S.1, Bernardi J.4, Unruh T.3, Libuda J.2, Berger T.1, Diwald O.1 (1) Chemistry and Physics of Materials, Paris Lodron University of Salzburg, Jakob-Haringer-Straße 2a, A-5020 Salzburg, Austria (2) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany (3) Lehrstuhl für Kristallografie und Strukturphysik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Staudtstraße 3, D-91058 Erlangen, Germany (4) University Service Center for Transmission Electron Microscopy, Vienna University of Technology, Wiedner Hauptstrasse 8-10, A-1040 Vienna, Austria

*e-mail: [email protected]

Keywords: hybrid materials, porphyrins, adsorption and ordering

The efficient functionalization of metal oxide nanostructures with organic and metal-organic dyes is a prerequisite to realize hybrid materials for photosensitization, for electrochemical sensors or for molecular switches. Unsupported nanoparticles typically exist in form of agglomerates and porous particle networks. As such, they provide surfaces and interfaces in all three dimensions and proximity effects may come into play during the adsorption of functional molecules. The associated complexity represents a major challenge for the rational optimization of functional interfaces in hybrids. On MgO nanocubes as model systems for adsorption studies we compared the adsorption behavior of the free base porphyrins without any linker group (TPP) with those having four carboxylic linker groups (TCPP). Without any linker group the TPP binds flat-lying on the MgO surface via metalation of the porphyrin center1 whereas the TCPP attaches via its carboxyl groups. The saturation for the flat-lying adsorption process is reached at approximately one monolayer, but is surpassed when TCPP adsorbs via its carboxyl groups pointing to an upright standing adsorption geometry. This allows for much higher coverages and suppresses the metalation reaction. Molecular spectroscopy studies (Diffuse Reflectance UV/Vis and FT-IR spectroscopy) are perfectly consistent with the conclusions from SAXS data analysis indicating a shell formation consisting of upright standing TCPP molecules on the MgO surface2. In this presentation we will discuss the influence of different adsorption geometries as well as the consecutive surface reactions and shell formation upon porphyrin adsorption.

References [1] Schneider, J.; Kollhoff, F.; Bernardi, J.; Kaftan, A.; Libuda, J.; Berger, T.; Laurin, M.; Diwald, O. ACS Applied. Materials and Interfaces 2015 7, 22962–22969. [2] Schneider, J.; Kollhoff, F.; Schindler, T.; Bichlmaier, S.; Bernardi, J.; Unruh, T.; Libuda, J.; Berger, T.; Diwald O. J. Phys. Chem. C 2016 120, 26879-26888

99 International Congress Engineering of Advanced Materials ICEAM2017 Session 14 10 - 12 October 2017 Talk 54 Erlangen, Germany

Thin films and their interfaces seen by x-ray techniques

Will, J. 1,*, H o u, Y. 2, Pfnür, A. 1, Lossin, F. 1, Brabec, C. 2 and Unruh, T.1

(1) Chair for Crystallography and Structural Physics, University of Erlangen-Nürnberg, Staudtstr.3, 91058 Erlangen, Germany. (2) Institute of Materials for Electronics and Energy Technology (I-MEET), University of Erlangen-Nürnberg, Martensstr. 7, 91058 Erlangen, Germany. *e-mail: [email protected]

Keywords: thin films, x-ray scattering, self-assembled monolayers, liquid anti-solvent precipitation Thin films and their interfaces were investigated by means of surface sensitive X-ray diffraction. The results were in part obtained by synchrotron radiation and in part by a newly acquired Rigaku 9kW Smartlab diffractometer (see Fig. 1 left), which was founded by EAM and is optimized for thin film characterization. Results of three different samples systems will be presented. First, we investigated ~40nm thick and highly oriented MAPbI3 films (see Fig. 1 right) and their interface in contact with different electron transporting layers (ETL). X-ray reflectivity reveals an only ~1 nm thick interface between the perovskite and the ETL. Moreover we were able to change the chemical composition of this interface by functionalizing the ETL by a self-assembled monolayer (SAM) [1]. These results are interpreted with respect to one of the mayor issues of hybrid organohalide perovskites, which is j-V hysteresis leading to a new level of understanding of this issue. Second, we utilized Octadecyltrichlorosilane (OTS) SAMs on top of Si as mimic for the surface of organic nanoparticles (NPs) fabricated by liquid anti-solvent precipitation (LAS). A clear layering of solvent and water close to the OTS interface was observed, which changes as function of the choice of the solvent (e.g. ethanol, acetone), as well as the concentration of the solvent. Experiments focusing on the interaction of those layers during a subsequent addition of typical ionic and steric surfactants are in preparation. Third, the formation of porphyrin SAMs on top of TiO2 was monitored as function of the porphyrin concentration and the chemical composition of the porphyrin. Distinct differences in the SAM coverage and structure as function of porphyrin concentration in an ethanolic solution were recorded. Moreover, we observed a strong influence of the porphin metallization as well as of the number of functional groups on the SAM structure.

Figure 1: Left: New state-of-the art thin film diffractometer funded by EAM and DFG. Right: Example

of a 2d thin film powder diffractogram of a ~40 nm thick and highly oriented MAPbI3 film. References [1] Will, J.; Hou, Y, Scheiner, S., Pinkert, U., Hirsch, A., Halik, M., Brabec, C., Unruh, T., ESS. 2017 (submitted)

100 International Congress Engineering of Advanced Materials ICEAM2017 Session 14 10 - 12 October 2017 Talk 55 Erlangen, Germany

STEM-EDS imaging of in situ cation exchange at solid state between diverse nanoparticles populations: how it works

Andrea Falqui 1,*, Alberto Casu 1 and Davide Deiana 2

(1) King Abdullah University of Science and Technology (KAUST), Biological and Environmental Sciences and Engineering (BESE) Divisin, NABLA Lab, 23955-6900 Thuwal, Saudi Arabia (2) Centre Interdisciplinaire de Microscopie Electronique (CIME), Ecole Polytechnique de Lausanne (EPFL), 1015 Ecublens, Lausanne, Switzerland

*e-mail: [email protected]

Keywords: in situ STEM-EDS, cation exchange, nanoparticles

A cation exchange (CE) reaction occurs whenever a cationic species in a crystalline structure is partially or completely replaced, leaving the anionic lattice unmodified. CE is usually performed as a fast reaction occurring in liquid between inorganic colloidal nanoparticles (NPs) and cationic species, but the liquid environment and the fast reaction kinetics hinder the possibility of direct imaging of the process. In the recent past we showed that in situ TEM/STEM approach at solid state gives a way to overcome these limitations. [1] In fact, when heated, spherical

Cu2Se NPs having cubic crystalline phase expel free Cu species, forming Cu-vacancies in the cation sublattice with subsequent variations in their stoichiometry (to about Cu1.8Se). Such a thermally-driven expulsion of free Cu species can be exploited to perform in situ CE reactions at solid state between the cubic Cu2Se NCs and CdSe nanowires (NWs) deposited on a common heated substrate. When reached by the free Cu species, CdSe NWs suffer a pervasive chemical and structural transformation, revealing the substitution of Cd species with Cu. As a consequence, Cu2Se constitutes the final, completely substituted NWs. However, while in the past we showed how this phenomenon occurs at 400ºC when the starting CdSe NWs have hexagonal crystalline phase, here we show that it could occur even when the NWs have cubic phase, being in such a case the activation temperature lowered down to about 200ºC. This means that this temperature, acting as a threshold for CE, is strongly dependent on the crystalline phase of the CdSe acceptor nanostructures: in the case of CE occurring to hexagonal CdSe NWs, due to the fact that the hexagonalcubic phase requires more energy to be completed, the activation temperature is higher, as well. Moreover, further insights were found by further studying via in situ STEM-EDS this phenomenon: first, the free copper, before entering the CdSe NWs and then giving rise to the CE reaction, surrounds the whole wires; second, it moves along the NWs’ axis with different speeds in the two opposite directions (Figure 1). Then, the application of the in situ STEM heating approach, combined with the slower kinetics of solid state CE reactions, allows to direct image the transient states leading to the final products of CE, which conversely would be the only observable step in the same CE reactions occurring in liquid state.

101 International Congress Engineering of Advanced Materials ICEAM2017 Session 14 10 - 12 October 2017 Talk 55 Erlangen, Germany

Figure 1: Solid State CE reaction between Cu2Se NPs and CdSe NWs having cubic crystalline phase, monitored at increasing temperature by in situ STEM-EDS maps (red color: copper; green color: cadmium). The copper proceeds inside the NWs following their axis, with different speeds in the two opposite directions.

References [1] A. Casu et al., ACS Nano 2016 10 (2), 2406-2414.

102 International Congress Engineering of Advanced Materials ICEAM2017 Session 14 10 - 12 October 2017 Talk 56 Erlangen, Germany

Atom Probe Tomography of Interfaces in Functional Nanomaterials

Johnson, K1, Josten, J1, Eder, K2, Cairney, J 2 and Felfer, P1,*

(1) Institute for General Materials Properties, Department of Materials Science, Friedrich-Alexander Universität Erlangen-Nürnberg, Martensstraße 5, D-91058, Germany. (2) Australian Centre for Microscopy and Microanalysis, The Univeristy of Sydney, Madsen Building F09, NSW 2006, Australia.

*e-mail: [email protected]

Keywords: Atom probe tomography, Microscopy, Field Ion Microscopy, Interfaces Atom Probe Tomography (APT) is an single atom mass spectrometry method where atomic resolution in 3D is achievable. Through the mass spectrometry principle, it is possible to detect both light and heavy elements potentially making APT an ideal tool for the analysis of functional nanomaterials such as optically active materials and catalysts [1]. However, the operational principle of the atom probe demands the sample to be in the form of a sharp needle with a tip radius smaller than 100 nm that is also able to withstand the mechanical stresses imposed by the high electric fields used. This poses great challenges to the experimentalist seeking to investigate such materials. In the past few years we have therefore developed schemes to transform nanostructured materials into field emitters suitable for APT analysis [2]. These schemes include the attachment of nanoparticles to pre-shaped field emitters, the inclusion of particles into thin films which are then crafted to APT samples using focused ion beam and filling of pores in nanoporous materials using electrochemnistry [3]. In this talk we will present results on the resulting analysis of interfaces and surfaces in functional nanomaterials such as nanoporous gold particles as well as results on catalytic experiments on tip surfaces.

Figure 1: Extraction method for nanoporous particles. (a) Peel-off of particles, (b) Backside of peeled Au film, (c) Backside after electrochemical deposition of Cu. References [1] K. Tedsree et al., Nat Nano 2011, 6, 302-307. [2] P. Felfer et al., Ultramicroscopy 2015, 159, 413-419. [3] A. El-Zoka et al., Mater. Charact. 2017, 128, 269-277.

103 International Congress Engineering of Advanced Materials ICEAM2017 Session 15 10 - 12 October 2017 Talk 57 Erlangen, Germany

Zeolitic Materials with Hierarchical Porosity: Synthesis pathways and Applications

Schwieger, W.1,*, Machoke, A.1, Weißenberger, T.1, Hartmann, M.2, Inayat,A.1

(1) Institute of Chemical Reaction Engineering, and (2) Erlangen Catalysis Resource Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3

*e-mail: [email protected]

Keywords: Hierarchy, Zeolites, Catalytic Properties

Hierarchy is an essential property of the nature. Natural systems like our lungs, the circulatory system and even bones are hierarchically structured. Moreover, hierarchical principles are found in ecological, social and technical systems. Many materials derive their function through a hierarchical organization of their structural elements. Today, porous materials also benefit from specifically designed hierarchically ordered porosity. In this vein, hierarchically-ordered structures are becoming increasingly important especially in relation to optimizing transport phenomena in technical processes involving a catalytic reaction. Thus, hierarchical zeolites do not only offer the possibility of reducing mass transfer limitations, but they also allow the catalytic conversion of large molecules using the advantages of the zeolite surfaces. Thus, introducing additional pores with an optimal size and specific surface properties is very crucial in the preparation of hierarchical zeolites. This will minimize the mass transport limitations and simultaneously prevent the formation of unwanted bulky products. Therefore, novel synthesis routes are required to prepare hierarchical zeolites with tunable porosity. In the first part such preparation pathways will be described, classified and compared [1]. In the second part of this talk, recent advances in the synthesis of hierarchical materials of two catalytically important zeolites, the MFI and FAU type zeolites, will be summarized and discussed. The effect of different experimental conditions like the influence of silica and aluminum source as well as the kind and the content of heteroatoms like aluminum or boron in tuning the textural will be in the focus of the talk. Thus, the syntheses under static and tumbling conditions of nanosheet assemblies of MFI type zeolites with Si/Al ratios of 25 to infinity [2] and the influence of different synthesis parameters like the content of the heteroatoms, alkalinity and aluminum source have be studied [2]. Furthermore, for the layered like FAU-type zeolites, synthesis pathways using different additives, organic and inorganic ones, and the impact of such addition on their morphology and porosity of the finally formed plate-like crystals and aggregates will be discussed [4]. References [1] W.Schwieger, A.G.Machoke, T.Weissenberger, A.Inayat, T.Selvam, M.Klumpp, A.Inayat, Chem. Soc. Rev., 2016, 45, 3353 [2] A.G. Machoke, I.Y. Knoke, S. Lopez-Orozco, M. Schmiele, T. Selvam, V.R.R. Marthala, E. Spiecker, T. Unruh, M. Hartmann, W. Schwieger, Microporous Mesoporous Mater. 190 (2014) 324. [3] A. Inayat, C. Schneider, W. Schwieger; ChemComm, 51 (2015) 279

104 International Congress Engineering of Advanced Materials ICEAM2017 Session 15 10 - 12 October 2017 Talk 58 Erlangen, Germany

Synthesis and characterization of hierarchical micro/macroporous MFI type zeolites

Weissenberger T.1*, Machoke A.1, Inayat A.1, Winter B.2, Spiecker E.2, Schwieger W. 1

(1) Chair of Chemical Reaction Engineering, University of Erlangen-Nuremberg, Egerlandstr. 3, 91058 Erlangen, Germany (2) Center for Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nuremberg, Erlangen, Germany

*[email protected]

Hierarchical zeolites, zeolites, catalysis, macroporous, TS-1, ZSM-5 Zeolite catalysts often suffer from mass transport limitation caused by the slow diffusion of educts and products in the micropores. A possibility to overcome this limitation is the utilization of zeolites with hierarchical pore structure. Due to the additional porosity, hierarchical structured zeolites exhibit a shorter characteristic diffusion path in the micropores and high external surface area. While the preparation and catalytic properties of hierarchical micro/mesoporous zeolites have been studied widely, utilization of micro/macroporous zeolites is still limited due to the lack of simple methods to create additional macropores in zeolites [1]. This contribution introduces a synthesis route for zeolite single crystals with additional intracrystalline macropores. The synthesis route consists of three-steps: synthesis of mesoporous silica particles (MSPs), impregnation with tetrapropylammonium hydroxide (TPAOH) solution and steam assisted crystallization (SAC) [2]. Figure 1. shows characterization data of the synthesized hierarchical micro/macroporous ZSM-5 (left) and titanium silicalite-1 (right). The SEM images (figure 1 a), d)) show crystals with additional macropores with diameters of 150 to 250 nm for ZSM-5 and 350 to 450 nm for TS-1, respectively. The TEM images shown in figure 1 c) and f) reveal the presence of macropores inside the zeolite crystals.

Figure 1: a) b) c) SEM image, powder XRD pattern and TEM image of hierarchical ZSM-5, d) e) f) SEM image, powder XRD pattern and TEM image of hierarchical TS-1 References [1] W. Schwieger, A. G. Machoke, T. Weissenberger, A. Inayat, T. Selvam, M. Klumpp and A. Inayat, Chem Soc Rev., 2016, 45, 3353-3376 [2] A. G. Machoke, A. M. Beltrán, A. Inayat, B. Winter, T. Weissenberger, N. Kruse, R. Güttel, E. Spiecker, W. Schwieger, Adv. Mater., 2015, 27, 1066

105 International Congress Engineering of Advanced Materials ICEAM2017 Session 15 10 - 12 October 2017 Talk 59 Erlangen, Germany

Thermal dewetting of Pt on anodic TiO2 nanotubes shows dramatically enhanced photocatalytic H2 generation with minimal co-catalyst amounts

Nguyen, N. T.;1,*, Altomare, M.;1 and Schmuki, P. 1,2

(1) Institute of Surface Science and Corrosion LKO-WW4, Department of Materials Science and Engineering, University of Erlangen-Nuremberg, Martensstraße 7, Erlangen D-91058, Germany (2) Chemistry Department, Faculty of Sciences, King Abdulaziz University, 80203 Jeddah, Saudi Arabia

*e-mail: [email protected]

Keywords: TiO2 nanotubes, dewetting, photocatalytic H2 generation

In the last decades TiO2 has received large attention due to its ability to “photocatalytically” split H2O into H2 and O2 [1]. Under “open-circuit” conditions, noble metal-modified (mainly Pt)

TiO2 is needed for H2 photo-generation. Not only the presence but also the size, amount and distribution of the noble metal particles at the TiO2 surface affect the overall photocatalytic efficiency [2,3]. There are several well explored methods to decorate Pt onto TiO2 nanotubes (NTs), mostly leading to a decoration of the full tube length with nanoparticles. Herein we show a different approach: we decorate by sputter-deposition only the outermost surface of anodic

TiO2 NT layers with very thin Pt films (nominally few nm-thick) [4]. Then, by a controlled thermal treatment, the Pt films are dewetted at the mouth of the tubes into Pt nanoparticles (NPs) that are as small as of 4-5 nm. This site-selective deposition (only at the tubes top) allows for minimizing the amounts of costly noble metal co-catalyst, while leads at the same time to significantly enhanced photocatalytic H2 generation in comparison with tubes that carry Pt NP decorations along their full length (decorated by e.g. photodeposition).

Figure 1: Formation of Pt NP decorations formed by dewetting of a Pt film over the mouths of TiO2 NTs

and b) photocatalytic H2 evolution results. References [1] Lee, K.; Mazare, A.; Schmuki, P. Chem. Rev. 2014 114, 9385. [2] Nguyen, N. T.; Yoo, J.; Altomare, M.; Schmuki, P. Chem. Commun. 2014 50, 9653. [3] Nguyen, N. T.; Altomare, M.; Yoo, J.; Schmuki, P. Adv. Mater. 2015 27, 3208. [4] Nguyen, N. T.; Altomare, M.; Yoo, J.; Taccardi, N.; Schmuki, P. Adv. Energy Mater. 2016 6, 1501926.

106 International Congress Engineering of Advanced Materials ICEAM2017 Session 15 10 - 12 October 2017 Talk 60 Erlangen, Germany

Design, processing and application of metal oxides fabricated in mesocrystalline habits Distaso M.1,*, Apeleo Zubiri B.,2 Inayat A.3, Zhuromskyy O.,4 Klupp Taylor R.,1 Peschel U.,4 Schwieger W. 3, Spiecker E.,2 and Peukert W. 1

(1) Institute of Particle Technology (LFG), Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany (2) Institute of Micro- and Nanostructure Research (WW9) & Center for Nanoanalysis and Electron Microscopy (CENEM), Department of Materials Science and Engineering, FAU Erlangen-Nuremberg, Cauerstraße 6, 91058 Erlangen (Germany); (3) Institute of Chemical Reaction Engineering, FAU Erlangen- Nürnberg, Egerlandstrasse 3, 91058 Erlangen (Germany) (4) Institute of Optics, Information and Photonics, FAU Erlangen-Nuremberg, Haberstrasse 9a, 91058 Erlangen (Germany);

*e-mail: [email protected]

Keywords: Structure-function relationship; electrodynamic simulations, electron tomography, hierarchical structures

Mesocrystals are superstructures comprising nano- or micron-sized primary building blocks sharing a common crystallographic orientation. The combination of different length scales paves the way toward the application of mesocrystals as functional materials, in particular as pigment for their interesting optical properties. In the current contribution the complex interplay between the structure function relationship of the nanocomposite mesocrystalline particles will be described focusing on two material systems, i.e. α-Fe2O3 (hematite) and ZnO, both synthesized in liquid phase in the presence of poly-N-vinyl-pyrrolidone (PVP).1-3 In the first part, it will be shown how the combination of experimental and simulation tools can be used to shed light on the nanocomposite nature and internal organization of primary particles and to explain and predict their extinction properties.1 The post-treatment of these materials gives access to particles with internal porosity that was assessed and quantified by 360 ° Electron Tomography.2 The coordination of PVP on ZnO was ascertained by ATR-FTIR and solid state 13C Nuclear Magnetic Resonance (SS 13C NMR) spectroscopy. The interplay between the hierarchical organization, the inorganic core and the organic matrix is correlated with the excellent UV emission of these particles. Finally, in situ analytical and spectroscopic techniques can be used to shed light on the formation mechanism of these complex systems. This design strategy can be applied to a broad range of material systems. References [1] M. Distaso, O. Zhuromskyy, B. Seemann, L. Pflug, M. Mačković, E. Encina, R. Klupp Taylor, R. Müller, G. Leugering, E. Spiecker, U. Peschel, W. Peukert J. Quant. Spectr. Rad. Transf. 2017, 189, 369. [2] M. Distaso, B. Apeleo Zubiri, A. Mohtasebi, A. Inayat, M. Dudák, P. Kočí, B. Butz, R. Klupp Taylor, W. Schwieger, E. Spiecker, W. Peukert Microp. Mesop. Mater. 2017, 246, 207-214. [3] M. Distaso, G. Bertoni, S. Todisco, S. Marras, V. Gallo, L. Manna, W. Peukert ACS Appl. Mater. Interfaces 2017, 17, 15182-15191.

107 International Congress Engineering of Advanced Materials ICEAM2017 Session 16 10 - 12 October 2017 Talk 61 Erlangen, Germany

Anisotropic self-assembly from isotropic building blocks

Rey M.1,2,*, Law A.3, Buzza M.3 and Vogel N.1,2.

(1) Institute of Particle Technology, Friedrich-Alexander University Erlangen-Nürnberg, Cauerstrasse 4, 91058 Erlangen, Germany (2) Interdisciplinary Center for Functional Particle Systems, Friedrich-Alexander University Erlangen-Nürnberg, Haberstrasse 9a, 91058 Erlangen, Germany (3) Department of Physics and Mathematics, Theory of Condensed Matter Group, The University of Hull, Hull, HU6 7RX, UK

*e-mail: [email protected]

Keywords: Self-assembly, Colloidal lithography,

The ability to control the assembly behavior of colloidal is of fundamental importance for a range of scientific disciplines and applications. At an air/water interface, spherical particles, generally form two-dimensional crystals with hexagonal symmetry [1]. However, theoretical predictions have shown that by introduction of a soft repulsion shoulder to a hard-sphere potential, complex, anisotropic assembly phases can be formed from simple, isotropic colloidal building blocks [2]. Here, we use an in-situ approach to observe the phase diagram of colloids in the presence of soft microgels at the air/water interface of a Langmuir trough equipped with a microscope. We find a rich phase diagram including chain-like and rhombohedral packing (Fig. 1). We discuss the appearance of these phases in terms of a soft repulsion potential induced by the presence of the microgel particles at the air/water interface.

Figure 1. Phase diagram of colloids mixed with microgels observed in situ at the air/water interphase a) compression isotherm b-g) Representative microscopy images taken at the air/water interface: Scale bar corresponds to 10 µm. References [1] N Vogel et al., Soft Matter (2012), 8, p. 4044-4061. [2] E. A. Jagla, Physical Review E (1998), 11, p. 1478-1486 [3] Funding by DFG through the Cluster of Excellence Engineering of Advanced Materials

108 International Congress Engineering of Advanced Materials ICEAM2017 Session 16 10 - 12 October 2017 Talk 62 Erlangen, Germany

Phase Field Crystal Model of Colloidal Quasicrystals

Decker, B.1,*, Schmiedeberg, M.1

(1) Institut für Theoretische Physik 1, Department für Theoretische Physik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Staudtstraße 7, 91052 Erlangen, Germany

*[email protected]

Keywords: Quasicrystal, Phase Field Crystal, Colloid

Phase field crystal models that employ a Swift-Hohenberg-like free energy are widely used to explore periodic pattern formation [1]. Recently, the phase field crystal model has been modified by adding a second preferred length scale such that quasicrystalline structures can be obtained [2,3,4]. Quasicrystals correspond to structures with long-ranged order but no translational symmetry. In addition, we explore another way to realize colloidal quasicrystals: A large variety of complex self-organized structures are observed in systems with patchy colloids. Patchy colloids usually carry attractive sites, such that the interaction depends on their orientation. We construct and explore phase field crystal models in order to study self-assembly of colloidal structures in two and three dimensions where the colloids either interact according to pair interaction potentials with multiple length scales or with patches.

Figure 1: Monomode approximations of quasicrystalline structures. References [1] Elder, K. R. et al.; Phys. Rev. Lett. 2012 88, 245701. [2] Rottler, J. et al.; Phys. Condens. Matter 2012 24, 135002. [3] Achim, C. V. et al.; Phys. Rev. Lett. 2014 112, 255501. [4] Subramanian, P. et al.; Phys. Rev. Lett. 2016 117, 075501.

109 International Congress Engineering of Advanced Materials ICEAM2017 Session 16 10 - 12 October 2017 Talk 63 Erlangen, Germany

Self-assembly and growth of soft quasicrystals

Martinsons, M.1, Decker, B.1, Achim, C.V.2, Sandbrink, M.4, Oğuz, E.C.3, Löwen H.4, and Schmiedeberg, M.1,*

(1) Institute of Theoretical Physics 1, Friedrich-Alexander University Erlangen-Nürnberg, Staudtstr. 7, 91058 Erlangen, Germany (2) Water Research Center for Agriculture and Mining (CRHIAM), University of Concepción, Concepción, Región del Bío Bío, Chile (3) School of Mechanical Engineering and The Sackler Center for Computational Molecular and Materials Science, Tel Aviv University, Tel Aviv 6997801, Israel (4) Institute for Theoretical Physics 2: Soft Matter, Heinrich-Heine University Düsseldorf, Universitätsstr. 1, 40225 Düsseldorf, Germany

*e-mail: [email protected]

Keywords: colloids, quasicrystals

Quasicrystals possess long-ranged order but lack periodicity. They have attracted large attention during the last three decades due to their sophisticated material properties such as low surface friction and high rigidity. By studying colloidal quasicrystals we obtain new insights into the question why only a few rotational symmetries occur in nature [1]. We are especially interested how the pair interaction of colloids has to be tailored in order to achieve the self-assembly of a quasicrystal with a desired symmetry. Furthermore, we study the consequences of the additional degrees of freedom. These so-called phasons correspond to complex rearrangements of the colloids [2] that do not cost free energy in the long-wavelength limit but affect a lot of properties of the quasicrystal. By employing a phase field crystal model we calculate how a quasicrystal grows from a seed and detect two different growth modes, namely defect-free growth and a mode dominated by phasonic flips which are incorporated as local defects into the grown structure [3]. Finally, we explore how the growth started by multiple seeds is affected by the possibility of stress relaxation via the phasonic degrees of freedom.

Fig ure 1: (a) Self-assembled colloidal quasicrystal (Monte-Carlo simulation). (b,c) Phasonic degree of freedom (Figure from [2]). (d,e) Different growth modes of a quasicrystal (Figures from [3]).

References [1] Mikhael, J.; Schmiedeberg, M.; Rausch, S.; Roth, J.; Stark, H.; Bechinger, C. PNAS 2010 107, 7214. [2] Kromer, J.A.; Schmiedeberg, M.; Roth, J.; Stark, H. Phys. Rev. Lett. 2012 108, 218301. [3] Achim, C.V.; Schmiedeberg, M.; Löwen, H. Phys. Rev. Lett. 2014 112, 255501.

110 International Congress Engineering of Advanced Materials ICEAM2017 Session 16 10 - 12 October 2017 Talk 64 Erlangen, Germany

Morphological properties of the epithelial tissue

Lovrić, J.1,2,*, Kaliman, S.2 and Smith, A-S.1,2

(1) Institute Ruđer Bošković, Division of Physical Chemistry, Group for Computational Biosciencies, Bijenička 54, Zagreb, Croatia (2) Institute for Theoretical Physics, PULS Group and Cluster of Excellence: EAM, FAU Erlangen-Nürnberg, Nägelsbachstraße 49b, 91052 Erlangen, Germany

*e-mail: [email protected]

Keywords: tissue modeling, random packings, Voronoi diagram

Properties of packing systems on various interfaces are of vital interest for many reasons like amorphous materials, liquids, 3D printing and in life sciences. We investigate morphology of randomly packed ellipses through whole phase-space of packing fractions and ellipse aspect ratios. Furthermore, we compare properties of random packings to the packings of MDCK II epithelial tissue nuclei on their interfaces. Cell nuclei can be approximated with ellipses and the Voronoi tesselation generated by those ellipses coincides well with the cell membranes. The comparison of tissue cells and random packing is done by studying the probability distributions of chosen morphological measures calculated from the cells. We find that randomly packed ellipses reproduce the morphology of the tissue well at the low cell density. At high cell density we observe more regular structure of the tissue an we see the deviations of the random model from the cell tissue.

Figure 1: Distributions of Voronoi cell area at high cell density. Red line represents randomly packed nuclei and blue line represents real tissue. References [1] S. Kaliman, C. Jayachandran, F. Rehfeld, and A.-S. Smith, Biophysical Journal, 2014, 106, L25-L28. [2] S. Kaliman, C. Jayachandran, F. Rehfeld, and A.-S. Smith, Frontiers in Physiology, 2016, 7, 551.

111 International Congress Engineering of Advanced Materials ICEAM2017 Session 17 10 - 12 October 2017 Talk 65 Erlangen, Germany

Capillary Suspensions – a generic platform for paste formulation and its application for 3D printed porous ceramics with high specific mechanical strength and highly conductive, printable silver pastes

Yüce, C.; Maurath, J.; Willenbacher, N.*

(1) Karlsruhe Institute of Technology (KIT), Institute for Mechanical Process Engineering and

Mechanics, Gotthard-Franz-Str. 3, 76131 Karlsruhe *e-mail: [email protected]

Keywords: capillary suspensions, porous ceramics, silver pastes for printed electronics

Capillary suspensions are three-phase fluids comprising a solid and two immiscible liquid phases. Addition of a small fraction of a second liquid to a suspension of particles leads to the formation of a sample spanning particle network. The resulting particulate gel gains its exceptional strength from the capillary forces inferred from the added secondary liquid, no matter whether it wets the particles better or worse than the primary liquid [1]. This generic concept can be used to stabilize suspensions, tune their flow behavior according to various processing demands, or to provide pre-cursors for highly porous solids with or without sintering [2]. A broad range of innovative materials based on this concept has been developed including novel low-fat food products, biomass slurries with improved stability and gasification properties, pastes for lithium-ion battery electrodes with superior coating and electrochemical properties, or highly conductive, porous graphite membranes. Here we focus on 3D printable ceramic pastes for hierarchically structured cellular porous ceramics with high specific strength and screen-printable silver pastes for front-side metallization of silicon solar cells. We manufactured cellular ceramics with overall porosities up to 88 % that exhibit fully open-porous struts with porosities between 45-60 % and pore sizes < 6 µm. An innovative processing strategy enabled manufacturing of crack-free, undeformed specimen. We printed hexagonal honeycomb structures showing exceptionally high specific strength under compression load. The strength-density range that was covered by sintered capillary suspensions so far was enlarged by about a factor of 2-3. With their high internal surface such 3D printed complex structures may find application in filtration and separation or as catalyst carriers. Silver pastes without non-volatile, organic additives that often deteriorate electrical properties were prepared from just 4 ingredients: silver particles, glass frit, two immiscible, volatile solvents. Yield stress, degree of shear thinning and paste homogeneity could be adjusted to provide long-term stability, continuous defect-free printability and high printing quality. Screen-printing was done at mesh sizes down to 25 µm, cell efficiency and grid resistance of Si solar cells was similar to that achieved with commercial silver pastes at a 25% reduced silver deposit. This novel concept can be easily applied to other systems using inorganic or organic conductive particles and represents a fundamental paradigm change to the formulation of pastes for printed electronics.

References [1] Koos, E.; Willenbacher, N. Science 2011 331, 897-900. [2] Dittmann, J.; Maurath, J.; Bitsch, B.; Willenbacher, N. Advanced Materials 2016 28 (8), 1689-1696.

112 International Congress Engineering of Advanced Materials ICEAM2017 Session 17 10 - 12 October 2017 Talk 66 Erlangen, Germany

Binary Indium-Zinc Oxide based Photoanodes for Dye-Sensitized Solar Cells

Kunzmann A.1*, Costa, R. D.1,3, Stanzel, M.2, Peukert, W.2 and Guldi, D.M.1

(1) Department of Chemistry and Pharmacy & Interdisciplinary Center for Engineering of Advanced Materials (EAM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany (2) Institute of Particle Technology, FAU Erlangen-Nürnberg, Cauerstr. 4, 91058 Erlangen, (3) IMDEA Materials Institute, Eric Kandel 2, 28906 Getafe, Madrid, Spain *e-mail: [email protected]

Keywords: Dye-Sensitized Solar Cells, Indium-Zinc Oxide photoanodes, flame spray pyrolysis

Several groups have demonstrated the benefits of incorporating binary metal-oxide electrodes en-route towards efficient DSSCs.(1-3) The current work aims at realizing efficient indium-zinc-oxide photoanodes by means of enhancing the charge injection and charge transport processes as well as reducing the recombination rates. Electrochemical impedance spectroscopy (EIS) confirms that the presence of indium reduces the charge transport resistance and increases the recombination resistance, resulting in a remarkable enhancement of the charge collection efficiency from 47% to 88% for devices with ZnO and

In0.2Zn0.8O electrodes coated with N719, respectively. As such, the latter reveal higher efficiencies (η) of 4% when compared with 3% for the former. Furthermore, when the dye is exchanged from N719 to porphyrins a further enhancement in the efficiency to 7.3% is realized. The latter constitutes the highest value reported up to date for IZO-based DSSCs and is state of the art for ZnO-based binary DSSCs.

References [1] Hanhong Chen, Aurelien Du Pasquier, Gaurav Saraf, Jian Zhong, Y. Lu, Semicond. Sci. Technol. 2008, 23, 45004. [2]Khalid Mahmood, S. B. Park, J. Mater. Chem. A 2013,1, 4826. [3]Sadia Ameen, Shaheer Akhtar, Hyung-Kee Seo, Young Soon Kim, H. S. Shin, Chem. Eng. J. 2012, 187, 351.

113 International Congress Engineering of Advanced Materials ICEAM2017 Session 17 10 - 12 October 2017 Talk 67 Erlangen, Germany

Functionalized Black Si for Water Photooxidation

M. E. Dufond,1,* M. Diouf, 1 M. K. S. Barr,1 B. Fabre,2 L. Joanny, 2 F. Gouttefangeas,2 L. Santinacci1 and G. Loget2

(1) Aix Marseille Univ, CNRS, CINaM UMR 7325, 13288, Marseille, France. (2) Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS/Université de Rennes 1, MaCSE, Campus de Beaulieu, 35042 Rennes Cedex, France.

*e-mail: [email protected]

Keywords: Porous Silicon, Atomic Layer Deposition, Water splitting

In recent years, a large activity has been focused on water photosplitting in order to store and transport the solar energy as solar fuels [1]. However no cost-effective photoelectrochemical devices have been reported yet. It is therefore required to optimize the photoelectrode performances. In addition to select a suitable and cheap material, it is possible to nanostructure the electrodes as well as to combine different materials to enhance their properties. Although the concept has been initially demonstrated on TiO2 [2], Si has become a highly appealing material for such target because it is an abundant and cheap element and also because its energy band structure is well suited for the solar radiation absorption. Conversely, silicon is not stable under the water photo-splitting conditions, it exhibits a high reflectance and it has a slow reaction kinetics. In the present work, we report a rapid, inexpensive two-step method for structuring n-Si (100) surfaces with micron-sized cavities. The process is based on the photoelectrochemical etching of the Si surface and its subsequent alkaline etching. This method produces a film of random macropores over a large area, which renders the Si surfaces highly antireflective over the visible spectrum: black Si. The structured Si is then conformally coated by a thin TiO2 layer grown by atomic layer deposition (ALD). Such functionalized electrodes can be used as stable photoanodes producing enhanced photocurrents under simulated sunlight with respect to their planar counterparts. These TiO2-protected Si microstructured surfaces were highly stable in strongly alkaline solutions and were used as photoanode for several hours under simulated sunlight. Such photoanodes surfaces showed 50 % photocurrent enhancements and ~ 400 mV negative shift of onset potential without any co-catalysts, demonstrating their high potential for solar energy conversion applications [3].

References [1] Lewis, N. S. and Nocera, D. G. Proc. Natl. Acad. Sci. 2006 103, 15729. [2] A. Fujishima and K. Honda, Nature 1972 238, 37. [3] Santinacci, L.; Diouf, M.; Barr, M.; Fabre, B. et al. ACS Appl. Mater. Interfaces 2016 8, 24810.

114 International Congress Engineering of Advanced Materials ICEAM2017 Session 17 10 - 12 October 2017 Talk 68 Erlangen, Germany

The electronic dynamics in main-chain alternating fullerene and dye oligomers for organic photovoltaics

Puscher, B. M. D.;1,* Dowland, S.;2,3 Stephen, M.;5 Osvet, A.;4 Brabec, C. J.;4 Hiorns, R. C.;5 Egelhaaf, H.-J.;3 Guldi, D. M.1

(1) Department of Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstr. 3, 91058 Erlangen, Germany (2) Institute for Materials Discovery, University College London, 107 Roberts Building, Malet Place, London, WC1E 7JE, United Kingdom (3) Energie Campus Nuremberg, Bavarian Center for Applied Energy Research, Fürther Str. 250, 90429 Nuremberg, Germany (4) Institute of Materials for Electronics and Energy Technology (i-MEET), Friedrich-Alexander-University Erlangen-Nuremberg, Martensstr. 7, 91058 Erlangen, Germany (5) IPREM, Université de Pau et des Pays de l’Adour (UPPA), 2 Avenue Président Angot, 64053 Pau, France

*e-mail: [email protected]

Keywords: organic photovoltaics; diketopyrrolopyrrole (DPP); phenyl-C61-butyric acid methyl ester

(PCBM); fullerene (C60); Transient Absorption Spectroscopy

The electron transfer dynamics in alternating fullerene-chromophore copolymer as main-chain oligomers were studied in femtosecond transient absorption spectroscopy (TAS) to understand and to improve their application as photo-active materials in organic photovoltaics. Our unique approach is based on the small band gap dye diketopyrrolopyrrole (DPP), which was combined in a repeating structure with the strong electron-acceptor C60 as well as its more soluble derivative phenyl-C61-butyric acid methyl ester (PCBM) to yield alternating DPP-C60 and DPP-PCBM macromolecules, respectively.[1] Femtosecond TAS was performed in solution and with films deposited onto glass to determine the kinetics of charge separation and recombination as well as their differences. Kinetics in binary blends of DPP and PCBM involve upon photoexcitation ultrafast energy transfer, charge separation (18-50 ps), partial population of the triplet excited state (800 ps), and charge recombination (0.8-15 ns).[2,3,4] Compared to the binary blends, the alternating DPP-PCBM macromolecules exhibit faster charge-separation (4 ps) and faster triplet excited state formation (100 ps). The relaxation to the ground state was not observed in the TAS on the 7.5 ns time scale due to very long-lived states. This relates to LUMOs, which are extensively delocalized over both moieties, which was corroborated by functional theory studies.[1]

115 International Congress Engineering of Advanced Materials ICEAM2017 Session 17 10 - 12 October 2017 Talk 68 Erlangen, Germany

References [1] Stephen, M.; Dowland, S.; Gregori, A.; Ramanitra, H. H.; Silva, H.S.; Combe, C. M. S.; Bégué, D.; Dagron-Lartigau, C.; Morse, G. E.; Genevičius, K.; Arlauskas, K.; Juška, G.; Distler, A.; Hiorns, R. C. Polym Int. 2017 66, 388-398. [2] Banerji, N.; Wang, M.; Fan, J.; Chesnut, E. S.; Wudl, F.; Moser, J.-E. J. Mater. Chem. 2012 22, 13286-13294. [3] Karsten, B. P.; Bouwer, R. K. M.; Hummelen, J. C.; Williams, R. M.; Janssen, R. A. J. Photochem. Photobiol. Sci. 2010 9, 1055-1065. [4] Ochsmann, J.; Chandran, D.; Gehrig, D. W.; Anwar, H.; Madathil, P. K.; Lee, K.-S.; Laquai, F. Macromol. Rapid Commun. 2015 36, 1122-1128.

116 International Congress Engineering of Advanced Materials ICEAM2017 Session 18 10 - 12 October 2017 Talk 69 Erlangen, Germany

Covalent Immobilization of Glycopeptides and Proteins onto Carbon Nano-onions (CNOs) via Maleimide-Sulfhydryl Ligation

Maffeis, V.1,2,*, Barnes, D.3, Scanlan, E.M.3 and Giordani, S.1

1 Nano Carbon Materials Lab, Istituto Italiano di Tecnologia (IIT), Via Morego 30, 16163 Genova, Italy 2 Department of Chemistry and Industrial Chemistry, University of Genova, Via Dodecaneso 31, 16146 Genova, Italy 3 School of Chemistry and Trinity Biomedical Sciences Institute, Trinity College Dublin, Pearse St, Dublin 2, Ireland

*e-mail: [email protected]

Keywords: Carbon nanomaterials, Bio-conjugation, Protein engineering

Carbon nanomaterials are emerging as smart nanostructures for biomedicine due to the possibility to incorporate multiple functionalities and moieties internally or externally. They can be modified at a precise physicochemical level to optimize targeting in the complex in vivo environment and also engineered for fluorescence detection[1], magnetic resonance imaging[2] and ablation of tumor cells[3]. Herein, we report a robust and versatile synthetic strategy for the modification of carbon nano-onions (CNOs), also known as multi-shell fullerenes, using cysteine as a ligation site for glycopeptide and protein conjugation. The development of novel CNO-glycopeptide/protein conjugates represent a promising platform for the realization of molecular transporters of fully synthetic carbohydrate-based vaccines for immunotherapy due to the large specific surface area and unique optical and electrochemical properties of CNOs. Through the methodology described, these smart nano-materials can envisage the realization of multi stimuli-responsive and dynamic architectures capable of changing their physicochemical behavior upon encountering specific micro-environmental signals becoming relevant for diagnosis, imaging and therapies of specific disease applications.

SH SH S O N O S S O O N N S S Glycopeptide O O Protein S

O N O References [1] Frasconi, M.; Maffeis, V.; Bartelmess, J.; Echegoyen, L.; Giordani, S. Methods Appl. Fluoresc. 2015, 3 (4), 44005. [2] Boncel, S.; Herman, A. P.; Walczak, K. Z. J. Mater. Chem. 2012, 22 (Copyright (C) 2012 American Chemical Society (ACS). All Rights Reserved.), 31–37. [3] Chakravarty, P.; Marches, R.; Zimmerman, N. S.; Swafford, A. D.-E.; Bajaj, P.; Musselman, I. H.; Pantano, P.; Draper, R. K.; Vitetta, E. S. Proc. Natl. Acad. Sci. U. S. A. 2008, 105 (25), 8697–8702.

117 International Congress Engineering of Advanced Materials ICEAM2017 Session 18 10 - 12 October 2017 Talk 70 Erlangen, Germany

Multiparameter flow cytometry as tool to simultaneously monitor cellular nanoparticle uptake and biocompatibility in nanosafety studies

Janko C1,*, Poller J1, Friedrich RP1, Distaso M2,3, Zaloga J1, Unterweger H1, Tietze R1, Peukert W2,3, and Alexiou C1 (1) Department of Otorhinolaryngology, Head and Neck Surgery, Section of Experimental Oncology and Nanomedicine (SEON), Else Kröner-Fresenius-Stiftung-Professorship, Universitätsklinikum Erlangen, Glückstraße 10a, 91054 Erlangen, Germany; (2) Institute of Particle Technology, FAU Erlangen-Nuremberg , Cauerstraße, 4, 91058 Erlangen, Germany; (3) Interdisciplinary Center for Functional Particle Systems, FAU Erlangen-Nuremberg , Haberstraße, 9a, 91058 Erlangen, Germany *e-mail: [email protected] Keywords: nanosafety, flow cytometry, multiparameter stainings, iron oxide nanoparticles Iron oxide nanoparticles have shown great potential in biomedical applications, e.g. as drug carriers or contrast agents. Depending on the intended application, specific characteristics of the nanoparticles are required. While particles used for imaging should circulate for extended periods of time in the vascular system, nanoparticles designed for use as drug carriers should be efficiently taken up by the target cells. Importantly, nanoparticles for medical (and several other) applications must be biocompatible, meaning that after contact with cells no adverse effects are elicited. Flow cytometry is a powerful technique to analyze multiple parameters on single cell level in parallel. Beside phenotypical alterations occurring during cell death, morphological features of the cells can be monitored easily by this method. Cells taking up nanoparticles increase their side scatter (SSc) reflecting granularity in a dose and time dependent manner. Parallel stainings of the cells with fluorescent viability and activation markers provide additional information, thus drawing a comprehensive picture of cellular health. Recording of the cell count indicates the proliferative capacity of the cells. Thus, our established multiparameter flow cytometry based approach is easy, fast, free of interferences and applicable to various nanoparticles and cellular systems. Importantly, it links the amount of engulfed nanoparticles to the elicited cellular effects, thus allowing us to perform reliable dose-dependent risk assessments of nanoparticles for diverse applications [1,2].

Figure 1: Analysis of Jurkat cells with engulfed iron oxide nanoparticles (50 µg/ml SPIONs, 60h).

References [1] Friedrich, RP; Janko, C, et al. Int J Nanomedicine, 2015, 10, 4185-4201. [2] Poller, JM; Zaloga, J, et al. Int J Nanomedicine, 2017, 12, 3207-3220.

118 International Congress Engineering of Advanced Materials ICEAM2017 Session 18 10 - 12 October 2017 Talk 71 Erlangen, Germany

Development of a Novel Cancer-on-a-Chip: Design and Performance of Micro-Featured Scaffolds to Study Cell Heterogeneity In Vitro

Lucas Hoene1, Andreas Schwab1, Ben Fabry1, Manuel Théry2, Aldo R. Boccaccini1, Aldo Leal-Egana1* 1Institute of Biomaterials, University of Erlangen-Nuremberg, Cauerstr. 6, 91058 Erlangen, Germany. 2CEA Research Institute. Paris, France.

*e-mail: [email protected]

Biomaterials mimicking the neoplastic milieu have become a straightforward alternative for assaying cancer progression and for testing cell pathogenicity in vitro. Our research is currently focused on performing new polymer-based tools to dynamically characterize the metastatic potential of cancer cells in vitro, based on single cell assays and the existence of cell heterogeneity within pathogenic phenotypes. To achieve this aim, soft polyacrylamide hydrogels, having an elasticity of 10 kPa (measured as Young's moduli) were patterned with thin migration lines of 4μm width and 100 μm length, made of collagen type I and fibronectin. Such scaffolds (having a dimension of a coverslip; 22 mm x 22 mm) were designed to mimic the mechanical and topographical cues found at the ECM of tumoral niches, which are sensed and used by malignant cells to undergo into metastasis. These biomimetic matrices were utilized to determine the cell morphology, migration speed and traction forces at single-cell scale during migration stages. Analyses were done by combining time-lapse and traction force microscopy. Our results are showing that wild-type cells (MCF10A; non-metastatic) exhibited two sub-populations within the original phenotype, differentiated in terms of length, speed, and exertion of traction forces. Nevertheless, this behavior is shifted in the case of highly metastatic cells (i.e. MCF10A-ErbB2), of those stimulated with growth factors to acquire a pathogenic behavior (i.e. MCF10A cultured in presence of TGF-β), being characterized by a small and round morphology, fast migration, and low mechanical energy. These results represent the first attempt to study in vitro cell heterogeneity on soft scaffolds, offering a new technological alternative to traditionally used microfluidic devices.

References. 1. Leal-Egana et al., (2017). The size-speed-force relationship governs migratory cell response to tumorigenic factors. Molecular Biology of the Cell. 28:1612-1621

119 International Congress Engineering of Advanced Materials ICEAM2017 Session 18 10 - 12 October 2017 Talk 72 Erlangen, Germany

Role of dispersive interactions at biointerfaces

1* 1,2 Blackwell, R. , and Smith, A-S. (1) PULS Group, Department of Physics and Cluster of Excellence: EAM, Friedrich-Alexander University Erlangen-Nuremberg, Erlangen, Germany (2) Division of Physical Chemistry, Ruder Boskovic Institute, Zagreb, Croatia

* [email protected]

Keywords: biointerfaces, dispersion forces, non-specific interactions

Of the many shared features among all forms of life, the cellular membrane stands out as one of central importance. Cellular membranes are, are their core, simple materials consisting of two polar surfaces with a non-polar "bulk" region between them. Despite membranes' simple structure, their interactions with other surfaces are incredibly diverse and in many cases remain poorly understood. Recent experimental studies have demonstrated non-specific membrane- protein interactions which are orders of magnitude larger in range than theory would typically suggest[1,2]. To probe at the nature of these interactions, we employ detailed Lifshitz theory calculations along with Monte Carlo simulations to demonstrate that careful treatment of the dispersive interactions is sufficient to explain many features of these recent experiments.

Figure 1: Schematic of interfaces (left) and a typical Monte Carlo simulation of the membrane (right).

References [1] Monzel, C.; Fenz, S.; Giesen, M.; Merkel, R.; Sengupta, K. Soft Matter. 2012 8, 6128-6138. [2] Monzel, C.; Schmidt, D.; Seifert, U.; Smith, A-S.; Merkel, R.; Sengupta, K. Soft Matter. 2016 12, 4755-4768.

120 International Congress Engineering of Advanced Materials ICEAM2017 Session 19 10 - 12 October 2017 Talk 73 Erlangen, Germany

Water Gas-Shift Reaction Catalysis in Supported Ionic Liquid Phase

Stepić, R.1,*, Vučemilović-Alagić, N.1,2, Berger, D. 1,3, Wick, C1,2., Bauer T.5, Haumann, M.6, Wasserscheid, P.6, Libuda, J.5, Harting, J. 3,4, Smith, A.-S. 1,2, Smith, D. M. 1,2

(1) Institute for Theoretical Physics I and Cluster of Excellence: EAM, PULS Group, FAU, Erlangen (2) Ruđer Bošković Instutite, Group for Computational Life Sciences, Zagreb (3) Forschungszentrum Jülich, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy, Nürnberg (4) Department of Applied Physics, Eindhoven University of Technology, Eindhoven (5) Lehrsthul für Physikalische Chemie II, FAU, Erlangen (6) Lehrstuhul für Chemische Reaktionstechnik, FAU, Erlangen

*e-mail: [email protected]

Keywords: Water-Gas Shift, Ruthenium Catalyst, Supported Ionic Liquid Phase

The Water-Gas shift reaction (WGSR) results in the conversion of carbon monoxide and water into hydrogen and carbon dioxide, usually in the presence of a catalytic material. This is a very important process in the industry [1], and finding and understanding catalytic systems which maximize the efficiency of the reaction is of great value. In this work we focus on a Ruthenium based class of catalysts, which show great performance in the supported ionic liquid phase (SILP) [2]. The problem of unresolved mechanism is tackled alongside the monomer-dimer equilibrium and potential active species. We utilize a wide variety of techniques from quantum chemistry, ranging from optimizations and vibrational analysis to nudged elastic band searches, to characterize this system. All of the calculations are done within the density functional theory framework using the augmented def2 basis sets which were shown to work well for these kinds of systems [3]. The goal of this study is to describe the reaction mechanism involving the species that show highest activities in SILP systems, in both the qualitative and the quantitative manner. Also the equilibrium between different monomeric and dimeric species and the effect of the solvent are estimated. These findings can later be applied within different theoretical frameworks to model the modern SILP reactors on multiple scales.

References [1] Ratnasamy, C.; Wagner J. P. Cat. Rev.: Sci. Eng., 2009, 51:3, 325-440 [2] Werner, S.; Szesni, M.; Kaiser, M.; Fischer R.W.; Haumann M.; Wasserscheid P. ChemCatChem. 2010 2, 1399-1402. [3] Sobota, M.; Schernich, S.; Schulz, H.; Hieringer, W.; Paape, N.; Wasserscheid, P.; Görling, A.; Laurin, M.; Libuda, J. Phys. Chem. Chem. Phys. 2012 14, 10603-10612.

121 International Congress Engineering of Advanced Materials ICEAM2017 Session 19 10 - 12 October 2017 Talk 74 Erlangen, Germany

Keeping an Eye on Equilibrium: Identifying [Ru(CO)xCly]z Species in SILP Catalysts for the Water Gas Shift Reaction

Bauer, T.1,*; Kollhoff, F.1; Karawacka, W. 1; Stepic, R.2; Wolf, P. 3; 2 4 3 3 1 Smith, A. ; Smith, D. ; Haumann, M. ; Wasserscheid, P. and Libuda, J.

(1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany (2) Lehrstuhl für Theoretische Physik I, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 49b, D-91052 Erlangen, Germany (3) Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058Erlangen, (4) Computer Chemie Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052 Erlangen *[email protected]

Keywords: SILP, WGSR; in-situ spectroscopy

Recent advance in hydrogen-based technologies has increased the demand for H2 production from hydrocarbon sources, which may serve as chemical hydrogen storage media. In the release reaction, a key step is the water gas shift reaction (WGSR) which decreases the CO concentration and increases the H2 concentration in the product gas. The WGSR describes the exothermic reaction of CO and H2O to CO2 and H2.[1] Werner et al. successfully applied the supported ionic liquid phase (SILP) concept for WGSR and demonstrated high activity at low temperature for [Ru(CO)3Cl2]2/[C4C1C1Im][OTf]/Al2O3 and RuCl3/[C4C1C1Im][OTf]/Al2O3. Interestingly, the last-mentioned system requires an induction period of 60 h until full activity is reached. Ex-situ spectroscopic investigations indicate the presence of Ru carbonyls also on this catalyst.[2] This finding suggests that new

[Ru(CO)xCly]z species - which show according to Tsuchiya et al. enhanced catalytic activity - are formed during the reaction itself.[3] However, the exact nature and concentration of these Ru carbonyls has not been identified so far. A detailed understanding of these species would be of major interest, as it would allow for further improvement of the performance of the catalyst system. We apply in-situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) to examine real SILP catalysts, in particular RuCl3/[C4C1C1Im]Cl/Al2O3 and

[Ru(CO)3Cl2]2/[C4C1C1Im]Cl/Al2O3. We identify an equilibrium of several [Ru(CO)xCly]z complexes in the SILP. This equilibrium responds to presence of CO and to changes of the temperature. Additionally, we investigate the influence of Cl- ions provided by the IL phase. With the IL serving as an “infinite” ligand reservoir, transformations between many different

[Ru(CO)xCly]z species are possible. References [1] Mattos, L. V., et al., Chem. Rev. 2012, 112 (7), 4094-4123. [2] Werner, S., et al., ChemCatChem 2010, 2 (11), 1399-1402. [3] Tsuchiya, K., et al., ACS Catalysis 2013, 3 (12), 2865-2868.

122 International Congress Engineering of Advanced Materials ICEAM2017 Session 19 10 - 12 October 2017 Talk 75 Erlangen, Germany

Ionic liquid/support interactions in ultrathin layers on metal surfaces

Lexow, M. *; Bhuin, R.; May, B.; Maier, F. and Steinrück, H.-P.

Chair of Physical Chemistry 2, Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstr. 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: ionic liquid, XPS, interface

Ionic liquids (IL) are ionic compounds with a relatively low melting point, often even below room temperature.[1] In addition to numerous applications as a solvent or electrolyte, the extremely low vapour pressure of ILs also led to the development of completely new concepts for catalytically active systems. Thin layers of ILs on solid materials are applied e.g. in SCILL (Solid Catalyst with Ionic Liquid Layer) catalysis. In this context, the structure and composition of the IL/solid interface is studied by our group combining in vacuo deposition of ultrathin IL films with angle-resolved X-ray photoelectron spectroscopy.[2, 3] The investigations show, how the ionic liquid/solid interface forms and how to control the process by the IL and substrate properties.[4] Aiming to understand the behaviour of applied systems where the liquid/solid interaction determines crucial parameters like pore filling, wetting and dewetting, the results shall allow for predicting and controlling the characteristics of specific systems. M.L., R.B., B.M. and H.P.S. thank the European Research Council (ERC) for financial support of this research in the context of an Advanced Investigator Grant to H.P.S.!

References [1] Wasserscheid, P.;Welton, T., Ionic Liquids in Synthesis, 2007 Wiley VCH, Weinheim. [2] Cremer, T.; Maier, F.; Steinrück, H.-P. et al., Langmuir, 2011 27, 3662-3671. [3] Cremer, T.; Maier, F.; Steinrück, H.-P. et al., Phys. Chem. Chem. Phys. 2012 14, 5153-5163. [4] Rietzler, F.; May, B.; Steinrück, H.-P.; Maier, F., Phys. Chem. Chem. Phys. 2016 18, 25143-25150.

123 International Congress Engineering of Advanced Materials ICEAM2017 Session 19 10 - 12 October 2017 Talk 76 Erlangen, Germany

Thermal lattice Boltzmann method for catalytic flows through porous media

Berger, D.1,*; Smith, A.2,3 ; Smith, D.2,3 ; Harting, J.1,4

(1) Forschungszentrum Jülich GmbH, Helmholtz-Institut Erlangen-Nürnberg for Renewable Energy, Fürther Straße 248, 90429 Nürnberg (2) Institute for Theoretical Physics I, University of Erlangen-Nürnberg, Nägelsbachstraße 49b 91052 Erlangen, (3) Ruđer Bošković Institute, Bijenička cesta 54, 10000, Zagreb, Croatia (4) Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513 5600 MB Eindhoven, The Netherlands *e-mail: [email protected]

Keywords: catalysis, micro-fluidics, simulation

Many catalyst devices employ porous or foam-like structures to optimize the surface to volume ratio and to maximize the catalytic efficiency. The porous structure leads to a complex macroscopic mass and heat transport. Local heat accumulation changes the local reaction conditions, which in turn affects the catalytic turn over rate and eventually compromises the stability of the catalytic device. We present a thermal multicomponent model based on the entropic lattice Boltzmann method [1] to simulate catalytic reactions through porous media. This method reproduces the Navier-Stokes equations and allows the tracking of temperature dynamics. The viscosity, diffusivity, and heat capacities are calculated from the Lennard-Jones parameters of the gases, while the chemical surface reactions are incorporated in a very flexible fashion through flux boundary conditions at the walls. To show the strength and flexibility of this model and our implementation, we will report the catalytic turn-over for a wide range of porosities and reaction conditions.

Figure: Reactive flow through a model porous medium.

References [1] J. Kang et al., Phys. Rev. B, 2014, 89, 063310.

124 International Congress Engineering of Advanced Materials ICEAM2017 Session 20 10 - 12 October 2017 Talk 77 Erlangen, Germany

A New Universal Toolkit for Robust Uncertainty Quantification, Data Analytics and Machine Learning in Material Engineering

Stummer, W. 1*

(1) Department of Mathematics, University of Erlangen-Nürnberg (FAU), Cauerstrasse 11, 91058 Erlangen *e-mail: [email protected]

Keywords: robust uncertainty quantification, Bregman distances, generalized entropies For the engineering of new materials under (prior) incomplete knowledge, the quantitative characterization and reduction of underlying uncertainties is sometimes crucial. This can involve several different tasks such as the principal search for appropriate models (model uncertainty), the recognition of likely patterns and their classification (clustering), the extraction of probable features, the synchronous calibration and testing of crucial parameters (parameter uncertainty and variability), the online detection of presumable (sharp or gradual) change points, the testing for independence respectively homogeneity, and many others. The (naturally random) future financial impact of production investments may have to be investigated, too. All these activities can be carried out in either a frequentist or a Bayesian way (the latter also includes well-known Monte Carlo simulation methods), and in the current state-of-the-art there is also a desire to incorporate (semi-) automated procedures such as statistical and machine learning. This typically amounts to the possible need of using a large spectrum of (quite) different methods of uncertainty quantification. Correspondingly, it would thus be helpful to have at hand some kind of underlying universal basic toolkit. Such one is presented in our talk together with applications to all of the uncertainty quantification tasks mentioned in the first paragraph above. Our toolbox is basically built from new, adaptively scaled, extensions of recently developed distances between (probability and non-probability) densities, respectively between arbitrary functions and vectors. Furthermore, we incorporate goal-specific robust handlings of ''surprising observations'' (outliers and inliers) and visualize the appearing effects by appropriate 3D plots. For instance, we cover as special cases the ordinary (total) Bregman distances (see e.g. [4],[6]-[8],[10]-[11]), the f-divergences (see e.g. [2]), and the more flexible scaled Bregman distances ([9],[2]-[3]); as a subcase, we also include cross-versions of entropy which is one of the most-used uncertainty quantification concept in physics, chemistry, biology, and thus in the corresponding material engineering (see very exemplarily [5]). References [1] Basu, A.; Shioya, H.; Park, C. Statistical Inference: The Minimum Distance Approach. CRC Pu. 2011. [2] Kißlinger, A.; Stummer, W. Lectures Notes in Computer Science. 2015 9389, 693-701. [3] Kißlinger, A.; Stummer, W. In: Recent Advances in Robust Statistics; Springer. 2016 pp. 81-113. [4] Liu, M.; Vemuri, B.; Amari S.; Nielsen, F. IEEE Trans. Pattern Anal. Mach. Intell. 2012 34, 2407-2419. [5] Nature Materials. 2002-2017: several dozens of papers containing entries on entropy. [6] Nock, R.; Menon, A.; Ong, C. Adv. Neural Information Processing Systems NIPS. 2016 29, 19-27. [7] Nock, R.; Nielsen, F.; Amari, S. IEEE Transactions on Information Theory. 2016 62, 527-538. [8] Nock, R.; Piro, P.; Nielsen, F.; Ali, W.; Barlaud, M. Int J. Comput. Vis. 2012 100, 294-314. [9] Stummer, W.; Vajda, I. IEEE Transactions on Information Theory. 2012 58, 1277-1288. [10] Teboulle, M. J. Mach. Learn. Res. 2007 8, 65-102. [11] Wu, L.; Hoi, S.; Jin, R.; Zhu, J.; Yu, N. IEEE Trans. Knowledge Data Engin. 2012 24, 478-491.

125 International Congress Engineering of Advanced Materials ICEAM2017 Session 20 10 - 12 October 2017 Talk 78 Erlangen, Germany

3D analysis of soft-matter functional materials using cryo-tomography

Macauley, C.*and Felfer, P.

Department Werkstoffwissenschaften, Lehrstuhl WW1: Allgemeine Werkstoffeigenschaften, Martensstraße 5, 91058 Erlangen

*e-mail: [email protected]

Keywords: cryo-tomography, PEM fuel cells, focused ion beam

Cryo-electron tomography has revolutionized the study of biological materials by enabling nanometer resolution of cells in their near-native shape [1]. Similar advances have yet to be realized in soft-matter functional materials such as proton exchange membrane (PEM) fuel cells, due to challenges in sample preparation. In this work, a cryo-transfer unit was designed and constructed to analyze polymeric materials using a dual-beam focused ion beam scanning electron microscope (FIB-SEM). A cross-section view of the transfer unit is shown in Figure 1. By maintaining samples at temperatures below -170°C, the pore structure of the catalyst layer and gas diffusion layers in PEM fuel cells can be determined using FIB-SEM serial sectioning. The cryo-transfer unit used in combination with a cryo-stage will facilitate further research into the transport properties in PEM fuel cells and other soft-matter functional materials.

Figure 1: Cross-section view of the cryo-transfer unit designed to attach to the load-lock chamber of a ZEISS FIB-SEM. References [1] Rigort, A.; Plitzko, J. Arch. Biochem. Biophys. 2015 581, 122-130.

126 International Congress Engineering of Advanced Materials ICEAM2017 Session 20 10 - 12 October 2017 Talk 79 Erlangen, Germany

Conceptual Design and Realization of a Laboratory Nano-CT based on a Field Emission Electron Microscope

Stahlhut, P.1,2*; Dremel K.1; Dittmann J.1; Engel J.M.1,3; Zabler S.1,3; Hoelzing A.1,3 and Hanke R.1,3

(1) Chair of X-ray Microscopy LRM, University of Würzburg, Josef-Martin-Weg 63, 97074 Würzburg, Germany (2) Joint Institute of Advanced Materials and Processes, Dr.-Mack-Str. 81, 90762 Fürth, Germany (3) Fraunhofer Institute for Integrated Circuits IIS, Project Group NanoCT systems (NCTS), Josef-Martin-Weg 63, 97074 Würzburg, Germany

*e-mail: [email protected]

Keywords: Laboratory nano-CT, geometric magnification, reflection target, electrochemical etching

We present a computed tomography (CT) setup for material characterization with significantly improved resolution as compared to state-of-the-art micro- or subµ-CT systems [1]. The introduced system is composed of a customized JEOL-JSM7100F scanning electron microscope. By using the focused electron beam of the system with a 30 kV acceleration voltage, we create a very small X-ray source spot in a tungsten or molybdenum tip with a curvature radius of about 60 nm. We formed and optimized the shape of the metal tips by a quick and reliable electrochemical etchingprocess [2]. Due to the ultra small X-ray sourcespot, a spatial resolution below 100 nm is approachable. The system is also capable of inline phase contrast imaging, which comes in handy especially for low contrast imaging. We will also present nano-CT volume images of microstructures within an AlCu29 sample, with a spatial resolution of at least 300nm [3].

Figure 1: Al-Cu29 alloy sample, cross section of the reconstructed volume. References [1] Salomon M.; Hanke R. Nucl. Instrum. Methods Phys. Res. Sect. A. 2008 591, 50-53. [2] Fotino M. Rev. Sci. Instrum. 1992 64, 159-167. [3] Stahlhut P.; Dremel K.; Dittmann J. et.al. Proc. SPIE 2016 9967, 99670I-2.

127 International Congress Engineering of Advanced Materials ICEAM2017 Session 20 10 - 12 October 2017 Talk 80 Erlangen, Germany

Characterization of nanorods dispersed in aerosol and colloidal systems Thajudeen, T.; 1,2*, Walter, J. 1,2; Lübbert, C1,2; Srikantharajah, R1; Peukert, W. 1,2

(1) Institute of Particle Technology, Cauerstr.4, Erlangen. 91058. (2) Functional Particle Systems, Haberstr. 9a, Erlangen. 91058. * [email protected]

Keywords: Electrical mobility classification, Analytical Ultracentrifugation, orthogonal characterization

The application properties of nanoparticles depend on the size and very often their shape. For non-spherical nanoparticles, characterization of geometric size requires the knowledge of at least two dimensions (e.g. length and diameter for nanorods). Information on the hydrodynamic size distribution can be accessed by characterizing the non-spherical particles dispersed in colloidal systems. Analytical Ultracentrifugation (AUC) characterizes particles based on their sedimentation coefficients which depend on their mass as well the hydrodynamic diameter. For particles dispersed in the gas phase, continuum theory cannot be accurately used for characterizing and molecular dynamics is required to represent the physics involved in the momentum transfer processes. It has been shown that the drag can be defined only with a combination of the hydrodynamic diameter (a continuum size parameter) and the respective orientationally average projected area (a non-continuum size parameter) (Zhang et al. 2011). The most common technique for characterizing nanoparticles dispersed in the gas phase is the differential mobility analyzer which measures the mobility of the particles (dependent on the drag acting on the particles). Nanoparticles can be transferred from colloidal systems to DMA using electrospray ionization (ES) or atomization techniques. Analyzing data from DMA and AUC simultaneously opens up the possibility of studying the different geometric size descriptors.

Table 1: Comparison of the dimensions of ZnO rods obtained from analysis of SEM images and the values retrieved using the

combination of AUC/SMPS measurements

ZnO dSEM / nm LSEM / nm dretrieved / nm Lretrieved / nm sample 1 14.9 ± 2.15 55.2 ± 11.0 15.9 60.4 2 25.3 ± 3.94 131.6 ± 44.68 25.4 127

In this study, we combine these techniques and the underlying theories to predict the size parameters of non-spherical nanoparticles with special emphasis on ZnO nanorods. Analysis is extended for gold nanorods as well and the results underline a promising technique for multidimensional characterization of non-spherical nanoparticles. References [1] C. Zhang, T. Thajudeen, et al. Aerosol Sci. & Tech., 2012, 46:10, 1065-1078. [2] J. Walter, T. Thajudeen, S. Süß, et al., Nanoscale, 2015, 7 (15), 6574-6587. [3] J. Walter, K. Löhr, E. Karabudak, et al., ACS Nano 2014, 8 (9), 8871-8886.

128

Poster Presentation Abstracts

in alphabetical order

129 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 36 Erlangen, Germany

Hybrid Organic-Inorganic Nanomaterial Formations via Supramolecular Recognitions

Ali, M.,1* Hasenӧhrl, D.,1 Przybilla, T.2 and Hirsch, A. 1

(1) Department of Chemistry and Pharmacy, Institute of Organic Chemistry, University of Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany (2) Department of Materials Science and Engineering, Institute of Micro- and Nanostructure, University of Erlangen-Nürnberg, Cauerstrasse 6, 91058, Erlangen, Germany

*e-mail: [email protected]

Keywords: Hybrid, Nanomaterial, Supramolecular

Aiming to construct a formation of hybrid organic-inorganic nanomaterials via supramolecular interactions, the gold nanoparticles were functionalized with Hamilton receptors and the titanium dioxide nanoparticles were modified with cyanurate molecules. Hamilton Receptor is well known as a supramolecular compound which used for constructing artificial hydrogen bond and can recognize cyanurate and barbiturate derivates via six complementary hydrogen bonds.[1],[2] The gold nanoparticles were connected to Hamilton receptors covalently using thiol ligands and the titanium dioxide nanoparticles were modified with cyanurate molecules employing phosphonic acid moieties as anchoring groups. Subsequently, the functionalized nanoparticles were utilized to build a hybrid formation via supramolecular recognitions in a semi polar solvent. Moreover, the reactions were followed using UV-Vis spectroscopy and the aggregate products were examined under scanning electron microscopy (SEM).

O NH N O NH O 5 H HN O Au S N N O P TiO HN O O 2 O O O NH N NH O

a b Figure 1: a. Concept of hybrid organic-inorganic nanomaterial formations, b. SEM image of functionalized nanoparticle formations. References [1] Chang, S. K.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 1318-1319. [2] Zeininger, L.; Lodermeyer, F.; Costa, R. D.; Guldi, D. M.; Hirsch, A. Chem. Commun. 2016, 52, 8842-8845.

130 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 10 Erlangen, Germany

A theoretical model to study quantitative properties of tissue growth

1,* 1 1 1,2 Aliee, Maryam ; Vurnek, Damir ; Kaliman , Sara ; and Smith, Ana‐Sunčana

(1) Cluster of Excellence: Engineering of Advanced Materials, Friedrich-Alexander-University of Erlangen-Nürnberg, Erlangen, Germany (2) Institute Ruder Bošković, Division of Physical Chemistry, Zagreb, Croatia *e-mail: [email protected]

Keywords: tissue growth, tissue mechanics, pattern formation

Living organisms represent fascinating materials with precise structures developed by collective dynamics of cells. It is still a big challenge to understand the exact mechanisms though which cells interact with each other as well as with the environment to form reproducible patterns. We would like to analyze carefully how tissue growth is controlled by cell properties putting together a theoretical model and quantitative analysis of experiments. We study growth problem in cultured Madin Darby canine kidney (MDCK) which is a single-layered epithelium and has been used for several years to study collective cell dynamics. Of our particular interests, we carefully measure growth properties of MDCK colonies. In these experiments a group of several cells will grow to a bigger colony distributed roughly in a circle. In such experiments the density of cells also increases and starts to polarize during time. Interestingly, these results demonstrate establishment of a bulk region in the center with high cell density. Beyond a certain size, the density of the bulk region remains constant during time which is a striking puzzle. It has also been observed that average velocity of cells decreases with cell density. In this presentation, I would present our approach to investigate growth control from a mainly theoretical viewpoint. We develop a continuum coarse-grained model to take into account cell mechanics as well as activity of cells to study dynamics of tissues. Our model is based on some fundamental rules established before to describe fluids and viscoelastic materials. We consider balance of cell number and forces modified by active terms coming from cell division and apoptosis. Putting everything together, our theory gives a good general description of growing tissues. Interestingly, our results show establishment of bulk and edge regions independent of many details. We study how the time- evolution and the relative size of bulk and edge are controlled by interaction of cells and their response to pressure and substrate. We also analyze how growth rate of the colony and local cell density change during time. We present a phase diagram and study how different parameters influence dynamics of cell colony, such as colony growth rate, cell densification and velocities. We particularly analyze the circumstances to achieve the observed tissue growth in different experiments.

131 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 82 Erlangen, Germany

Templated Dewetting-Dealloying of Metals: Designing Photocatalytic Platforms

Marco Altomare,1,* Nhat Truong Nguyen1 and Patrik Schmuki1,2

(1) Department of Materials Science and Engineering WW4-LKO, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen, Germany (2) Chemistry Department, Faculty of Sciences, King Abdulaziz University, 80203 Jeddah, Saudi Arabia Kingdom

*e-mail: [email protected]

Keywords: anodic metal oxide, metal dewetting, photocatalytic H2 generation In this contribution it is discussed how nanoscale processing tools such as electrochemical anodization,[1] metal dewetting[2] and dealloying[3] can be combined to design a platform for photocatalytic H2 generation. Highly-ordered arrays of anodic TiO2 nanocavities with periodicity and depth of some 100 nm[4] (Fig. a) are used as a substrate onto which thin metal films (thickness of few nm – few tens nm) are conformally sputter-coated. Then, a suitable thermal treatment is carried out that brings about morphological evolution of the metal film into periodically arranged metal particles. The periodicity of the TiO2 surface is key for templated dewetting: it leads to self-ordering of the dewetted metal nanoparticles into the TiO2 nanocavities.

Particularly interesting are combinations of sputter-coated metals. Depending on the selected elements, dewetting can lead to the formation of alloyed metal nanoparticles of controllable size/composition that are embedded into the TiO2 nanocavities (Fig. b). When one of the sputtered metals is less noble than the other (e.g. Ag vs. Au), the alloyed-dewetted structures can be dealloyed: the more (electro-)chemically active element (Ag) is selectively dissolved, leaving behind nanoporous noble metal (Au) particles with high specific surface area (Fig. c).[5] These structures combine the intrinsic photocatalytic features of TiO2 with cocatalytic ability of noble metals, thus providing a platform for photocatalysis.[6] It is outlined how self-ordering concepts such as anodization, alloying, dewetting and dealloying can be interlaced to reach a fine control over the resulting metal-TiO2 structures, in view of maximizing their photocatalytic efficiency. References [1] P. Roy, S. Berger, P. Schmuki, Angew. Chemie Int. Ed. 2011, 50, 2904–2939. [2] C. V. Thompson, Annu. Rev. Mater. Res. 2012, 42, 399–434. [3] A. J. Forty, Nature 1979, 282, 597–598. [4] J. E. Yoo, K. Lee, M. Altomare, E. Selli, P. Schmuki, Angew. Chemie Int. Ed. 2013, 52, 7514–7517. [5] N. T. Nguyen, M. Altomare, J. Yoo, P. Schmuki, Adv. Mater. 2015, 27, 3208–3215. [6] M. Altomare, N. T. Nguyen, P. Schmuki, Chem. Sci. 2016, 7, 6865–6886.

132 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 26 Erlangen, Germany

Fluid-jammed phase transitions of dense suspension of capsules: a model system for soft-glassy matter

Aouane, O.;1,*, Wouters, M.;2, Scagliarini, A.;1 and Harting, J.;1,2

(1) Forschungszentrum Jülich, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IEK-11) (2) Eindhoven University of Technology, Department of Applied Physics

*e-mail: [email protected]

Keywords: capsules, rheology, jamming

Soft-glassy materials are a class of material showing a solid-like behavior at rest and local yielding when subject to a high enough stress. While systems like foams, emulsions, colloidal and polymer gels have been widely studied in the last decades [1-2], still little is known about the flow behavior of dense suspensions (volume concentration above 0.6) of polymeric coated core-shells, i.e. capsules [3]. The rheology of capsules for volume fractions up to 0.9 is investigated numerically under inhomogeneous (Kolmogorov and Poiseuille) and homogeneous (shear) flows using the lattice Boltzmann method (BGK D3Q19) [4]. The fluid-interface coupling is achieved using the immersed boundary method and forces are computed on the surface of the capsules using a finite element scheme [5]. This study includes the effect of the mechanical properties of the individual capsules (stiffness/softness) on the local and global rheological behavior. Furthermore, the fluid-jammed phase transition is discussed for several sets of parameters.

References [1] Liu, A. J., & Nagel, S. R. (1998). Nature, 396(6706), 21-22. [2] Benzi, R., Bernaschi, M., Sbragaglia, M., & Succi, S. (2013). EPL (Europhysics Letters), 104(4), 48006. [3] Gross, M., Krüger, T., & Varnik, F. (2014). Soft matter, 10(24), 4360-4372. [4] Krüger, T., Frijters, S., Günther, F., Kaoui, B., & Harting, J. (2013). The European Physical Journal Special Topics, 222(1), 177-198. [5] Krüger, T., Varnik, F., & Raabe, D. (2011). Computers & Mathematics with Applications, 61(12), 3485-3505

133 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 81 Erlangen, Germany

A comparative study of the adsorption and reaction of formic acid on Ni(111) and Pt(111)

Bachmann, P. 1,*, Bauer, U. 1, Späth, F. 1, Düll, F.1, Papp, C.1 and Steinrück, H.-P. 1

(1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, Germany

*e-mail: [email protected]

Keywords: formic acid, XPS, hydrogen storage

Formic acid has favorable properties as hydrogen carrier. Therefore, we investigated the adsorption at 130/140 K and temperature-dependent hydrogen release of formic acid on Ni(111) and Pt(111) using high resolution X-ray photoelectron spectroscopy (HR-XPS), temperature-programmed desorption (TPD), and near edge absorption fine structure (NEXAFS). Our study reveals pronounced differences in the decomposition behavior between Ni(111) and Pt(111) surfaces, such as different desorption temperatures and the formation of CO. The work was supported by the Cluster of Excellence Engineering of Advanced Materials (EAM).

Figure 1: Reaction of formic acid on Pt(111) and Ni(111). References [1] R. Denecke, M. Kinne, C. M. Whelan, H.-P. Steinrück, Surf. Rev. Lett., 2002, 9, 797. [2] Q. Luo, G. Feng, M. Beller, and H. Jiao, J. Phys. Chem. C, 2012, 116, 4149–4156. [3] K. Kusafuka, H. Noguchi, K. Onda, J. Kubota, K. Domen, C. Hirose, A. Wada, Surf. Sci., 2002, 502– 503, 313-318. [4] C. Hirose, A. Bandara, S. Katano, J. Kubota, A. Wanda, K. Domen, Appl. Phys. B, 1999, 68, 559-565. [5] N. Abbas, R.J. Madix, Appl. Surf. Sci., 1983, 16, 424-440.

134 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 8 Erlangen, Germany

Relaxation of hydrogen bond network in water subject to E-field

Baer, A.; 1,* Miličević, Z.;1,2 Smith, D.; 2,3 and Smith, A-S.; 1,2

(1) PULS Group at the Institute for Theoretical Physics and EAM, FAU Erlangen-Nürnberg, Germany (2) Division of Physical Chemistry, Institute Ruđer Bošković, Zagreb, Croatia (3) Computer Chemistry Center, FAU Erlangen-Nürnberg, Germany *e-mail: [email protected]

Keywords: Multiscale Modeling and Simulation, Particle based fluid mechanics, Molecular Dynamics Microscopically, liquid water is a fluctuating, uninterrupted network of molecules connected by hydrogen bonds. Dynamical reordering of bonds, combined with restricted translations and rotations lead to a number of amazing macroscopic properties water. However, experimental characterization of the dynamic structure of liquid water is extremely challenging, which makes molecular dynamics simulations ideal to study structure of this complex liquid.1,2 Such work provided deep insight into the dynamics of the hydrogen bonds, however, the influence of an electric field is very poorly addressed, despite enormous technological implications. We address this problem by simulating pure water in GROMACS at ambient conditions. Water is represented by simple SPC/E, TIP4P2005 models, while small to medium-strength electric fields are applied along one axis.3 The orientational dynamics of water is quantified by calculating the time-dependent projection of the dipole moment to the field axis. This permits the analysis of correlated reorientations of molecules in the first hydration shell. Characteristic, anisotropic timescale for the reordering of hydrogen bonds, parallel and perpendicular to the field are retrieved. A novel relaxation process occurring on the picosecond timescale is characterized using bilateral filters. This field induced process is associated with cooperative fluctuations of neighboring molecules between states of zero torque on the dipole (orientation of 0° and 180° relative to E). The existence of this process can be related to field induced changes in macroscopic properties of water such as shear viscosity.4

Figure 1: Water molecules (SPC/E) partly aligned to Figure 2: Cosine of angle between polarization the electric field at E=0.6 V/nm. vector and electric field for a molecule (mid), its hydration shell (bot) and the filtered version (top). References [1] Luzar, A.; Chandler, D. Nature 1996 379, 55-57. [2] Nilsson, A.; Petterson, L. G. M. Nat. Commun. 2015 6, 8998. [3] Milicevic Z., Marrink S. J., Smith A.-S., Smith D. M. J. Mol Mod 2014 20, 2359 [4] Milicevic Z., Baer A., Smith D. M., Smith A.-S., PRX submitted

135 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 68 Erlangen, Germany

In-situ doctor-blading cell for synchrotron radiation studies

Berlinghof, M.1,*; Langner. S.2; Kassar, T.1 Bär, C1; Brabec, C.2; and Unruh, T.1

(1) Chair for Crystallography and Structural Physics, Friedrich-Alexander-University Erlangen-Nürnberg, Staudtstr. 3, 91058 Erlangen (2) Institute Materials for Electronics and Energy Technology, Friedrich-Alexander-University Erlangen-Nürnberg, Martenstr. 7, 91058 Erlangen

*e-mail: [email protected]

Keywords: GID, in-situ, thin-films

We propose to present our flexible custom made doctor-blading cell, which was especially designed for grazing incidence studies at synchrotrons like PETRA III (DESY). In addition to be temperature controlled, it is also capable of solvent vapor annealing and of hydration of samples. Besides the technical details, capabilities and limitations of the cell, we intend to focus our presentation on three example scientific examples. One being the in-situ crystallization of organic photovoltaics, e.g. DRCN5T:PC71BM, by solvent vapor annealing or thermal annealing, which has an high impact on the efficiency of organic photovoltaics (OPVs) [1]. The second example are in-situ drying studies of OPVs, which shows the structure formation during the drying process. We would present the insight on the kinetics of the crystallization process achieved by in-situ GID . The other example would be the in-situ drying and hydration of phospholipid, e.g. DMPC, multilayer samples, which are a model system for biological membranes [2]. For these liquid crystalline samples fully hydration of is essential, which is achieved by creating 100% humidity in the sample cell.

Figure 1: Temperature and atmospheric controlled doctor-blading cell installed at our lab-source VAXSTER. References [1] Min, J.; Jiao, X; et al., Nano Energy. 2016 28, 241-249. [2] Salditt, T.; Li, C.; et al., Eur. Phys. J. E. 2002 7, 105-116.

136 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 54 Erlangen, Germany

Surface Phase Behavior of [PPh4][Tf2N] / Cs[Tf2N]- and [PPh4][Tf2N] / Ni[Tf2N]2 Low-Temperature Molten Salt Mixtures

Schreiber, P. 1; Scheuermeyer, M. 2; Bhuin, R. G. 1,*; Wasserscheid, P. 2; Steinrück, H.-P. 1; Maier, F. 1

1Lehrstuhl für Physikalische Chemie II, FAU, Erlangen, Germany 2Lehrstuhl für Chemische Reaktionstechnik, FAU, Erlangen, Germany

*e-mail: [email protected]

Keywords: molten salt, angle-resolved X-ray photoelectron spectroscopy

We report on surface investigations using a new class of organic/inorganic molten salt mixtures based on a tetraphenylphosphonium bis(trifluoromethylsulfony)•imide compound. Depending on composition, these mixtures combine low melting points with exceptionally high thermal stability, and thus, exhibit considerably enlarged reaction windows compared to conventional ionic liquids.[1] To elucidate their surface behavior, temperature-dependent angle-resolved X-ray photoelectron spectroscopy (ARXPS) investigations were performed using our new and unique labo•ratory electron spectrometer DASSA (“Dual Analyzer System for Surface Analysis”), dedicated for investigations of macroscopic liquid samples mounted horizontally.[2] The DASSA comprises an ultra-high vacuum chamber equipped with two electron analyzers (ARGUS, Scienta-Omicron) for simulta•neous measurements at 0° (bulk sensitive with information depth 7-9 nm) and 80° (surface sensitive, 1-1.5 nm) emission conditions. We followed temperature-induced changes in bulk and surface composition for mixtures of

[PPh4][Tf2N]/Cs[Tf2N] and [PPh4][Tf2N]/Ni[Tf2N]2. Interestingly, the surface of the shown Cs-containing mixture in the liquid state favors the presence of [Cs]+ on expense of the bulky + [PPh4] ions as shown by ARXPS.

RGB and HPS thank the ERC for financial support through an Advanced Investigator Grant to HPS.

References: [1] Scheuermeyer et al., New J. Chem. 2016 40, 7157. [2] Niedermaier et al., Rev. Sci. Instrum. 2016 87, 045105.

137 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 15 Erlangen, Germany

QM/MM study of the inactivation of the B12-dependent dehydratases by substrate glycerol

Bilić L.1,*, Barić D.1, Sandala M. G.2, Radom L.3, Smith M. D.1 and Kovačević B.1

(1) Ruđer Bošković Institute, Bijenička 54, Zagreb, 10000, Croatia (2) Allison University, Sackville, Canada (3) The University of Sydney, Sydney, Australia

*e-mail: [email protected]

Keywords: B12-dependent dehydratases, inhibition, reaction mechanism

Some bacteria use alcohol as a source of carbon and energy in order to grow in anaerobic conditions via fermentation. The fermentation of alcohol starts with the dehydration (Figure 1). This reaction is catalyzed by two enzymes: glycerol dehydratase (GDH) and diol dehydratase [1] (DDH), which use coenzyme B12 as an essential cofactor. As with most B12-dependent reactions, the reaction mechanism of these two enzymes involves a formation of radical intermediates. It is known that both GDH and DDH undergo substrate-induced inactivation by glycerol, the rate of which is higher for DDH than for the GDH.[2] Possible inactivation mechanism is recently reported by Yoshizawa et al. It states that glycerol C1 radical can abstract hydrogen from C3 hydroxyl group forming unstable O-centered radical which undergoes homolytic cleavage to form formaldehyde and glycol radical.[3,4] In this work we propose and explore another mechanism of inactivation for GDH and DDH that does not require energetically expensive intramolecular hydrogen transfer from hydroxyl group to C1 radical. The energy profiles of the proposed inactivation mechanism for both enzymes yielded activation energies that are more consistent with the experimental data providing better explanation to underlying mechanism for the unusual “suicidal” inactivation of GDH and DDH.

Figure 1: Dehydration of an alcohol; a first step in fermentation catalyzed by GDH and DDH.

References [1] H. A. Lee, Jr., R. H. Abeles, J. Biol Chem., 1963, 238, 2367, J. Pawelkiewicz, B. Zagalak, Acta Biochim. Polon. 1965, 12, 207. [2] W. W. Bachovchin, R. G. Eagar, Jr., K. W. Moore, J. H. Richards, Biochemistry, 1977, 16, 1082. [3] K. Doitomi, T. Kamachi, T. Toraya, K. Yoshizawa, Biochemistry, 2012, 51, 9202. [4] K. Doitomi, T. Kamachi, T. Toraya, K. Yoshizawa, Bull. Chem. Soc. Jpn. 2016, 89, 955.

138 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 89 Erlangen, Germany

TRACKING DOWN THE ANSWER TO THE NANOSTRUCTURE- MECHANICS RELATIONS

Böhm, C. F.1*, Harris, J1. Feldner, P.2, Sui, X.M.3, Wagner, H. D.3, Wolf, S. E.1

1) Friedrich-Alexander University Erlangen-Nürnberg, Department of Materials Science and Engineering, Institute of Glass and Ceramics, Martensstr. 5, 91058 Erlangen, Germany 2) Friedrich-Alexander University Erlangen-Nürnberg, Department of Materials Science and Engineering, Institute of General Materials Properties, Martensstr. 5, 91058 Erlangen, Germany 3) Weizmann Insitute of Science, Department of Materials and Interfaces, Rehovot 76100, Israel

*e-mail: [email protected]

Keywords: structure-property relationship, biogenic, bioinspired

The outstanding impact of the microstructural architectures of sea shells on their mechanical properties is known for centuries, especially for the most prominent example of the brick-and- mortar structure in nacre. Beside nacre, many other microstructures exist and are known to contribute in different ways to the mechanical properties of natural composite material. However, in addition to the contribution of the microstructure, an essential contribution to the shells mechanical properties arises from the nanostructure. Understanding the nanostructure- property relationship in biogenic materials is consequentially of great importance to the field of bio-inspired materials design. This project focuses on the establishment of enhanced cross-correlative measurement techniques for characterization of both, the nanostructure as well as the properties caused by the nanostructure based on the biogenic material of our model organism Pinna nobilis. Having unambiguously identified the nanostructure-property relationship in on our model organism, the enhanced techniques are then transferred to bio-inspired materials, i.e. materials assembled by the highly promising nonclassical colloid attachment and transformation processes (CAT). The established techniques not only allow the unambiguous characterization of the nanostructure- property relationship in bio-inspired materials, but also to optimize their properties in the future.

References [1] Wolf, S. E., Böhm, C. F., Harris, J., Demmert, B., Jacob, D. E., Mondeshki, M., Ruiz-Agudo, E., Rodriguez-Navarro, C., J. Struct. Biol., 2016, 196, 244-259. [2] Harris, J, Mey, I., Hajir, M., Mondeshki, M., Wolf, S.E., CrystEngComm, 2015, 17, 6831-6837.

139 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 59 Erlangen, Germany

Synthesis of bis(methylammonium) sulfidoantimonate perovskites from antimony sulfide thin films made by ALD for photovoltaics

Both Engel, A.1,*, Bachmann, J.1

(1) Department of Chemistry and Pharmacy, Friedrich Alexander University Erlangen-Nürnberg, Egerlandstr. 3 - 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: perovskite, antimony sulfid e, photovoltaics

Perovskite solar cells (SCs) are emerging as a new type of photovolt aics, with similar operating principle as dye-sensitized SCs, but in which the light absorber layer is a solid perovskite material. Perovskites present a crystal structure with the formula ABX3 (A and B are cations, X is an anion). One advantage of perovskites over traditional inorganic light absorbers is the possibility of tuning the band gap by changing the cation. So far, methylammonium lead halide perovskites have enabled the construction of photovoltaic devices with low cost and good efficiencies (up to more than 20 %). This brought new perspectives to the field, although with the downside of the inherent lead toxicity and limited stability. In the quest for lead-free perovskite materials, bis(methylammonium) sulfidoantimonate perovskite – (CH3NH3)2Sb8S13 – emerges as a suitable alternative for photovoltaics, presenting a predicted direct optical bandgap of 2,08 eV. This material has been synthesized in the past in bulk form, which proved its feasibility. However, for the production of ETA (extremely thin absorber) SCs, the synthesis of thin films of (CH3NH3)2Sb8S13 becomes a challenge. In this context, the expertise of our group in the Atomic Layer Deposition (ALD) of Sb2S3 proves useful. Therefore, the objective of this work is to synthesize for the first time (CH3NH3)2Sb8S13 from thin films of Sb2S3 made by ALD, and test its performance in an ETA SCs. We have shown the possibility of achieving a new crystal structure by reacting Sb2S3 with a precursor we synthesized. Mild temperatures between 100 °C and 180 °C were employed for the reaction, whereas to crystalize pure Sb2S3 higher temperatures of 315 °C are necessary. Different precursor compositions were also tested, and the product was characterized by GIXRD, SEM/EDX, diffuse optical absorption spectroscopy and Hall measurements, before the assembly and test of a complete ETA cell. Figure 1 compares the GIXRD diffractograms recorded from the perovskite structure we obtained to pure Sb2S3, showing that a new phase has been achieved.

Figure 1: GIXRD of Sb2S3 and (CH3NH3)2Sb8S13 film (experimental).

140 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 60 Erlangen, Germany

Parallel arrays of cylindrical, coaxial p-i-n heterojunctions as ETA solar cells

Pascal Büttner and Julien Bachmann

Extremely thin absorber (ETA) solar cells are a promising concept for low-cost photovo ltaics. In the ETA community, nanoparticular titanium dioxide films are often used to meet the requirement for large surface area to volume ratios. However, using nanoparticular films as scaffolds relies on the trap-limited diffusion of charge carriers, which restricts device efficiency. Thus, the utilization of highly ordered titania nanotube arrays is a promising approach to provide short, di rect carrier pathways. In this work, titanium dioxide nanotubes are grown by anodization of sputtered titanium thin films on indium tin oxide (ITO) glass. An “interrupted anodization” procedure is presented as a novel facile approach to producing open nanotubes without the disordered initiation layer. The n-TiO2 nanotube arrays are subsequently coated with intrinsic, light-absorbing, antimony sulfide via atomic layer deposition (ALD) to realize a uniform absorber thickness over the whole nanotube surface. p- CuSCN is deposited as hole conductor by solution evaporation and a sputtered gold layer is used as a back contact. The device structure is characterized after each processing step, and the performance of final devices is investigated by I-V curves, quantum efficiency, and impedance spectroscopy. This system allows for systematic investigation of geometric effects on ETA solar cell performance parameters.

141 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 75 Erlangen, Germany

Application of precious-metal free immobilized polyoxometalate catalysts

Bukowski A. 1,*, Albert J. 1 and Wasserscheid, P.; 1

(1) Department of Chemical Engineering, Friedrich-Alexander-University Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany

*e-mail: [email protected] Keywords: Polyoxometalates, heterogeneous catalysis, biomass oxidation

Biomass is commonly recognized as one of the most important renewable resources. Therefore, various strategies for producing chemicals and fuels from biomass are under investigation as alternative, non-fossil feedstock. Among the types of biomass available for energetic applications, lignocellulosic biomass is highly desirable as it is not in direct or indirect competition with food production.1 Furthermore, catalytic oxidation chemistry of biomass is a growing field of research. The main effort is to overcome the recalcitrant nature of the feedstock by acid-catalyzed depolymerization followed by oxidative cleavage of the carbon bonds in the biomolecule.2 A promising material class for oxidative conversion of biomolecules are polyoxometalates (POMs). POMs are molecular metal oxides whose structural and chemical variability results in a vast compound class where properties can be tuned on the molecular level. POMs are typically based on early, high valent transition metals (e.g. V, Mo, W) with applications in energy conversion and storage, molecular electronics and catalysis. POMs are often superior to more familiar catalysts in terms of activity and selectivity and their use in oxidation and photooxidation catalysis is well established.3 In this contribution, we present our latest results on the immobilization of various POM catalysts (H3PMo12O40, H8PV5Mo7O40) on different supports like apts-functionalized SiO2, metal oxides like gamma-Al2O3 and TiO2, activated carbon, metal-organic frameworks (MOFs) like MIL-100 and polymer-resins. We have performed a detailed characterization of all synthesized structures using ICP, FT-IR, XRD SEM, TGA and different sorption techniques. For their catalytic application, we used them in one technical relevant oxidation reaction - the OxFA-process4. First results show interesting correlations between the different POMs and the various heterogenization methods, combined with promising catalytic performance under moderate reaction conditions, which offers great opportunities for future technical applications. References [1] D. Alonso, J. Bond and J. Dumesic, Green Chem., 2010, 12, 1493. [2] A. Sutton, Nature Chem., 2013, 5, 428. [3] C. L. Hill, J. Mol. Catal. A Chem. 2007, 262, 2. [4] J. Albert, R. Wölfel, A. Bösmann, P. Wasserscheid, Energy Environ. Sci., 2012, 5, 7956.

142 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 24 Erlangen, Germany

Numerical simulations of bubble flow and size distribution in the Elbow

Nan Chen 1,*, Manuel Münsch1, Cornelia Rauh1,2, Ladan Zoheidi1, Antonio Delgado1

(1) Institute of Fluid Mechanics, Friedrich-Alexander University, Erlangen, Germany (2) Department of Food Biotechnology and Food Process Engineering, Technische Universität Berlin, Berlin, Germany

*e-mail: [email protected]

Keywords: Foam, Numerical Investigations, Elbow

Protein foams play an important role in both natural systems and industrial applications. Although a large body of publications related to foams exists, most of the contributions in literature deal with the diffusive transport of proteins. In contrast to this, there is still lack of knowledge regarding the convective transport of foams.

Recent research shows that protein foams exhibit a complex rheological behavior, whose transport results in rheological parameters, elasticity and yield stress even in pure Newtonian liquid. These phenomena represent a consequence of material properties as well as topology. In addition, the flow process may induce a rearrangement of the topology because of the centrifugal forces as well as normal and tangential stresses exerted by the bended tube.

The present contribution deals with the numerical prediction of foam movement under the impact of centrifugal force gradients as induced in a flow bending. Foam is initialized in a vertical channel. The succeeding convective transport procedure within the elbow section is predicted numerically. Numerical results are first validated by comparing the bubble velocity and drag coefficient with the experimental results. One of the prominent experimental results related to effect of the bending on the foam flow consists in the rearrangements of the bubbles with respect to their size. From the experimental results, rearrangement related secondary flows occurs because the gradient of the centrifugal forces prevailing in the flow bending reorder the bubbles with respect to the local densities. Consequently, large bubbles move to region of smaller radii while smaller bubbles tend to migrate to the radially outer region of the blending geometry. The numerical results of the size distribution are compared to the experimental data, which obeys a skewed distribution. Bubble coalescence as well as rearrangement phenomena is also observed in this region. References [1] Zoheidi L, Panradl C, Rauh C, Delgado A, J Food Process Eng. 2017;00:e12563.

143 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 16 Erlangen, Germany

Doping calcium carbonate with divalent ions

Demmert, B. 1,*; Schüssler, M.1 and Wolf, S. E.1,2

(1) Department of Materials Science and Engineering, Institute of Glass and Ceramics (WW3), Friedrich-Alexander-University Erlangen-Nuremberg, Martensstrasse 5, 91058 Erlangen, Germany. (2) Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander University Erlangen-Nürnberg (FAU), Haberstrasse 9a, 91058 Erlangen, Germany.

*[email protected]

Keywords: Amorphous Calcium Carbonate, Doping, Transformation into crystalline material

Formation of crystalline phases of calcium carbonate via pseudomorphic transformation of an amorphous precursor phase (ACC) allows for incorporation of dopants, such as Ba2+ and Sr2+, at much higher rates than standard approaches via direct precipitation. This route of synthesis is of interdisciplinary interest. First, paleo-environmental reconstruction rests on the incorporation rates of different trace elements into calcium carbonate. Second, this method offers enhanced uptake of dopant ions at low temperature providing a low-cost method for waste extraction or even for the purposeful design of resorbable biomaterials. In this contribution, we demonstrate the changes in incorporation rates of different ions in amorphous calcium carbonate and after the transformation into crystalline materials.

Figure 1: Sr2+ doping of calcium carbonate. (a) and (b) XRD measurements of amorphous calcium carbonate phase doped with Sr2+ and the crystalline phase after transformation via heat. (c) SEM image of amorphous calcium carbonate. References [1] Littlewood, J. S.; Shaw, S. Cryst. Growth Des. 2017 17(3), 1214–1223. [2] Whittaker, M. L.; Joester, D. Adv. Mater. 2017, 1606730. [3] Zou, Z.; Bertinetti, L. Small 2017, 1603100.

144 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 84 Erlangen, Germany

Lightweight ultrafine-grained Al-Ti laminates produced by accumulative roll bonding

Diepold B. 1,*, Schunk S. 1, Fey T.2, Höppel H.W., Göken M. 1 (presenting author specified with an asterisk *) (1) , Friedrich-Alexander-University Erlangen-Nürnberg FAU, Materials Science & Engineering, Institute I, 91058 Erlangen, Germany (2) Friedrich-Alexander-University Erlangen-Nürnberg FAU, Materials Science & Engineering, Glass & Ceramics, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: ARB, ultrafine grained, fatigue

Ultrafine-grained laminated metallic composites (LMC) consisting of alternating layers of aluminum AA2024 and titanium grade 1 alloys have been produced by the well-known Accumulative Roll Bonding (ARB) process [1]. The obtained LMCs exhibit high strength paired with a high fracture strain [2]. By repeating the ARB process up to three times, composites with up to 16 individual layers were produced. Under flexural loading the different elastic moduli of the individual layers play a major role for the stress distribution. This was calculated for each type of layer-architecture by FEM-simulation and compared to its mechanical properties. Especially for three-point bending fatigue tests the tension stresses in the outer layers play a major role for crack initiation and thus determine the whole fatigue life. The obtained fatigue lives for the laminates with the Al-layer at the outer side are deteriorated compared to the LMCs with Ti as the outer layer. For a better understanding, the fatigue crack propagation behavior was investigated by SEM (Figure 1) and micro-CT. Further mechanical properties of each architecture were investigated. The tensile strength increases with increasing number of ARB-cycles. Architectures with an outer aluminum layer show here higher strength combined with a lower fracture elongation, caused by faster hardening in the ARB process. Especially the local hardness measurements by nanoindentation show the different hardening behavior of both materials with dependency on the architecture. Future applications might be in light-weight aircraft structures to replace monolithic aluminum sheets with these high strength laminates.

Figure 1: Fatigue crack propagation in ARB processed Al-Ti laminates with 16 individual layers.

References [1] Saito, Y.; Tsuji, N; Scripta Mater 1998 39, 1221 [2] Hausöl, T.; Höppel, H.W.; J Mater Sci 2010 45, 4733

145 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 79 Erlangen, Germany

Reactivity of CO on Sulfur-Passivated Graphene-Supported Platinum Nanocluster Arrays

Fabian Düll1,*, Florian Späth1, Udo Bauer1, Philipp Bachmann1, Johann Steinhauer1, Hans-Peter Steinrück1, and Christian Papp1

(1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: Heterogeneous Catalysis, Poisoning, XPS

Poisoning of heterogeneous catalysts by sulfur and sulfur-containing compounds is of high importance for various processes in industry and therefore a hot topic in catalysis for decades. Platinum is a widespread catalyst material for various applications and sulfur a common impurity in many feedstocks. Utilizing the intrinsic Moiré pattern that is formed by graphene on Rh(111) as a template and chemically inert support, platinum nanocluster arrays were grown. These clusters were then poisoned by sulfur via thermal reduction of SO2. To understand the changes that occur upon sulfur poisoning, the adsorption and desorption of the common probe molecule CO were investigated. The changes in the adsorption behavior for several preadsorbed sulfur coverages were investigated with in situ high-resolution X-ray photoelectron spectroscopy. Three different CO species can be distinguished; top and bridge bonded CO on terrace sites and CO at step sites. Sulfur blocks those adsorption sites to different degrees. While on-top and step sites are highly affected, bridge sites are affected to a lower degree. These results will be compared to measurements on the stepped Pt(322) and Pt(355) surfaces.[1] Upon annealing CO on the sulfur poisoned clusters, a displacement of sulfur from step to terrace sites by CO is observed around 330 K. This displacement is reversed after desorption of the CO. Such a behavior was also found on stepped platinum crystals. References [1] Streber, R.; Papp, C; Lorenz, M; Bayer, A; Denecke, R; Steinrück, H.-P. Chem. Phys. Lett. 2008, 452, 94–98.

146 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 77 Erlangen, Germany

Investigation of the Formation of Metal-Organic Framework MIL-53(Al) via in situ Raman, FTIR Spectroscopy and Turbidity Measurements under Solvothermal Conditions

Embrechts, H.1,2*; Kriesten, M.3; Distaso, M.1,2; Hartmann, M.2,3; Peukert, W.1,2

(1) Department of Chemical and Biological Engineering, Institute of Particle Technology, Cauerstr. 4, 91058 Erlangen, Germany (2) Interdisciplinary Center for Functional Particle Systems, FAU Erlangen-Nürnberg, Haberstraße 9a - 91058, Erlangen, Germany (3) Erlangen Catalysis Resource Center, Egerlandstr. 3, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: In situ Spectroscopy, Metal-Organic Frameworks, Formation mechanism

Metal-Organic Frameworks (MOFs) show great promise in the fields of catalysis [1], gas separation [2] and storage [3], due to their high specific surface area, uniform pore size distribution and the possibility to modify their chemical properties by linker functionalization. Furthermore, some of these coordination networks exhibit unique framework dynamics like ligand rotation or guest- and temperature-induced structural transformations due to the so called “breathing effect”. Despite their widespread application potential, the formation mechanism of these materials is, as of yet, poorly understood and largely unaddressed. Indeed, a better understanding of MOF formation in solution would enable the development of novel MOF structures tailored to a variety of applications. In this contribution, the physico-chemical processes that occur during MOF formation are elucidated through simultaneous FTIR, Raman and turbidity measurements collected by immersed dip probes during the solvothermal synthesis of the aluminum terephthalate MIL-53(Al) in DMF. The deprotonation of the linker terephthalic acid, formation of an aluminum-based intermediate, evolution of MOF nuclei species in solution, precipitation of the bulk MOF phase, and ensuing decomposition of DMF to formic acid are followed with in situ FTIR and Raman spectroscopy. A “self-healing process” is observed, involving incorporation of linkers into the MOF structure and depletion of unreacted terephthalic acid from the pores. The MOF samples taken at different synthesis times are analyzed by complementary ex situ characterization techniques in order to support the in situ observations and further shed light on the formation mechanism of MOF MIL-53 in solution. References [1] Hartmann, M.; Fischer, M. Microporous Mesoporous Mater. 2012 164, 38-43. [2] Hartmann, M.; Böhme, U.; Hovestadt, M.; Paula, C. Langmuir 2015 31, 12382-12389. Figure 1: Structure of MIL-53 [3] Himsl, D.; Wallacher, D.; Hartmann, M. Angew. Chem. Int. Ed. 2009 48, 4639-4642.

147 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 88 Erlangen, Germany

Investigations of the early stage of precipitations in additive manufactured Ni and Cu based alloys with Small Angle Scattering using synchrotron X-Ray radiation

F. Galgon1*, C. Körner1, A. Stark², P. Staron 2, S. Gayer2, M. Müller2

(1) Chair of Materials Science and Engineering for Metals, Friedrich-Alexander-Universität Erlangen-Nürnberg, Martensstr. 5 91058 Erlangen (2) Helmholtz Zentrum Geesthacht Centre for Materials and Costal Research, Max-Planck-Straße 1 21502 Geesthacht

* [email protected]

Keywords: small angle scattering, synchrotron, precipitations Interest in additive manufacturing (AM) has dramatically expanded in the last several years, owing to the paradigm shift that the process provides over conventional manufacturing with the possibility to generate complex components just from CAD-data using a layer by layer process [1]. Until now there are no alloys available that were specially developed for additive manufacturing, therefore cast or wrought alloys are used. During additive manufacturing of the studied Nickel and Copper based precipitation hardening alloys crack formation is a serious issue. Generally the precipitation and resultant hardening effect is thought to govern crack susceptibility. The main aim of the experiments is to gain real-time information of the growth and dissolution dynamics of the precipitations. In previous investigations by Gilles et al [2] the early stage γ´ precipitation in a tungsten-rich nickel based alloy using SAXS has been investigated in the as-cast state. In the presented research the precipitations are investigated in the as-built AM state. Therefore additive manufactured samples are in-situ heat treated while the SAXS measurement. Figure 1 shows the scattering curves of additive manufactured CMSX-4 during in-situ quenching. An in-situ camber is in construction enabling future measurements of the phase fraction evolution under AM conditions. This knowledge is essential to optimize the chemical composition of alloys specially designed for AM.

148 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 88 Erlangen, Germany

1300°C 1274°C 1196°C 1078°C 800 966°C 865°C 769°C 683°C 605°C Intensity in arbitrary units arbitrary in Intensity

80 0,25 0,75 1,25 1,75 2,25 Q in inverse nanometers

Figure 1: Small Angle X-Ray Scattering detector image (left) and azimuthal integrated scattering curves (right) of additive manufactured Nickel based super alloy CMSX-4 measured during in-situ quenching from 1300°C to 600°C.

References [1] Körner C., International Materials Reviews, 2016, 61:5, 361-377 [2] Gilles et al, Alloys and Compounds, 2014, 612, 90-97

149 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 13 Erlangen, Germany

Stress-Strain Relation in tissues grown on functional surfaces

Gehrer, S.;1,*, Vurnek, D.; 1 Kaliman, S.; 1 Aliee, M.;1 Dudziak, D.;² Hoffmann, B.;3 Merkel, R.; 3 and Smith, A.-S.1,4

(1) PULS Group at the Institute for Theoretical Physics and EAM, FAU Erlangen-Nürnberg, Germany (2) Biologie Dentritischer Zellen, Hautklinik, Universitätsklinik Erlangen, Germany (3) Institute of Complex Systems-7: Biomechanik, Forschungszentrum Jülich, Germany (4) Division of Physical Chemistry, Ruđer Bošković Institute Zagreb, Croatia

*e-mail: [email protected]

Keywords: Functional Particle Systems, Multi-cellular Systems, Functional Surface

Epithelial sheets are active interfaces between different tissues and organs. Often they operate under high mechanical stress to which they quickly respond and adapt by changing its internal organization, proliferation and growth properties.1,2 To study this process we grow two-dimensional sheets of Madin-Darby canine kidney (MDCK II) epithelial cells on fibronectin coated polydimethylsiloxane (PDMS) elastomer chambers. The cells assemble into a circular confluent cell layer within a day. These round colonies are then exposed to a uniaxial mechanical stress by stretching the underlying PDMS gel for 10, 20 and 30%. The resulting deformation and reaction of the system is imaged using phase contrast microscopy in intervals of minutes to days. A comprehensive analysis of epithelial interface development is performed using a home written MATLAB routine.³ The overall shape of the colony as well as the morphology of individual cells and their connectivity is analyzed before and after stretching. We find that the initial response of the epithelial sheet is purely elastic and driven by the deformation of the underlying substrate to which the colony is attached. The connectivity of the cells does not change upon stretch. In the immediate period after the deformation is applied, the growth rate is affected significantly. However, after 24-48 hours of continuous deformation, the tissue adapts, and resumes a structure characteristic for the undisturbed layer.

References [1] Fredberg, J. et al. Ann Biomed Eng. 2009 37, 847-859. [2] Brunette, D.M. J Cell Sci. 1984 69, 35-45. [3] Kaliman S.; Jayachandran C.; Rehfeldt F.; Smith A-S.; Front Physiol. 2016 7, 551.

150 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 43 Erlangen, Germany

Excitonic transitions in heterostructured Mo and W transition metal dichalcogenides from first principles

Gillen, R. 1,*, Maultzsch, J. 2

(1) Institute of Solid State Physics, Technische Universität Berlin, Berlin, Germany (2) Department of Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany

*e-mail: [email protected]

Keywords: TMDCs, optical properties, DFT

Novel two-dimensional materials from the group of layered transition metal dichalcogenides (TMDC) have recently attracted scientific interest for their unusual physical properties, such as their strong optical response. Two possible ways to tailor the electronic and optical properties are (i) the combination of different TMDCs to form lateral and stacked heterostructures and (ii) creation of alloys containing different metal or chalcogen atoms. Recent experiments have suggested the occurrence of long-lived interlayer excitons in stacked heterostructures, with spatial separation of electrons and holes across the layers, possibly allowing for exploitation in solar cells [1,2]. Based on a recent work on single- and few-layer dichalcogenides [3], we show theoretical absorption spectra of bilayer MoSe2-WSe2 and MoS2-WSe2 heterostructures as obtained from ab initio simulations including electron-hole and spin-orbit interaction. In accordance with experimental observations, we find contributions related to interlayer excitons below the absorption onset of the monolayer materials. Our calculations allow us to estimate the binding energy of these electron-hole pairs to be on the order of 0.2 eV for both studied heterostructures

[4]. We will further show recent calculations of the absorption spectra of alloyed MoWS2 materials.

References [1] Rivera et al. Nature Comm. 2015 6, 6242 [2] Chen et al. Nature Comm. 2016 7, 12512 [3] Gillen et al. IEEE JSTQE 2017 23, 1; arXiv:1605.01972 (2016) [4] Gillen et al. in preparation

151 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 2 Erlangen, Germany

A widely applicable multi-component and multi-phase population balance model for simulating precipitation processes

Güldenpfennig A.1,*, Haderlein M.1, Hartig M.1 and Peukert W. 1

(1) Institute of Particle Technology (LFG), Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Multiscale Modeling and Simulation, Population balances, Precipitation

During precipitation of nanocrystals various processes such as mixing, nucleation and growth occur simultaneously on small time scales in the sub second range. Understanding the interaction of these complex processes is crucial when tailoring disperse properties of particles. Since experimental analysis methods are limited on such time scales, predictive models are powerful tools to understand and optimize processes. A multicomponent and multiphase population balance model was applied to simulate the simultaneous precipitation of competing solid phases. The model includes a symmetric mixing model for T-mixers which describes the mixing process in a numerically highly efficient way. Further, reaction equilibria of dissolved ion complexes in aqueous media are included to calculate supersaturations of respective solid phases. Solid formation is considered by solving the population balance equation for each solid phase simultaneously with the Direct Quadrature Method of Moments (DQMOM). This way the average particle size and the precipitated mass of each solid can be calculated [1-3]. For validation of the mixing model, simulated mixing times were compared to experimentally estimated times obtained from a mixer characterization by the Villermaux-Dushmann reaction. The hydrochemistry model was validated numerically by comparing its accuracy with the commercial software CHEAQS and experimentally by comparing measured and calculated pH values as a global parameter influenced by the liquid phase species distribution. The precipitation tool was further applied to the co-precipitation of Cu/Zn-hydroxy-carbonates as precursor phases for methanol synthesis catalysts. Here the model can help to predict and control the phase composition of the precursor phases which is known to be a crucial parameter for the final Cu-ZnO catalyst’s performance.

Acknowledgments: The authors acknowledge funding from the Deutsche Forschungsgemeinschaft (DFG) through the Cluster of Excellence Engineering of Advanced Materials and Clariant for fruitful discussions and financial support.

References: [1] Hartig M. et al., Chem. Eng. Sci. (2014) 109, 158-170 [2] Hartig M. et al., AIChE J. (2015) 61 (7), 2104–2116 [3] Haderlein M. et al., Comput. Chem. Eng. (2017) 98, 197-208

152 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 90 Erlangen, Germany

A New Algorithm for Material Optimization Applied on a Two-Scale Optimization Approach for Lattice Structures

Guess, T. 1,* and Stingl, M. 2

Department Mathematik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstr. 11, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Lattice structures, Two-scale Optimization

We present an algorithm, based on the idea of sequential convex programming [1], and its application in two-scale material optimization using lattice structures.

We apply the algorithm on a coupled two-scale material optimization problem in linear elasticity, based on [2]. For a chosen lattice base cell, we calculate the homogenized material tensor on a microscopic scale. We vary the shape of the base cell by thickness and rotational design parameters. For computational efficiency, we precompute a homogenized material catalog for a discretized set of design values beforehand. During the solution of the optimization problem, we interpolate the macroscopic material tensor for the design parameters on each finite element by a C1 interpolation model from the precomputed material catalog.

We focus on the effectiveness of the algorithm in terms of computational time as well as quality of the solution with respect to global lower bounds and alternative parametrizations by a various numerical examples.

References [1] Stingl, M.; Kočvara, M.; Leugering, G.; International Series of Numerical Mathematics 2009 Vol. 158, 275-295. [2] Bendsøe, M.; Kikuchi, N.; Computer Methods in Applied Mechanics and Engineering 1988 Vol. 71, 197-224.

153 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 44 Erlangen, Germany

Computational study of the fundamental properties of chalcopyrite semiconductors, for photovoltaic applications: Density Functional Theory

Moufdi Hadjab*, Samah Boudour, Fayçal Bouzid, Abderrahim Hadj Larbi, Hassene Nezzari

Research Center in Industrial Technologies CRTI, P. O. Box 64, Cheraga 16014, Algiers- Algeria

*e-mail: [email protected]

Keywords: Chalcopyrite; FP-LAPW; Physical properties; Thin-films solar cells; Wien2k. The scope of this work is the investigation of the physical properties of chalcopyrite materials using ab-initio methods in order to simulate a new structure of thin-films photovoltaic cells with high conversion efficiency. In the first framework, we obtained the results of calculations based on Density Functional Theory (DFT)1 using the full-potential linearized augmented plane wave method (FP-LAPW) as implemented in the WIEN2K computational package. For the exchange-correlation (XC) potential, the local density approximation (LDA)2 and the one of Wu and Cohen generalized gradient approximation (GGA-WC)3 were used to calculate the structural, electronic and optical properties of the chalcopyrite semiconductors materials Copper-Indium- Gallium-Selenium (CIGS). The semi-local Becke-Johnson (mBJ) potential and its modified form proposed by Tran and Blaha (TB-mBJ)4 were also used for electronic band structures and the linear optical properties. The achieved results were compared to computational works and other data acquired experimentally. The second framework, proposes a study of design, simulation and analysis to predict the possibility of achieving an ultra-thin-films based (CIGS) solar cells with high photovoltaic conversion efficiency using the popular solar cell simulation tool AMPS-1D.

Metal electrode (e.g., Aluminum) Sunlight

n-Zinc-oxide layer (windows layer)

- Electricity Buffer layer (e.g., CdS or MgZnO) +

p-Cu(InxGa1-x)Se2 (Absorber layer)

Molybdenum electrode (Back contact) (a) (b)

Glass or ceramic or plastic substrate

Figure 1: a) CIGS unit cell. Red = Cu, Yellow = Se, Blue = In/Ga, b) Configuration of a CIGS solar cell.

References [1] Hohenberg P.; Kohn, W., Phys. Rev. B, 1964, 136, 864. [2] Perdew J. P.; Wang Y., Phys. Rev. 1992, B 45, 13244. [3] Wu Z.; Cohen R. E., Phys. Rev. 2006, B 73, 235116. [4] Tran F.; Blaha P., Phys. Rev. Lett. 2009, 102, 226401.

1

154 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 9 Erlangen, Germany

The Influence of Chemical Change on Protein Dynamics: A Case Study with Pyruvate Formate-lyase 1,* 2 1,3 1,3 Hanževački, M.; Čondić-Jurkić, K.; Smith, A.-S.; and Smith, D. M.;

(1) Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička 54, 10000, Zagreb, Croatia (2) Research School of Chemistry, Australian National University, Canberra, ACT, Australia (3) Institute for Theoretical Physics, FAU Erlangen-Nürnberg, Staudtstraße 7, Erlangen, 91058, Germany

*e-mail: [email protected]

Keywords: Pyruvate Formate-Lyase, Molecular Dynamics, Proteins Pyruvate formate-lyase (PFL) is a glycyl radical enzyme requiring activation by a member of the radical SAM enzyme superfamily.[1] Such radical enzymes are receiving increased interest because of their possible applications in biotechnology.[2] PFL catalyzes the break down of pyruvate into formate and the acetyl group upon the addition of a thiyl radical located at Cys418.[3] The radical is initially stored at Gly734 is shuttled to Cys418 via Cys419. The addition of radical Cys418-S∙ to pyruvate leads to C-C bond dissociation, resulting with formation of formyl radical and acetyl-Cys418. The latter species acts as a temporary acetyl carrier and a reactant in the subsequent half-reaction with the second substrate CoA to produce acetyl-CoA. [4] Formation of AcCoA, the final product, closes the catalytic cycle of PFL.

The investigated aspect of this mechanism concerns the process that allows CoA to enter the active site, which is a prerequisite for the second half-reaction. The problem with this step is that the binding site of CoA is located at the protein surface, while the active site is buried in the protein interior.[5] In search for possible solutions to this problem, the PFL system was subjected to long unrestrained molecular dynamics simulations. The models representing the PFL system before and after the first half-reaction with pyruvate were used to examine the possible effect that acetylation of the enzyme has on the necessary conformational changes.

[1] Buis, J. M.; Broderick J. B. Archives of Biochemistry and Biophysics 2005, 433 (1), 288. [2] Zelcbuch, L.; et al. Biochemistry 2016, 55 (17), 2423. [3] Knappe, J.; Blaschkowski, H. P.; Gröbner, P.; Schmitt, T. Eur. J. Biochem. 1974, 50, 253. [4] Guo, J.-D.; Himo, F. J. Phys. Chem. B 2004, 108, 15347. [5] Becker, A.; Kabsch, W. J. Biol. Chem. 2002, 277, 40036.

155 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 63 Erlangen, Germany

Nanomorphology characterization of organic binary and ternary solar cells using energy-filtered transmission electron microscopy

1,* 1 2 2 2 2 1 Harreiß, C. , Rechberger, S. , Zhang, C. , Ke, L. , Ameri, T. , Brabec, C.J. and Spiecker E.

(1) Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), Friedrich-Alexander Universität Erlangen-Nürnberg, Cauerstr. 6, 91058 Erlangen, Germany (2) Institute of Materials for Electronics and Energy Technology, Friedrich-Alexander Universität Erlangen-Nürnberg, Martensstr. 7, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: organic solar cells, morphology, energy-filtered TEM The morphology of organic bulk heterojunction (BHJ) solar cells highly influences the device performance and efficiency. Therefore it is an important factor that needs to be investigated in order to gain a better understanding of the devices. Energy-filtered transmission electron microscopy (EFTEM) is a powerful analytical technique to characterize the nanomorphology of the active layer concerning its material distribution. Here we present the results of an organic binary BHJ solar cell based on a new mid band gap polymer (OPV-46) as electron donor and [1] [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM) as electron acceptor. In order to further improve the device performance of such organic binary solar cells silicon phthalocyanines (SiPCs) are incorporated as near IR sensitizers in the polymer:fullerene host system. The effects of this incorporation on the nanomorphology are investigated by EFTEM (cf. Figure 1) and correlated to the device performance.

Figure 1: TEM bright field images (first row) and elemental maps based on energy-filtered TEM imaging

of sulfur (middle row) and of carbon (last row): binary OPV-46:PC70BM (a-c) and ternary films blended with sensitizer SiPC-3 (d-f).

References [1] Ke, L.; doctoral thesis, Friedrich-Alexander-Universität Erlangen-Nürnberg 2017.

156 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 31 Erlangen, Germany

Phason modes in intrinsic colloidal quasicrystals

Hielscher, J.;1,* Martinsons, M.;1 Schmiedeberg, M.;1 and Kapfer, S.1

(1) Theoretische Physik I, FAU Erlangen-Nürnberg, Staudtstr. 7, 91058 Erlangen

*e-mail: [email protected]

Keywords: colloids, quasicrystals, phonons, phasons

In the higher-dimensional space image of quasicrystals, phasons, i. e. displacements perpendicular to the physical space, occur as additional hydrodynamic degrees of freedom. The excitation of an extended phasonic mode corresponds to a concerted rearrangement of particles with possibly large distances in physical space. We conduct Brownian dynamics annealing of colloidal quasicrystals with short-ranged pair potential interactions. We find that phonon and phason modes are excited thermally. A finite phononic strain is found to be pinned by phasonic excitations even after cooling down to zero temperature. By embedding into extended higher-dimensional space, the phononic and phasonic movements can be separated. We then apply a multi-mode harmonic ansatz [1] to extract the phasonic excitation spectra which are underlying the non-local defect patterns. We observe the decay of an artificial phason wave into thermal equilibrium. The inherent decoherence of the phason field points to fundamental limitations of description of phasonic excitations by low-frequency plane waves.

Figure 1: Phasonic flips (squares) and the underlying phasonic field (as reconstructed by a multi-mode fit [1]) in a thermally annealed decagonal quasicrystal (dots and squares). References [1] Hielscher, J; Martinsons, M.; Schmiedeberg, M.; Kapfer, S. C. J. Phys. Cond. Matt. 2017 29, 094002.

157 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 17 Erlangen, Germany

Development of Sonosensitive Poly-(L)-lactic Acid Nanoparticles

Hiltl, P.-T. 1*, Fink, M.2, Rupitsch, S.2, Ermert, H.2 and Lee, G.1

(1) Departement of Chemistry and Pharamcy, Division of Pharmaceutics, University of Erlangen, Cauerstrasse 4, Bld No 6, 91058 Erlangen (2) Department of Electrical, Electronic and Communication Engineering, Division of Sensor Technology, University of Erlangen, Paul-Gordan-Strasse 3/5, 91052 Erlangen

*e-mail: [email protected]

Keywords: Inertial Cavitation, PLLA Nanoparticle, Ultrasound

Cancer therapy normally has serious side- effects, which is why new treatments like targeted drug delivery are investigated to lower the overall dose and achieve higher local concentration. Nanoparticles with surface bound drugs accomplish accumulation due to the EPR effect in the tumourous tissue. We produce poly-(L)-lactic acid nanoparticles with a size of 110 nm which would show the wanted EPR effect. After freeze drying and reconstitution they show inertial cavitation under ultrasound pressure which could be used to release drug from the NP surface directly into the tumor by using medicinal ultrasound. To measure acoustic emission a hydrophone in a water bath was positioned 90° to the ultrasound transducer aimed to a cuvette containing sample. For inertial cavitation frequencies much lower than 500 kHz are normally required which are poorly focusing. To improve focusing, more than 500 kHz and nuclei in the range of micrometers are needed. Using higher frequencies leads to necessitation of either bigger particles or higher pressures. However, due to thermal and mechanical effects on biological tissue high pressure is unsuitable for clinical application. Our PLLA NP synthesized via solvent evaporation technique show reproducible inertial cavitation at moderate acoustic pressure of 1.5 MPa and high frequencies of 800 kHz over 10 min. In this contribution we characterize the designed particles and present the production process. Furthermore, we show the inertial cavitation of the nanoparticles at different acoustic pressures and frequencies which are commonly used in clinical ultrasound and compare them with brand products.

Figure 1: Schematic drawing of the setup used for determination of the inertial cavitation References [1] Kwan, J. J.; Graham, S.; Coussios, C. C. Phys Rev E. 2015 92, 023019. [2] Chen, W.-S.; Matula, T. J.; Brayman, A. A.; Crum, L. A. J. Acoust. Soc. Am 2013 113, 643-651.

158 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 69 Erlangen, Germany

Crack formation in carbon black/ionomer layers

Hoffmann, E. 1,*, Zhang, S. 1, Thoma, M. 1, Damm, C. 1 and Peukert, W. 1

(1) Institute of Particle Technology, FAU Erlangen-Nürnberg, Germany

*e-mail: [email protected]

Keywords: PEM fuel cell, film formation, cracking The electrodes of proton exchange membrane fuel cells (PEMFCs) consist of catalyst particles on carbon black (CB) carrier particles imbedded in an ionomer network. The aim of this work is to investigate the processes occurring during film formation and drying of PEMFC electrodes, especially in terms of cracking. The layer structure is a function of the suspension properties (inter-particle and particle-medium interactions) and film formation parameters (substrate wetting, film thickness) and significantly impacts PEMFC efficiency.

CB as well as CB/ionomer suspensions in a solvent matrix (alcohol and water) are produced and deposited on a substrate via doctor-blading. We found that a critical coating thickness exists for CB layers, below which crack-free layers are obtained. With CB 1 (low surface area) cracks arise for a layer thickness > 7-10 µm (see Fig. 1). Moreover, the type of CB has a significant impact on suspension and layer properties. CBs with a high specific surface area (CB 2 in Fig.1) form large aggregates (CB 1: x50,3 = ca. 0.1 µm; CB 2 x50,3 = ca. 7 µm (when applying ultrasound)) and result in higher viscosities of the suspension (CB 1: ̇γ1000 1/s = 14 mPa∙s;

CB 2: ̇γ1000 1/s = 253 mPa∙s), which leads to thicker layers with more cracks. At given CB type and concentration with increasing ionomer content the critical coating thickness increases, as the ionomer acts as a “soft particle” within the layer. When adding ionomer, the drying stress is not released by appearance of cracks but by deformation of the ionomer particles. [1, 2]

Figure 1: Dry layer thickness of carbon black layers with different types of carbon black

References [1] Tirumkudulu, M.; Russel, Langmuir 2004 29, 2947-2961. [2] Singh, K.; Tirumkudulu, M. PRL 2007 98, 218302.

159 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 5 Erlangen, Germany

Effects of a flexible pinning on the statics and dynamics of a thermalized thin sheet

Janeš, J. A.;1,2,* , Schmidt, D.;1 and Smith, A.-S.;1,2

(1) PULS Group, Department of Physics & Cluster of Excellence: EAM, Friedrich-Alexander University Erlangen-Nürnberg, Nägelsbachstrasse 49b, 91052 Erlangen, Germany (2) Department of Physical Chemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, Croatia

*e-mail: [email protected]

Keywords: 2D interfaces, fluctuations, membranes, modeling and simulations

Mechanical characteristics of freely suspended 2D membranes are commonly determined from their fluctuation spectrum [1]. However, this task is significantly more challenging for the case of membranes attached by proteins to underlying scaffolds. Actually, a complete theoretical description of the effect of a pinning on the dynamic correlations in a membrane is still missing. The difficulty lies in the coupling of plane wave modes by the bond [2]. Here we rectify this situation by modeling the static and dynamic correlations by several complimentary analytic methods. We construct a complete theoretical framework for the problem in question and validate our approach by obtaining excellent agreement with the explicit Langevin simulations [3].

References [1] Monzel, C.; Schmidt, D.; Kleusch, C.; Kirchenbüchler, D.; Seifert, U.; Smith, A.-S.; Sengupta, K. Nat. Commun. 2015 6, 8162. [2] Schmidt, D.; Bihr, T.;Seifert, U.; Smith, A.-S. EPL. 2012 99, 38003. [3] Janeš, J.A.; Schmidt, D.; Smith, A.-S. J. Stat. Mech. 2017 submitted

160 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 49 Erlangen, Germany

Thin-Film Transistors from Group IV Nanoparticles

Rumler, M.1; Meric, Z.1; Weis, S., Mehringer, C.2; Wergen, L.2; Jank, M.P.M.3*; Peukert, W.2; Frey, L.1,3

(1) Chair of Electron Devices, FAU Erlangen-Nürnberg, Cauerstr. 6, 91058 Erlangen, Germany (2) Institute of Particle Technology, FAU Erlangen-Nürnberg, Cauerstraße 4, 91058 Erlangen, Germany (3) Fraunhofer Institute for Integrated Systems and Device Technology IISB, Schottkystr. 10, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: nanoparticles, silicon, germanium, thin-film transistor, carrier transport, surface engineering Dispersions of silicon and germanium nanoparticles allow for the processing of semiconducting thin films from solution. As the material formation is separated from layer deposition, high temperatures can be employed for the growth of high-quality, crystalline particles [1] whereas the fabrication of considerable devices can be executed at 150°C to 350°C or even below [2]. Within EAM we investigated into the challenges and prospects of particle-based group IV semiconductors for application in thin-film transistors. Electrical characterization of TFTs reveals drain currents decreasing stronger than expected from geometrical considerations when increasing the channel length (Fig. 1 a)). This is most likely attributed to the intrinsic porosity of nanoparticle thin films. Furthermore, electrical conduction is guided by particle-particle interactions as well as the large integrated particle surface defining the relevant carrier densities inside the system. Based on materials/contact optimization (Fig. 1 b)) we show how to separate contact effects from the electrical behavior of the semiconductor layer and discuss the underlying carrier transport mechanisms. The electrical behavior of the particle surfaces could be controlled by dedicated prost-processing schemes. Depending on the surface coating, and temperature of the post process, carrier densities along with corresponding device parameters as well as the conduction type of the transistors could be controlled [3]. Besides ambipolar devices, the realization of CMOS NOT gates from Ge nanoparticles will be presented (Fig. 1 c)).

Figure 1: a) W/L-normalized drain currents of Si nanoparticle TFTs depending on channel geometry; b) Output characteristics of Si nanoparticle TFTs employing different contact schemes at identical gate

overdrive (VG-VT); c) Definition of n- and p-type Ge nanoparticle TFTs by thermal post processing [3] References [1] Körmer, R. et al., J. Aerosol Sci. 2010 , 41 , 998; [2] Weiss, S., et al., small 2011 7, 2853-57; [3] Meric, Z., et al., Phys. Chem. Chem. Phys. 2015, 17, 22106

161 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 46 Erlangen, Germany

Sample Preparation Technique Development for Atom Probe Tomography Characterization of Nanoporous Materials and Nanoparticles

Johnson, K.; 1, 2,*, Felfer, P.; 1 and Gorman, B.; 2

(1) First Affiliation: Material Science, Friedrich-Alexander-Universität Erlangen-Nürnberg, Martensstraße 5 91058 Erlangen, Germany (2) Second Affiliation: Material Science, Colorado School of Mines, 15th St 920, 80401 Golden, Colorado USA

*e-mail: [email protected]

Keywords: Atom Probe Tomography, Nanoporous, Nanoparticles

Atom Probe Tomography (APT) can produce 3D chemical analysis on the atomic scale and there is an increasing interest for the analysis of nanomaterials including nanoporous materials and nanoparticles (NPs) but there has been limited success with special geometry, non-bulk, nanomaterials.[1] [2] In this work several APT sample preparation techniques were trialed on zirconia, goethite, platinum and nanoporous gold (NPG) NPs and copper aluminum (CuAl) nanoporous alloys, the main characterizations were performed using scanning electron microscopy (SEM) and Focused Ion Beam (FIB). Electrophoresis and NP encapsulation methods were trialed for NPs and copper and nickel metallization parameters were tested for the filling of the NPG and CuAl porous networks. [3][4] Optimal success was achieved with a CuAl 50wt% aluminum nanoporous alloy after a 10 minute 2.3V nickel electrodeposition by analyzing 136 million ion hits during a laser pulse mode APT analysis.

A B C

Figure 1: Images (a)-(c) demonstrate the continuous progression from after the pore filling of a CuAl nanoporous alloy with nickel electrodeposition; FIB Cross section (a), Pillar lift out (b) and final FIB milling to create an APT specimen (c). References [1] Gault, B.; Moody, M.; Atom Probe Microscopy. Springer Science & Business Media 2012. [2]Felfer, P.; Li, T.; Ultramicroscopy. 2015 159, 413-419. [3] Mouton, I.; Printemps, I. Ultramicroscopy 2017, 182, 112-117. [4] El-Zoka, AA.; Langelier, B. Mater. Charact. 2017 128, 269-277.

162 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 94 Erlangen, Germany

Atom-by-atom nanoparticle analysis using high-field methods: in-situ sample preparation using the ES-FIM set-up

Josten, Jan Paul 1,* and Felfer, Peter 1

(1) Department Materials Science and Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute I, Martensstraße 5, 91058 Erlangen, Germany

*[email protected]

Keywords: field ion microscopy, atom probe tomography, electrospray deposition, nanoparticles, in-situ sample preparation

Atom probe tomography (APT) of nanoparticles has shown great potential with its atomic resolution for chemical and structural characterization [1]. In order to contribute significantly to nanoparticle (NP) research, the challenge of reliable and reproducible preparation of clean and well defined field emitters from NP samples has yet to be met for high field methods like APT and field ion microscopy (FIM). Based on an approach where single NPs have been attached to pre field evaporated field emitters directly in the analysis chamber (in-situ) [2,3], we developed an FIM set-up (ES-FIM) where NPs can be introduced into ultra-high vacuum (UHV) as an aerosol through a differentially pumped transfer system that enables the deposition of single NPs onto clean metal tip field emitters. The set-up is illustrated in Figure 1. As the primary means to create the aerosol, electrospray ionization is used. In contrast to the NP source (multiple expansion cluster source) used in ref. [2,3], electrospray deposition is able to deposit a broad range of colloidal nano-sized solids without a limitation to the fabrication routine [4-6]. NP samples prepared by the ES-FIM are characterized using high field methods (APT, FIM) and results are presented.

1

2 3 4

Figure 1: overview of the ES-FIM set up: main chamber (1), sample holder ( 2), Detector (3), differentially pumped transfer system with electrospray unit (4). References [1] Tedsree, K. et al., Nat. Nanotechnol. 2011 6, 302-307. [2] Castro, T. et al., J. Vac. Sci. Technol. 1989 7, 2845-2849. [3] Lovall, D. et al., Phys. Rev. B. 1998 58, 15889-15896. [4] Fenn, J. et al.; Science. 1998 246, 64-71. [5] Lenggoro, I. W. et al., Langmuir. 2002 18, 4584-4591. [6] Swarbrick, J. C. et al., Appl. Surf. Sci. 2006 252, 5622-5626.

163 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 3 Erlangen, Germany

Cooperative Motion of Molecular Motors

Jung, D.1,2,*, Blackwell, R.1,2 and Smith, A.1,2

(1) Friedrich-Alexander University: Theory I, PULS group, Erlangen (2) Cluster of Excellence Engineering of Advanced Materials, Erlangen

*e-mail: [email protected]

Keywords: molecular motors, traffic effects, simulation

A molecular motor in general is simply a contraption of molecular size capable of directed mechanical work. The applications of such motors would be numerous in medicine and manufacturing. Their inspirational prototypes are found in all animal life forms, fulfilling such diverse roles as powering cell mitosis, propelling sperm cells, contracting muscles or transporting neurotransmitters. Recent theoretical approaches in modeling these biological machines tend to agree on common principles for how a motor might move, but otherwise allow for a number of different rate formulations to generate explicit stochastic motor trajectories. In comparing the dynamics produced by different rate formulations, we discovered peculiarities inherent to each of them. When allowing for hard-shell motor-motor collisions (crowded regime), the rate formulations vary in the number of motors needed to achieve maximum velocity and in the degree by which transport is slowed down with respect to the unloaded motor. When motors interact only via the cargo but do not collide, certain rate formulations cause loaded motor groups to travel faster than an unloaded motor. Testing whether this effect occurs in vitro may be a good way to narrow down the options in terms of viable rate formulations for modeling specific motors.

Figure left: Influence of motor stiffness k on groups of motors interacting via hard-shell interactions. Three different rate formulations are shown called D-AsEx (full lines), P-AsEx (dotted, slightly below D-AsEx) and Glauber (dashed). Right: Groups greater or equal to 2 non-colliding motors can move a cargo faster than the single unloaded motor moves under D-AsEx rates, but not when using either of the other rates. The speed-up can be 30% or more.

164 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 7 Erlangen, Germany

Dynamics of self-induced structuring in an epithelial interface layers

Kaliman, S.1,*, Damir, V.1, Alyee M.1, Wollnik, C.2, Rehfeldt, F.2, Duzdiak D.3, and Smith A.-S.1

(1) PULSE group; Cluster of Excellence; Engineering of Advanced Materials, FAU Erlangen-Nürnberg (2) 3rd Institute of Physics-Biophysics, University of Göttingen (3) Department of Dermatology, University Hospital at FAU Erlangen

*e-mail: [email protected]

Keywords: Simulation, Cell packing, Lloyd relaxation Epithelial sheets are monolayers of epithelial cells whose biological role is to provide protection and separate organs from the surroundings. From biophysical point of view, epithelial cells are adhering particles with a diameter of 10-5 m that spontaneously organize in large structures with a diameter of 10-2 m when seeded in-vitro. This organization, governed by cell divisions and cell movements, is always a 2D circular structure with a high cell density in the central region and decaying cell density toward the edge of the agglomerate. Yet, the exact distribution of the cell density within those structures was never understood. By growing such colonies in a controlled environment, we analyze the dynamics of the emerging 2D structure, determine the proliferation rate as a function of the local cell density and velocity distribution within the cluster. We use this data as input parameters for our simulation where biological cells are represented by the Voronoi tessellation [1]. Seeds of the tessellation are initially randomly distributed and consequently the tessellation is relaxed by the Lloyd's algorithm. One step of the simulation corresponds to four hours during which cells have a probability to divide and velocity that depends on the cell position and local surrounding. Upon eight days those structures spontaneously organize into circular sheet with the bulk and the edge region. We successfully reproduce cell density distribution throughout the cluster in real time and investigate necessary conditions for such organization.

Figure 1: Typical cell density distribution profile in spontaneously structured epithelial sheet.

References [1] Kaliman, S.; Jayachandran C.; Rehfeldt F.; Smith, A.-S.. Front Physiol. 2016 7: 511.

165 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 56 Erlangen, Germany

Novel p-type anodic NiO sponges for photocatalytic applications

Killian, M.S. 1,*, Ahmadloo, F. 1, Winhard, B. 1 and Schmuki, P. 1,2

(1) Department of Materials Science, Friedrich-Alexander University Erlangen-Nürnberg, Martensstr. 7, 91058 Erlangen, Germany (2) Department of Chemistry, King Abdulaziz University, Jeddah, Saudi Arabia

*e-mail: [email protected]

Keywords: DSSC, p-type, NiO, anodic nanostructures

Dye sensitized photocathodes have the potential to significantly contribute to the efficiency of the solar light-to-current conversion in photoelectrochemical cells (PECs).[1] Suitable photoactive cathodes for hydrogen production should consist of earth-abundant elements and show high incident photon-to-current conversion efficiencies (IPCEs). NiO is a photostable and cheap material, has suitable band positions for catalyzing hydrogen evolution and shows sufficiently high photocurrents.[2] Anodic nanostructures facilitate fast charge separation and a directional charge transport. We developed a novel, highly porous, sponge-like nanoarchitecture of NiO, reaching layer thicknesses of up to 6.5µm. XPS and XRD confirmed that the oxide composition is NiO. The nanosponge shows high thermal stability, the surface morphology was not altered even after exposure to 600°C. The oxide exhibits p-type behaviour and a bandgap of 3.4eV. Several dyes for p-type photocatalytic materials were tested in combination with the newly developed NiO nanosponge. The developed dye sensitized p-type NiO based cathodes are promising for application in tandem cells for photocatalysis and water splitting.

Figure 1: Ion milled SEM cross section of anodic NiO nanosponge (sub-maximum thickness). References [1] Li, L.; Gibson, E.A.; Qin, P.; Boschloo, G.; Gorlov, M.; Hagfeldt, A.; Sun, L. Adv. Mater. 2010, 22, 1759. [2] Odobel, F.; Pellegrin, Y. J. Phys. Chem. Lett. 2013, 4, 2551.

166 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 20 Erlangen, Germany

Water soluble ferrite and cobalt - ferrite nanoparticles with a novel surface coating method Kizaloglu, Melek1*; Portilla, Luis2; Hümmer, Julian3; Meyer, Karsten3; Hock, Rainer4; Halik, Marcus2;

Kryschi, Carola1 (1) Department of Chemistry and Pharmacy, Chair of Physical Chemistry 1, Egerlandstr. 3, 91058, Erlangen (2) Department of Materials Science and Engineering, Institute of Polymer Materials, Martenstr. 7, 91058, Erlangen (3) Department of Chemistry and Pharmacy, Chair of Inorganic and General Chemistry, Egerlandstr. 1, 91058, Erlangen (4) Department of Physics, Chair of Crystallography and Structural Physics, Staudtstr. 3, 91058, Erlangen *e-mail: [email protected] Keywords: ferrite nanoparticles, cobalt – ferrite nanoparticles, positive charge coating

Ferrite and cobalt-ferrite nanoparticles have significant attention in various fields from technology to biomedical applications because of their exclusive physical and chemical properties. In this study, superparamagnetic ferrite and cobalt-ferrite nanoparticles with a size range between 5 nm to 15 nm were synthesized via co-precipitation. We wish to present a new ligand addition method of ferrite and cobalt-ferrite nanoparticles which results a positive charge on the surface of the nanoparticle. As a ligand 1-methyl-3-(dodecylphosphonic acid) imidazolium bromide (Imidazolium-PA) was used. Uncoated ferrite and cobalt-ferrite nanoparticles are unsoluble in water. But after ligand addition they become water soluble with positively charge on the surface. Also this ligand coating prevents the agglomeration of the nanoparticles. The average size, size distribution, morphology, crystallinitiy, colloidal stability and magnetic properties of the prepared nanoparticles were studied using high resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), superconducting quantum interference device (SQUID), zeta-potential analysis, Fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRD). Our studies demonstrate that the as-synthesized ferrite and cobalt-ferrite nanoparticles have a highly positive surface charge and a good water solubility. Due to the good water solubility and effective positive charge coating of the ferrite and cobalt-ferrite nanoparticles, they can be used in several applications in biomedicine. References [1] Massart, R.; IEEE Transactions on Magnetics. 1981 17 (2), 247–1248. [2] Portilla, L.; Functionalization of Metal Oxide Nanostructures via Self – Assembly Implications and Applications (Doctoral Dissertation), 2017.

167 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 53 Erlangen, Germany

Adsorption and Thermally Induced Metalation of Carboxy-Porphyrins on MgO Nanocubes

Kollhoff F. 1,*, Schneider J. 2, Berger T. 2, Diwald O. 2 and Libuda J.1

(1) Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU); Egerlandstraße 3, 91058 Erlangen (2) Chemistry and Physics of Materials, Universität Salzburg; Jakob-Haringer-Strasse 2a, 5020 Salzburg

*e-mail: [email protected]

Keywords: nanoparticles, porphyrin, infrared Metal oxide surfaces functionalized with organic molecules are of great interest for various applications, for example in catalysis, in sensor technology or in solar cells. For devices such as dye-sensitized solar cells, functionalization with porphyrins is a common procedure. However, the influence of the surface structure of the oxide on the binding to the linker groups and the reactivity of the organic molecules are poorly understood, especially for particulate systems. In a previous research effort we explored the reactivity of the non-functionalized free-base tetraphenyl-porphyrin (2HTPP) on well-defined MgO nanocubes of very small (~ 10 nm) size and found metalation by Mg ions from defect sites such as particle edges.[1] Additionally, the concentration-dependent adsorption behaviour was evaluated using various methods for both carboxy-functionalized and unfunctionalized porphyrins. [2] In this project, we investigated the binding of carboxy-functionalized free-base porphyrins to said MgO nanocubes. Free-base porphyrins functionalized with a single (MCTPP) and four carboxy-groups (TCPP) were adsorbed from solution on MgO nanocubes. The adsorption behaviour was analysed using diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) as well as UV-VIS spectroscopy. Specifically, we explored the behaviour upon heating via temperature-programmed DRIFTS. In contrast to non-functionalized 2HTPP, we found that MCTPP and TCPP bind to the oxide surfaces via the carboxylic acid groups. Interestingly, no indications for metalation were found for either sample at room temperature. Upon heating, however, we observed partial metalation for TCPP. MCTPP even showed almost complete metalation after heating. In view of the fact that complete metalation occurs for 2HTPP on the nanocubes, this finding demonstrates the influence of the surface structure and the adsorption geometry on the metalation reaction.

Figure 1: Schematic of adsorption and metalation of MCTPP on MgO NCs References [1] Schneider J.; Kollhoff F.; Bernadi J.; Kaftan A.; Libuda J.; Berger T.; Laurin M.; Diwald O. ACS Appl Mater Interfaces, 2015 7, 22962-9 [2] Schneider J.; Kollhoff F.; Schindler T.; Bichlmaier S.; Bernadi J.; Unruh T.; Libuda J.; Berger T.; Diwald O. J. Phys. Chem. C, 2016 120 (47), 26879–26888

168 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 76 Erlangen, Germany

Screening and selection of various solvents for selective oxidation of glucose to formic acid

Kumpidet, C.1,*, Albert, J. 1 and Wasserscheid, P 1

(1) Lehrstuhl für Chemische Reaktionstechnik der Universität Erlangen-Nürnberg, Egerlandstrasse 3, D-91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: polyoxometalate, oxidation, formic acid, OxFA process

Different solvents for the homogeneously catalyzed oxidation of glucose to formic acid (OxFA process) have been selected based on the 12 Principles of Green Chemistry. Afterwards, they have been tested in a 10-fold screening plant using the homogeneous Keggin-type polyoxometalate (H8PV5Mo7O40) (HPA-5) as a homogeneous catalyst (see Figure 1). Each reaction was carried out in 20 mL Hastelloy C276 batch type reactor. In order to evaluate the different solvents, the optimized system of HPA-5 in water, which showed high selectivity for formic acid under mild conditions [1] was set as a benchmark. All experiments were performed o at 90 C under 20 bar O2pressure and stirred with 1000 rpm for 24 h reaction time. The most promising solvents besides water were methanol, dimethylsulfoxide, n-butanol and ethanol. They also showed excellent selectivity to formic acid in the liquid product phase [1],[2],[3]. Only minor amounts (below 5%) of side products such as acetic acid and oxalic acid could be obtained by Ion Chromatography (IC). In methanol as a solvent, the reaction reaches to 100 % conversion with 65% yield of formic acid.

Figure 1: Keggin-type polyoxometalate (H8PV5Mo7O40) (HPA-5) a) Keggin-type Structure, b) synthesized HPA-5

References [1] Reichert, J.; Brunner, B; Jess, A; Wasserscheid, P. and Albert, J. Energy Environ. Sci. 2015 8, 2985-2990. [2] Albert, J.; Wölfel, R.; Bösmann, A.; Wasserscheid, P. Energy Environ. Sci. 2012 5, 7956-7962. [3] Albert, J.; Wasserscheid, P. Green. Chem. 2015 17, 5164-5171.

169 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 87 Erlangen, Germany

The role of clusters in creep resistant magnesium alloys

Lamm, S. 1,*, Amberger, D. 1 and Felfer, P.1

(1) First Affiliation: Department General Materials Properties, Friedrich-Alexander University Erlangen-Nuremberg, Martensstraße 5, 91058 Erlangen *e-mail: [email protected]

Keywords: magnesium alloy, creep, clustering

Due to its low density and high specific strength, magnesium alloys are very promising materials for lightweight applications. In the last years, magnesium alloys also gained interest for automotive powertrain applications where good mechanical properties at elevated temperatures up to 190°C are required. The work presented here, compares the microstructures and mechanical properties of a series of magnesium alloys (AZ91+Ca and MRI230D) after creep deformation. A focus of the presented work will be lying on the analysis of atom probe data and the extraction of clusters from the reconstructed microstructures.

Figure 1: Ca-rich clusters in AZ91+3Ca in as cast condition. References [1] Backes, B.; Durst, K.; Amberger, D.; Göken, M. Metall Mater Trans A 2009 Vol.40A, 257-261. [2] Amberger, D.; Eisenlohr, P.; Göken, M. Acta Mater 2012 Vol.60, 2277-2289. [3] Felfer, P.; Ceguerra, A.V.; Ringer, S.P.; Cairney, J.M. Ultramicroscopy 2015 Vol.150, 30-36.

170 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 58 Erlangen, Germany

New routes towards efficient CuO-based p-DSSCs – Optimization of device interfaces Langmar, O.;1,* Ganivet, C. R.;2 Torres, T.;2 Costa, R. D.;3 and Guldi, D. M.1

(1) Department of Physical Chemistry and Pharmacy & Cluster of Excellence Engineering of Advanced Materials (EAM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany (2) Universidad Autónoma de Madrid, C/Francisco Tomás y Valiente 7, 28049 Madrid, Spain (3) IMDEA Materials Institute Eric Kandel 2, 28906 Getafe, Madrid, Spain

*e-mail: [email protected]

Keywords: p-type dye-sensitized solar cell, CuO, photocathode

Nickel(II)oxide (NiO) is the most studied photocathode material for p-type dye-sensitized solar cells (p-DSSCs), but efficiencies are still moderate due to some inherent drawbacks of this material.[1] Thus, the search for new p-type semiconductors, in order to replace NiO, is of high interest. In recent years, copper(I)delafossites (CuXO2, X = Cr, Ga, Al) have emerged as a competitor due to superior properties, such as higher achievable open-circuit voltages (Voc). Still major issues remain, due to expensive synthesis methods, which produce large particle sizes limiting the amount of dye loading.[2] Recently, we have revisited the suitability of copper(II)oxide (CuO) as photocathode material, which shows higher conductivities and equal valence band energies with respect to NiO.[3] Optimized CuO-based p-DSSCs based on novel electron-accepting phthalocyanine sensitizers showed efficiencies of 0.11%.[4,5] In order to further improve the efficiency of CuO-based p-DSSCs we present herein two novel approaches. Firstly, we developed photocathodes based on small CuO nanoparticles, which showed enhanced dye loadings and, thus, higher achievable photocurrents compared to previous studies. - - Secondly, we screened the suitability of various additives and ionic liquids for the I /I3 -based electrolyte, which lead to an overall increase of the device performance for the optimized electrolyte solution. Standard device characterization was supported by electrochemical impedance assays, which provided a detailed insight into charge injection and recombination properties. To this end, optimized devices show efficiencies of 0.15%, which are competitive to p-DSSCs based on CuXO2. References [1] Odobel, F.; Pellegrin, Y. J. Phys. Chem. Lett. 2013 4, 2551 - 2564. [2] Mingzhe, Y.; Draskovic, T. I.; Wu, Y. Phys. Chem. Chem. Phys. 2014 16, 5026 - 5033. [3] Zhang, Q.; Zhang, K.; Xu, D.; Yang, G., Huang, H.; Nie, F.; Liu, C.; Yang, S. Prog. Mater. Sci. 2014 60, 208 - 337. [4] Langmar, O.; Ganivet, C. R.; Lennert, A.; Costa, R. D.; de la Torre, G.; Torres, T.; Guldi, D. M. Angew. Chem., Int. Ed. 2015 54, 7688 - 7692. [5] Langmar, O.; Ganivet, C. R.; Costa, R. D.; de la Torre, G.; Torres, T.; Guldi, D. M. Nanoscale 2016 8, 17963 - 17975.

171 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 37 Erlangen, Germany

Flexible Thermoplastic Elastomer Optical Fibers for Sensing of Extreme Deformations

Leber, A.;1,2* Cholst, B.;1 Sandt, J.;1 Vo ge l , N . 2 and Kolle, M. 1

(1) Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA (2) Department of Chemical and Biological Engineering, Friedrich-Alexander-University of Erlangen-Nuremberg, 91058 Erlangen, Germany

*[email protected]

Keywords: optical fibers, soft materials, sensing

Optical fibers are promising sensors due to their advantageous properties such as low weight, immunity to electromagnetic interference, and the ability to sense across large distances with a single unit.[1] However, standard optical fiber materials, such as silica glass or poly(methyl methacrylate) exhibit low deformability, prohibiting their use in mechanically demanding settings.[2] Here, we report the development of an optical fiber sensor sensitive to mechanical stimuli based on reversibly deformable thermoplastic elastomers. The fibers are fabricated by a custom one-step co-extrusion process with km-scale material throughput. The selected core and cladding materials exhibit a contrast in refractive index, resulting in light guiding in the fibers by total internal reflection. The wavelength-dependent attenuation coefficient ranges from 0.13 dB/mm at 475 nm to 0.05 dB/mm at 875 nm. The fibers are extremely stretchable with an elongation at break of 480 %. In a mechano-optical characterization, a strong wavelength-dependent correlation between the transmission of light and deformation by stretching, bending, and indenting is found. The relationship persists during large cyclic deformation. Building upon these findings, we developed an intensity-based optical fiber sensor for extreme deformations that can be integrated in carrier textiles. In an exemplary application, a wearable sensing system is employed to monitor human body movement.

Figure 1: Flexible optical fiber. Radiation of guided light occurs at extreme bends and the fiber end face. References [1] Selm, B.; Gurel, E. A.; Rothmaier, M.; Rossi, R. M.; Scherer, L.J. J. Intell. Mater. Syst. Struct. 2010, 21, 1061-1071. [2] Kalli, K.; Webb,D. J. in Adv. Fiber Opt., 2011, pp. 345–388.

172 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 62 Erlangen, Germany

Iodine-Pseudohalogen Ionic Liquid-Based Electrolytes for Quasi-Solid-State Dye-Sensitized Solar Cells Lennert, A.; 1,*, Sternberg, M.2 Meyer, K.2; Costa, R.1,3 and Guldi, D. M.1

(1) Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany (2) Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany (3) IMDEA Materials Institute Eric Kandel 2, 28906 Getafe, Madrid, Spain *e-mail: [email protected]

Keywords: ionic liquids, quasi-solid-state electrolyte, quasi-solid-state dye-sensitized solar cells

For more than two decades dye sensitized solar cells (DSSC) have kept researchers interest with their potential in the field of green, renewable energies. Easy fabrication out of low cost materials render them a promising candidate for commercialization to supply future energy demands.[1] To circumvent this and to create long lasting devices the concept of solid state electrolytes has been at the focal points in recent years.[2] To this end, ionic liquids are a popular choice due to their low volatility and easy handling. In this contribution novel symmetrically alkyl-substituted ionic liquids were synthesized and implemented as quasi-solid-state electrolytes. Combining them with an iodine-pseudohalogen redox couple, avoids the problem of low open-circuit voltage

(VOC) commonly associated with solid- or quasi-solid-state electrolytes. Overall, in quasi-solid-state DSSCs (qssDSSC) the VOC are increased by up to 70 mV in comparison with qssDSSCs lacking the mixed redox couple. Decisive is a good balance between dye regeneration and hole transport. Devices with iodine-pseudohalogen electrolyte featured a 70% higher energy conversion efficiency compared to the reference device and were stable with an energy output of 7-8% over 1000 h under 1 sun illumination.

References [1] Wu, J.; Lan, Z.; Lin, J.;Huang, M.; Fan, L.; Luo, G. Chem. Rev., 2015, 115, 2136-2173. [2] Docampo, P.; Guldin, S.; Leijtens, T.; Noel, N.K.; Steiner, U.; Snaith, H.J. Adv. Mater. 2014, 26, 4013-4030.

173 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 74 Erlangen, Germany

Structural and microstructural related evolution of bimetallic single-crystal nanoparticles

Leonardi, A.1,*; Engel, M.1

(1) Institute for Multiscale Simulation, Friedrich-Alexander University Erlangen-Nürnberg, Nägelsbachstraße 49B, Erlangen 91052 (Germany)

*e-mail: [email protected]

Keywords: Bimetallic Single-Crystal Nanoparticles; Structure and Microstructure; Non-equilibrium Transformations;

Understanding the evolution of single-crystal nanoparticles as they react to the alterations of the surrounding physical-chemical environment allows to optimize the design of stable high-energy catalysts. However, in addition to the difficulties of performing accurate in-situ experiments, available techniques have limited access to these non-equilibrium processes either for their statistical reliability or their time-scale sensitivity. The present study aims at attaining fundamental insights in structural-microstructural related transitions of bimetallic nanoparticles by exploiting numerical simulations to rationalize available experimental data. Atomistic simulations corroborated by in-situ experimental data revealed characteristic features of the structural and microstructural evolution path, providing the bases for a targeted designed synthesis of optimal nanocrystallites for catalysis. The combined role of crystallite’s size and bimetallic alloy’s structures was explored in a phase-like diagram to isolate characteristic behaviors and guide further experimental investigations. Indeed, the suitable choice of environmental parameters and precursors allowed the controlled synthesis of complex crystallite’s microstructures. In addition, the data modelling gave access to detailed information on surface physical-mechanical properties (i.e., surface atoms energy, lattice distortion, structural order-disorder), eventually related to the local structure coordination. The distortion of the lattice bond energy provided by the combination of different chemical elements was directly exploited in the synthesis and controlled transformation of Core-Shell single crystal microstructures. The chemical activity of the particles was thus optimized by an effective computationally-based design of the resulting crystallites structural-microstructural features.

174 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 72 Erlangen, Germany

En route to knowledge-based design of particle surfaces via resolving ligand adsorption in colloids on a molecular level

Lin, W.;1,2* Mahler, M.;1 Schmidt, J.;1 Walter, J.;1,2 Burger, A.;3 Maid, H.;3 Hirsch,A.;2,3 Peukert, W.;1,2 and Segets, D.1,2

(1) Institute of Particle Technology (LFG), (2)Interdisciplinary Center for Functional Particle Systems (FPS), (3) Institute of Organic Chemistry Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstr. 4, 91058 Erlangen, Germany *e-mail: [email protected] (presenting author)

Keywords: ZnO, electronegativity, thermodynamics, functionalization, interface engineering Although being of major importance for various semiconductor nanocrystals based applications, the characterization of nanoparticle (NP) surfaces in colloids especially with respect to ligand exchange reaction is still an open and highly challenging question.[1] Therefore, a general strategy to study the thermodynamics of ligand adsorption to colloidal surfaces was established by means of catechol (esterCAT) binding to ZnO NPs.[2] The thereby derived toolbox was applied to tailor the ZnO surface by CAT derivatives with different functionalities First, isothermal titration calorimetry (ITC) was used to extract all relevant thermodynamic parameters, namely association constant, enthalpy, entropy and free energy of the ligand binding. To confirm the characterization of ligand binding by measuring the heat of adsorption, the free energy was cross-validated by mass-based adsorption isotherms. To close the mass balance, analytical ultracentrifugation (AUC) was applied to detect the amount of free, unbound catechol in solution. Then, Raman spectroscopy and nuclear magnetic resonance spectroscopy (NMR) were performed to quantify the replaced amount of acetate which is the ligand from synthesis with esterCAT (65%) and to distinguish bound (chemisorbed) and unbound (physisorbed) esterCAT. Finally, based on a collection of all our results, the in-depth picture of ligand binding to the ZnO colloid was obtained. In a follow up study, the toolbox was applied to tailor the ZnO surface by CAT derivatives with different functionalities namely hydrogen (pyroCAT), t-butyl group (tertCAT), aromatic ring (naphCAT), ester group (esterCAT), and nitro group (nitroCAT). The results showed that the binding enthalpies of the CAT molecules follow the order of tertCAT < pyroCAT < naphCAT < esterCAT < nitroCAT, which is in agreement with the electronegativity of tail groups (keeping in mind the superimposed steric effects of tertCAT). Moreover, the efficiency of quenching visible emission by the binding of different CAT molecules was investigated which resulted in the same order as binding enthalpy. As all our results are in good agreement with each other and highly complementary, it is possible to get the full picture of ligand binding in various nanocrystal-ligand systems even if only parts of our approach can be applied. We believe that this wide applicability of our concept will provide strong encouragement for similar studies in the field of colloidal surface chemistry. It will also pave the way to knowledge-based design of ligands for tailoring colloidal NP surfaces for various particle-based applications.

[1] Lin, W.; Haderlein, M.; Walter, J.; Peukert, W.; Segets, D.; Angew. Chem. Int. Ed. 2016, 55, 932-935.

[2] Lin, W.; Walter, J.; Burger, A.; Maid, H.; Hirsch, A.; Peukert, W.; Segets, D.; Chem. Mater, 2015, 27, 358–369

175 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 71 Erlangen, Germany

A supramolecular nanocarrier for the highly efficient entrapment and release of hydrophobic water contaminants

Luchs, T. 1,*, Sarcletti, M. 2, Zeininger, L. 1, Halik, M.2 and Hirsch, A.1

(1) Institute of Organic Chemistry, Department of Chemistry and Pharmacy, Friedrich-Alexander Universität Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen (2) Organic Materials and Devices (OMD), Department of Materials Science, Friedrich-Alexander Universität Erlangen-Nürnberg, Martenstrasse 7, 91058 Erlangen

*e-mail: [email protected]

Keywords: nanocarrier, non-covalent interactions, water contaminants

Long lasting environmental effects, resulting from the transportation or extraction of crude oil and oil products require the provision of a simple, robust, efficient and inexpensive method for the binding of hydrocarbon based water contaminants.[1] Due to the high surface area to volume ratio and the tunability of the surface properties, nanoparticles are an excellent platform for this task. Herein we report on a facile method for the reversible entrapment of hydrophobic water contaminants via the recently established shell by shell (SbS) coating of inorganic nanoparticles.[2] The SbS coated nanoparticles display a double shell architecture consisting of a hydrophobic first monolayer and a hydrophilic outer shell. Resulting from the supramolecular nature of this architecture, the reversible binding and release of hydrophobic molecules depending on the surrounding media was achieved. The facile access to nanocarriers with magnetic and semiconducting nanoparticle cores as well as the high uptake potential of up to 300 % of their mass provides an excellent tool for water purification.

hydrophobic pocket hydrophilic shell

NP Core: TiO2 or Fe3O4 H2O

st Covalently attached 1 ligand shell

Non-Covalenlty attached 2nd ligand shell: Amphiphilic building blocks

toluene + G1 - Na O SO3 2 H C H 12 25 G2 G5 = 1 = Cl O Cl G3 O OH Cl C11H23 O O

2 Cl G6 G4 Figure 1: Schematic representation of the SbS coated nanocarrier assemblies. References [1] Bagby, S.; Reddy, C.; Aeppli, C.; Fisher, G.; Valentine, D. Proc. Natl. Acad. Sci. U. S. A. 2017 114, E9-E18. [2] Zeininger, L.; Petzi, S.; Schönamsgruber, J.; Portilla, L.; Halik, M.; Hirsch, A. Chem. Eur. J. 2015 21, 14030-14035.

176 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 92 Erlangen, Germany

Automated High-Throughput Synthesis and Characterization of Quantum Dot Nanocrystals: Investigation on the role of Mixing

Mahmoud Salaheldin, A.1*, Walter, J.1, Herre, P. 1, Levchuck, I.2, Brabec, C.2, Peukert, W. 1, and Segets, D.1 (1): Institute of Particle Technology (LFG), Interdisciplinary Center for Functional Particle Systems(FPS) (2): Institute of Materials for Electronics and Energy Technology (iMEET) Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Germany

*e-mail: [email protected] Keywords: Automated Synthesis, Hot Injection, Reproducibility, Influence of Mixing Quantum confined semiconductor nanoparticles, known as quantum dots (QDs), have experienced much attention during the past decades due to their outstanding optoelectronic properties. Especially size dependent absorption and emission properties make them highly promising candidates for electronic devices and photovoltaics. However, a scalable production of well-defined materials with high quality is still missing. To address this issue, a robot for automated particle synthesis under inert conditions was installed that enables unrivaled reproducibility, fast sampling (6 s) and gives unique insight to process-structure and therefrom based structure-property relationships. CdSe QDs synthesis by hot injection were selected as a well-studied benchmark system. This involves fast injection of a cold reactant (~25 °C) into a hot precursor solution (260 °C).

Figure 1: a) Image of robotic synthesis setup; b) absorbance spectra of 15 successful CdSe QD syntheses produced from a total of 16 (four runs with each of them operated with four reactors in parallel); c) waterfall diagram of selected PSDs derived from absorbance spectra of b). Synthesis by hot injection routine was performed which is based on the fast injection of a cold reactant under vigorous stirring.1 Outstanding reproducibility of the robotic system was demonstrated by comparison of optical properties and particle size distributions (PSDs)2 calculated from optical absorbance spectra as well as independent results of analytical ultracentrifugation (AUC).3 Especially the latter clearly revealed reproducible samples on a Å-level. Based on those findings, together with inline temperature monitoring and rapid sampling, systematic studies on process-structure relationships were conducted. Special emphasis was spent on the evolution of the dispersity of the samples regarding focusing and defocusing processes in dependence of stirring rates.4 We believe that by the combination of high throughput experimentation (HTE) with careful evaluation of process-structure-property relationships unique insights to nanoparticle formation in the liquid phase are within reach which are of major importance for optoelectronic applications. References

[1]. Chan, EM, et al. Nano Lett 2010, 10(5), 1874-1885. [2]. Segets, D, et al. ACS Nano 2009, 3(7), 1703-1710. [3] Walter, J, et al. ACS Nano 2014, 8(9), 8871-8886 [4] Salaheldin, A.M., et al. Chem. Eng. J., 2017, 320, 232-243 177 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 35 Erlangen, Germany

Tuning the adsorption and self-assembly of terpyridine derivatives: From metal to bulk insulator surfaces

Tuan Anh Pham 1, Yi Liu 1* , Manh-Thuong Nguyen 2 and Sabine Maier1

(1) Department of Physics, University Erlangen-Nürnberg, Erwin-Rommel-Str. 1, 91058 Erlangen, Germany (2) Center for Computational Physics, Institute of Physics, Vietnam Academy of Science and Technology, 10 Dao Tan St., Hanoi, Vietnam *e-mail: [email protected]

Keywords: self-assembly, bulk insulator, NC-AFM

Controlling and understanding the on-surface self-assembly of organic molecules are of utmost importance for the effective usage of molecular systems in potential future electronic devices. On metal surfaces, it is well-known that the structure of the on-surface self-assembly is strongly dependent on the subtle balance between molecule-molecule and molecule-substrate interactions. On bulk insulators, however, the role of the molecule-substrate interaction on the structure formation is widely unexplored. Herein, we report the self-assembly of 1,4-Bis(2,2’:6’,2”-terphyridin-4’-yl)benzene, on both, metal (Au and Cu) and bulk insulator surfaces (KBr), by a combination of high-resolution noncontact atomic force microscopy at low temperatures and density functional theory. We achieved to selectively tune the dimensionality of the molecular structures depending on the choice of the substrate: monomeric species on Cu(111), linear chains on Au(111), and two-dimensional networks on KBr were obtained. More interestingly, we found that the substrate may induce the rotation of pyridine rings around the σ bond axis in the terpyridine units of the molecules and thus, generating the formation of H-bonds stabilizing the self-assembled networks.

178 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 32 Erlangen, Germany

Melting, growth and surfaces of colloidal quasicrystals

Martinsons, M. 1,* and Schmiedeberg, M.1

(1) Institut für Theoretische Physik I, Friedrich-Alexander Universität, Staudtstraße 7, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: quasicrystals, phase transition, grwoth, surfaces

Quasicrystals are structures with long range order but missing translational symmetry. They may possess any rotational symmetry including those that are not allowed in periodic crystals. Due to additional degrees of freedom that do not exist in periodic crystals, additional hydrodynamic modes called phasons arise supplemental to the phononic modes known from periodic crystals. Phasonic excitations correspond to correlated rearrangements of the particles. We study the development of defects close to the melting transition. It has been predicted that dislocations and disclinations cause the melting of the quasicrystal (cf. KTHNY theory [1, 2]). We observe a first order phase transition. We analyze orientational and positional correlation functions and reveal the similarities and differences of the melting process of quasicrystals in comparisson to the melting of periodic crystals. Furthermore, for low densities quasicrystals coexist with the gas phase. We study the shape of the surface as well as the dynamics of the particles at the surfaces. In addition, we analyze the growth process (cf. [3]).

References [1] De, P.; Pelcovits, R. A. J. Phys. A: Math. Gen. 1989 22, 1167. [2] De, P.; Pelcovits, R. A. Phys. Rev. B 1988 38, 5042. [3] Achim, C. V.; Schmiedeberg, M.; Löwen, H. Phys. Rev. Lett. 2014 112, 255501.

179 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 68 Erlangen, Germany

In-situ doctor-blading cell for synchrotron radiation studies

Berlinghof, M.1,*; Langner. S.2; Kassar, T.1 Bär, C1; Brabec, C.2; and Unruh, T.1

(1) Chair for Crystallography and Structural Physics, Friedrich-Alexander-University Erlangen-Nürnberg, Staudtstr. 3, 91058 Erlangen (2) Institute Materials for Electronics and Energy Technology, Friedrich-Alexander-University Erlangen-Nürnberg, Martenstr. 7, 91058 Erlangen

*e-mail: [email protected]

Keywords: GID, in-situ, thin-films

We propose to present our flexible custom made doctor-blading cell, which was especially designed for grazing incidence studies at synchrotrons like PETRA III (DESY). In addition to be temperature controlled, it is also capable of solvent vapor annealing and of hydration of samples. Besides the technical details, capabilities and limitations of the cell, we intend to focus our presentation on three example scientific examples. One being the in-situ crystallization of organic photovoltaics, e.g. DRCN5T:PC71BM, by solvent vapor annealing or thermal annealing, which has an high impact on the efficiency of organic photovoltaics (OPVs) [1]. The second example are in-situ drying studies of OPVs, which shows the structure formation during the drying process. We would present the insight on the kinetics of the crystallization process achieved by in-situ GID . The other example would be the in-situ drying and hydration of phospholipid, e.g. DMPC, multilayer samples, which are a model system for biological membranes [2]. For these liquid crystalline samples fully hydration of is essential, which is achieved by creating 100% humidity in the sample cell.

Figure 1: Temperature and atmospheric controlled doctor-blading cell installed at our lab-source VAXSTER. References [1] Min, J.; Jiao, X; et al., Nano Energy. 2016 28, 241-249. [2] Salditt, T.; Li, C.; et al., Eur. Phys. J. E. 2002 7, 105-116.

180 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 42 Erlangen, Germany

Surface-induced changes in the thermodynamic transformation of an ionic liquid cobalt thiocyanate complex

May, B.1,*, Hönle, M. 1, Schreiber, P. 1, Heller, B.1 Hans-Peter Steinrück, H-P1, and Maier, F1

(1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: ionic liquids, transition metal complex, surface influence

The transformations of transition metal complexes in aqueous solution are well studied. Techniques such as NMR, IR and UV-Vis spectroscopy are standard techniques for investigation a wide range of transition metal techniques. Vacuum techniques, such as X-ray Photoelectron Spectroscopy (XPS), cannot be applied to the traditional aqueous solution, due to the volatility of the solutions. Ionic liquids (ILs) exhibit extremely low vapor pressures, a property that has already been taken advantage of in the study of these salts and their reactions by ultra-high vacuum techniques.[1] These studies have utilized the ILs as non-volatile solvents, carriers for an attached reactive functional group, and as direct reaction participants. In this study the transformation of the 2- [Co(SCN)4] complex in a [C2C1Im][SCN] / [C2C1Im][Co(SCN)4] mixture was monitored as a function of temperature with XPS.[2]

The IL [C2C1Im][Co(SCN)4] was first reported by Peppel et. al.[3] The thermochromatic behavior of the mixture used in this study was first reported by Osborne et. al.[4]: In the - 2- presence of excess SCN ions, the [Co(SCN)4] ion shows a temperature dependent complex equilibrium shift accompanied by a change in color. Using surface sensitive XPS, we find that the temperature-driven transition from the blue- 2− 4− colored tetrahedral [Co(II)(NCS)4] to the red-colored octahedral [Co(II)(NCS)6] complex already occurs within the outermost nanometers at around +4°C, as compared with −25°C in the bulk. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general. References [1] H.-P. Steinrück, Phys. Chem. Chem. Phys. 2012, 14, 5010-5029. [2] B. May, et al., J. Phys. Chem. Lett. 2017, 8, 1137-1141. [3] T. Peppel, et al., Angew. Chem. Int. Ed. 2010, 49, 7116-7119. [4] S.J. Osborne, et al., Dalton Trans. 2015, 44, 11286-11289.

181 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 28 Erlangen, Germany

Characterization of functionalized self-organized TiO2 nanostructures

Mazare, A.; 1,* and Schmuki, P; 1

(1) Department of Materials Science, LKO, University of Erlangen-Nuremberg, Erlangen, Germany

*e-mail: [email protected]

Keywords: TiO2 nanotubes, functionalization, morphology characterization

Titanium and titanium alloys represent one key class of lightweight materials and nanostructuring of such materials has attracted extensive scientific and technological interest in the past years in a wide range of applications from the photoelectrochemical to the biomedical field. One elegant method of generating porous structures (nanopores, nanotubes) is self-organizing electrochemical anodization – the structures are grown directly on the substrates, it has a good control over the nano-geometry and ease of application, and the principles can be applied to a broad range of other elements and alloys (e.g. Al, Ta, Nb, etc. or to alloys as TiTa, TiZr, TiNb, Ti6Al7Nb, etc .) [1]. Such porous materials can be used as substrate material, as a template for building hierarchical structures or for decoration with various active molecules (proteins, growth factors, drugs, etc.). For biomedical applications the current state-of-the-art lies in building hybrid structures (organic/inorganic structures) to enhance their properties and use; hence, there is a need to characterize such structures and to evaluate the presence of the active substance inside the layers. This can be achieved by a combination of microscopy (e.g. scanning electron microscopy) with ion-milling techniques to evaluate the morphology, and with surface and depth characterization techniques (X-ray Photoelectron Spectroscopy, Time of Flight Secondary Ion Mass Spectroscopy) to evaluate the chemical composition at the top and throughout the layers. The evaluation of hybrid structure is crucial for optimizing their properties in view of their further use, and in this respect a good control over the resulting morphology and functionalization properties is necessary.

References [1] Lee, K.; Mazare, A.; Schmuki, P.; Chem. Rev. 2014 114, 9385–9454. [2] Kulkarni, M.; Mazare, A.; Park, J; Gongadze, E.; Killian, M.S.; Kralj, S.; von der Mark, K.; Iglič, Schmuki, P.; Acta Biomater 2016 45, 357-366. [3] Ionita, D.; Bajenaru-Georgescu, D.; Totea, G.; Mazare, A.; Schmuki, P.; Demetrescu, I.; Int. J. Pharm. 2017 517, 296-302.

182 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 30 Erlangen, Germany

Simulation of hard spheres clusters in confinement

Mbah Chrameh, F.1* , Wang, J. W.2, Vogel, N. 2, Engel, M. 1

(1) Institute for Multiscale Simulation, FAU, Nägelsbachstr. 49b, Erlangen (2) Institute of Particle Technology, FAU, Cauerstr. 6, Erlangen

*e-mail: [email protected]

Keywords: Monte Carlo simulation, confinement,

Colloids in suspended emulsion droplets is a promising approach for synthesizing hierarchical assemblies with interesting photonic properties [3]. Evaporation causes the packing fraction of the colloids to increase, thereby forming a number of crystalline structures. The packing density influences the stability of the resulting structures, revealing icosahedral geometries [1]. These structures include Mackay type, anti-Mackay type, truncated icosahedral, and face-centered cubic clusters.

In this study, we explain the formation of the colloidal clusters by means of had spher Monte Carlo computer simulations and free energy calculations [2]. In hard sphere systems, there are no interaction between the spheres, thus the formation of these clusters is indicative of the influence of the confinement. First, we construct a computer model of the observed structures in the emulsion droplet. By using our model, we then study the interplay between interfacial patterning, which depends on the number of spheres on the surface, the number of spheres in a given cluster, and the packing fraction.

References

[1] B. de Nijs, S. Dussi, F. Smallenburg, J.D. Meeldijk, D.J. Groenendijk, K. Filion, A. Imhof, A. van Blaaderen, M. Dijkstra, Nature Materials, 2015, 14, 56. [2] Haji-Akbari, A., Engel, M. and Glotzer, S.C., Journal of Chemical Physics, 2011, 135, 194101.

[3] N. Vogel, S. Utech, G.T. England, T. Shirman, K.R. Phillips, N. Koay, I.B. Burgess, M. Kolle, D.A. Weitz, J. Aizenberg, PNAS, 2015, 112, 0845.

183 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 41 Erlangen, Germany

In situ Raman monitoring of α-FeOOH particles with controlled size distribution synthesized by air oxidation of iron precipitates

Michaud, M.;1,2,*, Güldenpfennig, A.;1,2, Distaso, M.;1,2, Klupp-Taylor, R.;1,2, Peukert, W.;1,2

(1) Institute of Particle Technology (LFG) Cauerstraße 4, 91058 Erlangen (2) Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) *e-mail: [email protected]

Keywords: Oxidation, precipitation, nanoparticles Goethite (α-FeOOH) is an iron oxy-hydroxide polymorph largely applied as a yellow pigment and as a precursor for acicular magnetite. For both applications the particle size distribution (PSD) and particle shape play an important role in determining the final properties of the product. The phase purity has to be carefully controlled through the adjustment of the experimental conditions since the main side product of the reaction i.e. γ-FeOOH, also known as Lepidocrocite, has vastly different properties. More possible phases are β- and δ-FeOOH. In order to control the phase purity and to shed light on the phase evolution during the formation of Goethite, the reaction mixture was monitored by in situ Raman spectroscopy and pH measurements. The latter showed a pH drop from 7 to 6 over time, and from 6 to 3.8, leading to, respectively, two well-defined reaction plateaus. Normalizing the reaction time revealed the first plateau taking 33% of the total reaction time, while the second plateau takes 66%. Investigation by in situ Raman revealed several intermediate iron phases at different times of the reaction. The Iron sulfate used as precursor and Iron-(II) hydroxide were detected at the mixing point. On plateau I Green rust I, Ferrihydrite and Lepidocrocite were detected, while on plateau II Green Rust I & II, Ferrihydrite, Goethite and Lepidocrocite were clearly identified [2]. The area of Raman peaks corresponding to the different phases was plotted as function of time, showing that new peaks only occur at the beginning or at the end of each pH plateau. Changes in the area of the peaks of a specific phase during one plateau were always constant. After the reaction, Lepidocrocite and Goethite are present in variable amounts according to the experimental conditions. The formation of Goethite only on plateau II indicates that the mixing phase and the Goethite formation are well-separated by time. As a next step, a process parameter study was carried out to control the PSD and hence the particles properties. Increasing the initial iron concentration, the particle length and standard deviation increased while XRD measurements showed no additional phases. Experiments including the addition of carbonate salts yielded spindle-shaped particles with a higher median length and narrower PSD. The XRD analysis showed Goethite, with the main reflections shifted towards smaller angles. Experiments using hydrogen peroxide as an oxidizing agent yielded needles and aggregates with a very narrow PSD. The XRD diffractogram showed peaks of δ- FeOOH, whose formation may have been caused by the increased rate of the side reaction that leads to the formation of Lepidocrocite phase.

References [1] Encina E., Distaso M., Klupp Taylor R., Peukert W. Cryst. Growth Des. 2015 15, 194. [2] Cornell R., Schwertmann U., The Iron Oxides. Structure, Properties, Reactions, Occurrence and Uses, VCH – D-69451 Weinheim (Federal Republic of Germany), 1996.

184 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 65 Erlangen, Germany

Large-range order pre-patterned alumina nanochannel templates for photovoltaic applications

Minguez-Bacho, I. 1,*; Drya, M. 2; Bley, K 2; Vogel, N. 2 and Bachmann J. 1

(1) Department of Chemistry and Pharmacy, Friedrich-Alexander University of Erlangen-Nürnberg, Egerlandstr. 1, 91058 Erlangen, Germany. (2) Institute of Particle Technology, Friedrich-Alexander University of Erlangen-Nürnberg, Haberstr. 9a, 91058 Erlangen, Germany.

*e-mail: [email protected]

Keywords: anodic alumina, self-assembly, photovoltaics

Ordered nanoporous anodic alumina films are widely useful templates for nanofabrication. However, the self-ordering conditions of anodic alumina nanopores are restricted to very specific experimental parameters and the domain sizes are not larger than few micrometers. These limitations can be overcome by pre-patterning the surface of aluminum with ordered structures. We present a new methodology for the fabrication of large-range ordered alumina nanochannels with geometric parameters unreachable using conventional anodization regimes. Polystyrene (PS) spheres are self-assembled into monolayers at the air-water interface [1]. These PS spheres monolayers are transferred to aluminum substrates (Figure 1 a,b) and are used as a template for the deposition of an insulating material coating. A pre-patterned aluminum surface remains after the removal of the PS spheres. Consequently, hexagonally ordered areas of aluminum are exposed for subsequent anodization of aluminum. Pre-patterned alumina nanochannels are then rationally grown for its use as templates (Figure c) for the fabrication of highly ordered coaxial heterojunctions, which will be integrated, eventually, in photovoltaic devices [2].

Figure 1: a) PS spheres monolayer on aluminum substrate, b) SEM magnification and c) cross-sectional view of pre-patterned alumina nanochannels.

References [1] Vogel, N.; Goerres, S.; Landfester, K.; Weiss, C.K. Macromol. Chem. Phys. 2011 212, 1719-1734. [2] Wu, Y.; Assaud, L.; Kryschi, C.; Capon, B.; Detavernier, C.; Santinacci, L.; Bachmann, J. J. Mater. Chem. A. 2015 3, 5971-5981

185 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 27 Erlangen, Germany

Modelling heterogeneous catalysis in open-cell porous foam structures

Mühlbauer, S.1,*, Strobl, S.1 and Pöschel, T.1

(1) Institute for Multiscale Simulation, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 49b, 91052 Erlangen, Germany

*e-mail: [email protected]

Keywords: heterogeneous catalysis, open-cell foam structures, particle based simulation methods

Heterogeneous catalysis in metallic or ceramic foam structures represents a very promising alternative to catalysis in packed beds or monoliths. Due to high porosity, specific surface and tortuosity, these structures provide excellent mass transport properties at moderate pressure drops [1]. Simulating catalysis in foam structures requires to merge reaction kinetics into gas dynamics within complex geometries. Particle based simulation methods are eminently suitable for this, allowing us to decouple the boundary representation from the simulation grid by means of constructive solid geometry.

flow velocity u/umax 0.0 0.25 0.5 0.75 1.0

reactant concentration 0.58 0.79 1.0 We investigate the low temperature water gas shift, which is assumed to follow the Langmuir-Hinshelwood reaction mechanism [2]. The foam structure shown above is modelled as inverse sphere packing. The chemical reactions take place in a CuO/ZnO/Al2O3 washcoat layer. The effective reaction rate in this washcoat layer is determined using precomputed look-up tables for the effectiveness factor [3].

References [1] Lucci, F.; Della Torre, A.; Montenegro, G; Dimopoulos Eggenschwiler, P. Chem. Eng. J. 2015 264, 514-521. [2] Ayastuy, J. L.; Gutiérrez-Ortiz, M. A.; González-Marcos, J. A.; Aranzabal, A.; González-Velasco, J. R. Ind. Eng. Chem. Res. 2005 44, 41-50. [3] Roberts, G. W.; Satterfield, C. N. Ind. Eng. Chem. Fundamen. 1966 5, 317-325

186 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 45 Erlangen, Germany

Optoelectronics properties of oxidized tin sulphide thin films prepared by spray ultrasonic method

Hassene Nezzari 1,*, Yacine Bouachiba 2, Adel Taabouche3, Moufdi Hadjab1 and Mohamed Salah Aida1,4

(1) Research Center in Industrial Technologies CRTI, P. O. Box 64, Cheraga 16014, Algiers, Algeria (2) Department of Materials Science Engineering, National Polytechnic School of Constantine, Nouvelle Ville Universitaire Ali Mendjeli, Algeria. (3) Faculty of Hydrocarbons, Renewable energies, Earth and Universe sciences, University Kasdi Merbah, 30000 Ouargla, Algeria (4) Thin Films and Interfaces Laboratory, University of Frères Mentouri Constantine, 25000 Constantine, Algeria.

*[email protected] / *[email protected]

Keywords: SnS, SnOx, Oxidation, Ultrasonic spray, Raman analysis, Opto–electronics

The aim of this research work is to investigate the fundamental properties (electrical and optical properties) of tin sulphide (SnS) thin films deposited onto glass substrates using ultrasonic spray method. hence, the effect of deposition temperatures on the optoelectronics properties in correlation with the Raman analysis is studied. The Raman spectroscopy, absorption spectroscopy and Hall effect measurements are utilized to define respectively; the existing modes of vibrations, absorbance - energy band gap and the electrical properties. At low deposition temperatures, Raman analysis shows the oxidation of SnS thin films into SnOx phases, but the increasing in deposition temperature up to 400°C reduces this oxidation and promotes the formation of SnS. The spectroscopic absorption analysis has shown the reciprocal relationship between the deposition temperature and the optical band gap energy, where the increasing of deposition temperature from 300 to 400°C, provoke the decreasing of band gap values from 2.0 to 1.73 eV. From the Hall effect measurements, where the increasing of deposition temperature guide to increase the carrier concentration of the films considerably from 2.947×1013 to 1.767 ×1018 cm-3, which leads to decrease the resistivity from 1.621 ×103 to 1.449 Ω. The elaborated sample at 400°C have an excellent Ohmic behavior over larger range of voltage and current as compared to other samples. Therefore, our obtained results prove that the SnS is promising materials for optoelectronics devices.

6x104 300°C 350°C 4 400°C 5x10

4x104

3x104 SnS SnOx 4 Intesity (a, u) (a, Intesity 2x10 SnS 1x104

0

100 150 200 250 300 350 400 450 500 Raman Shift (cm-1) Figure 1: Raman spectra of SnS thin films deposited at different temperatures.

187 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 40 Erlangen, Germany

Functionalization of oxide nanocrystals and composites with transition metal ions

Niedermaier, M. 1,*, Gheisi, A. 2, Bernardi J. 3 and Diwald O. 1

(1) Paris Lodron University of Salzburg: Chemistry and Physics of Materials, Jakob-Haringer-Str. 2a, A-5020 Salzburg (2) Friedrich Alexander University: Institute of Particle Technology, Cauerstr. 4, D-91052 Erlangen (3) Vienna University of Technology: USTEM, Wiedner Hauptstrasse 8-10, A-1040 Vienna *e-mail: [email protected]

Keywords: non-equilibrium solids, nanocomposites, metal-oxide nanoparticles

Structure and functional properties of composite metal oxide nanoparticle systems are subject to stability and composition of related surfaces and interfaces. For vapor phase grown non-equilibrium solids, annealing induced ion diffusion provides efficient means to adjust the surface composition and, thus, the functional properties of the material. Insights into the underlying transformation processes, which can be controlled by annealing in different gas atmospheres, are essential for both nanomaterial design and material applications at elevated temperatures.

In the present contribution we will discuss properties and transformation behavior of metal oxide composites, such as Fe-Mg-O or Co-Mg-O nanoparticles, which were prepared by a hybrid chemical vapor synthesis approach using organic transition metal compounds as precursors. In addition to their combustion in the MgO formation flame, we also explored the feasibility of adsorption of transition metal oxides on MgO nanocubes in liquid particle dispersions followed by subsequent annealing in different chemical environments.

We used an integrated characterization approach involving electron microscopy (SEM, TEM), X-ray diffraction (XRD), electron dispersive X-ray spectroscopy (EDX) and Mößbauer as well as X-ray absorption spectroscopy (XAS) to study the ensemble properties of nanoparticle composites, on the one hand, and structure and morphological features of characteristic local structures, on the other. The complex evolution of the composite nanostructures as a result of annealing induced segregation and phase separation was characterized for samples with different thermal processing histories. These can give rise to a variety of material types in the range between nanostructures with bulk and surface admixed transition metal oxides to phase separated systems such as Fe-Mg-O - magnesioferrite MgFe2O4 particles.

188 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 73 Erlangen, Germany

Spaced TiO2 NTs with Nb2O5 conformal coating for supercapacitor applications

Ozkan, S. 1,*; Mazare, A. 1 and Schmuki, P. 1,2

(1) Department of Materials Science and Engineering, WW4-LKO, University of Erlangen-Nuremberg, Martensstrasse 7, D-91058 Erlangen, Germany (2) Chemistry Department, Faculty of Sciences, King Abdulaziz University, 80203 Jeddah, Saudi Arabia

*e-mail: [email protected]

Keywords: Anodization, Spaced TiO2 nanotubes, Nb2O5, Supercapacitors

The TiO2 nanotubes obtained by electrochemical anodization offer a high specific surface area combined with ion and charge transport directionality, as these oxide structures are vertically aligned on the substrate. The highly ordered structure of NTs with a wide range of properties can be utilized in many applications i.e. photocatalysis, solar cells, supercapacitors [1]. However, mostly self-ordered TiO2 nanotube arrays grow close-packed (CP), i.e. have no or only very narrow intertube spacing. This limits the use of such nanotubes as a scaffold for building up defined hierarchical structures. Key is the growth of a nanotube array with regular tube-to-tube interspacing that enables an optimized decoration with secondary metal or metals oxides [2-3]. In the present work, we address this point by establishing self-organizing conditions that lead to a defined tube-to-tube spacing and by increasing the electrical properties through a nitridation heat treatment. As a decoration material, we have selected Nb 2O5 since it can provide a high switching capability with different valence states and it shows a high chemical and electrochemical inertness [4]. We observed that a highly conducting hierarchical interspaced nanotube array with Nb2O5 conformal decoration can achieve a good supercapacitor performance (37 mF cm-2) and improved stability [5].

8 -1 Ref-TiO2 (100 mV s ) 6 -1 -2 TiO2 / Nb2O5 / NH3 (100 mV s ) 4

2

0

-2 Current density / mA cm / mA density Current -4

-6 TiO2/Nb2O5 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Potential / V vs Ag/AgCI

Figure 1: HR-TEM image of TiO2 NTs conformally coated with Nb2O5. Cyclic voltammograms of bare

TiO2 and nitrided TiO2/Nb2O5 nanotubular layers [5]. References [1] Lee, K.; Mazare, A.; Schmuki, P., Chem. Rev. 2014 114, 9385–9454. [2] Ozkan, S.; Nguyen, N. T.; Mazare, A.; Cerri, I.; Schmuki, P., Electrochem. Commun. 2016 69, 76-79. [3] Ozkan, S.; Nguyen, N. T.; Mazare, A.; Hahn, R.; Cerri, I.; Schmuki, P., Electrochem. Commun. 2017 77, 98–102. [4] Kim, J. W.; Augustyn, V. ; Dunn, B., Adv. Energy Mater. 2012 2, 141-148. [5] Ozkan, S.; Nguyen, N.T.; Hwang, I.; Mazare, A.; Schmuki, P., Small 2017 13, 1603821.

189 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 86 Erlangen, Germany

Microstructure and mechanical properties of B4C particulate reinforced aluminum matrix composites produced by stir casting

Plötz, S.1,*, Lohmüller, A.2 and Singer, R. F.1,2

(1) Chair of Materials Science and Engineering for Metals (WTM), Joint Institute of Advanced Materials and Processes (ZMP), Dr. Mack-Str. 81, 90762 Fürth (2) Neue Materialien Fürth GmbH, Dr. Mack-Str. 81, 90762 Fürth

*e-mail: [email protected]

Keywords: Metal Matrix Composites, Aluminum, Boron carbide The outstanding performance of aluminum matrix composites (AMCs) regarding stiffness/weight ratio makes AMCs attractive material for lightweight construction. Low density boride compounds promise simultaneously an increase in stiffness and decrease in composite density. This is why boron carbide is chosen for composite manufacturing. The composites are fabricated with the stir casting process. To avoid gas entrapment during mixing partial vacuum is adapted during particle feeding and stirring. Poor wettability of boron car bide with liquid aluminum hinders particle incorporation, but adapted stirring parameters and impeller geometries support particle incorporation.

A lloying elements such titanium are added to improve wettability by the formation of a TiB2 interface between B4C particle and aluminum matrix (Fig. 1a). The interfacial TiB2 layer prevents the reaction of B4C with liquid aluminum to AlB2 and Al3BC. AMCs with up to 15 vol.% of boron carbide particles are produced via melt stirring, resulting in an increase in stiffness up to 25 % (Fig. 1b).

(a) (b)

Figure 1: (a) Interface between an Al99,5 alloy and B4C substrate: Impurity diffusion of Ti in liquid aluminum leads to the formation of TiB2. (b) The addition of B4C particles leads to an increase in stiffness for pure aluminum Al99,9 and AlSi10Mg(Fe) alloy.

190 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 85 Erlangen, Germany

Improving fatigue properties of ARB-fabricated Al/Cu laminates: Determination of suitable laminate architectures with a reverse engineering approach using in-situ characterization of fatigue testing via SEM and FEM-analysis

Pohl, P.M.*, Krechel, C., Höppel, H.W. and Göken, M.

Friedrich-Alexander-University Erlangen-Nürnberg FAU, Materials Science & Engineering, Institute I, 91058 Erlangen, and Joint Institute for New Materials and Processes ZMP, 90762 Fürth, Germany

*e-mail: [email protected]

Keywords: accumulative roll bonding, in-situ fatigue characterization, FEM-analysis

Accumulative roll bonding (ARB), a process that allows the manufacturing of ultrafine grained (UFG) sheet metals, was first introduced by Saito et al. in 1998 [1]. In recent years this process was used to produce and characterize multilayered laminates out of a variety of material combinations [2]. This research project will focus on the mechanical properties and flexural fatigue behavior of different architectures of AA5754 aluminum (AlMg3) and OFE copper (oxygen-free copper) laminates fabricated via the ARB process route, since these alloys exhibit similar strength. The goal is to understand the fatigue behavior and onset of fatigue damage, i.e. crack initiation and propagation or/and delamination at bonding layers, to be able to determine optimized laminate architectures regarding fatigue life. To simulate the stress distribution for the laminates in a three point flexural fatigue test, a FEM-Model was created. After evaluating the stress distribution of different laminate architectures with FEM-Simulation, several architectures were manufactured via the ARB process and flexural fatigue experiments were conducted while observing microstructural phenomena, crack initiation and propagation in-situ with a large chamber SEM. We observed that in the LCF region the location where the fatigue damage starts strongly depends on the architecture of the laminate. Performing tensile tests on monolithic ARB processed AA5754 and OFE-Cu specimen, we were able to include the phenomenon of fatigue failure due to the occurring flexural tensile stress at the extreme fiber into our FEM-Model to evaluate suitable architectures more precisely.

191 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 85 Erlangen, Germany

Figure 1: Linear Elastic FEM-Simulation: Stress distribution within a N4 (16 layered) AA5754 / OFE-Cu laminate during flexural loading with a 172.5 N load.

Having a layer of AA5754 with a smaller Young’s Modulus than OFE-Cu as the outmost layer creates a lower flexural tensile stress in the extreme fiber and thus improves the fatigue life in the LCF region.

References [1] Saito, S.; Tsuji, N. Scripta Mater. 1998 Vol. 39, pp. 1221-1227. [2] Li, L.; Nagai, K. Sci. Technol. Adv. Mater. 2008 Vol. 9 No. 2

192 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 66 Erlangen, Germany

Integrating Cheaper Silane Synthesis with Silicon Composite Nanoparticle Production Enables Local-Scale Li-ion Battery Fabrication

Preston, T.1,*, Klette, H.1 , Nordseth, Ø.1 , Mongstad, T.1, Hansen, J.2 , and Vedde, J.2,3

(1) Solar Energy Department, Institute for Energy Technology, Instituttveien 18, 2007 Kjeller, Norway (2) Danica Silicon, Store Standstræde 21.3.tv, 1255 Copenhagen, Denmark (2) SiCon – Silicon & PV consulting, J N Vinthersvej 5, 3460 Birkerød, Denmark

*e-mail: [email protected]

Keywords: lithium-ion anode, silane production, silicon nanomaterial production

Silicon-based nanomaterials can be used for lithium storage in anodes of lithium-ion batteries. Tailoring the electronic and structural properties of the particles by mixing in other elements to make tuneable silicon ceramics enables flexible synthesis routes to robust materials. Rather than demand excessive purities of starting materials, as is current practice in the silicon industry, we realize better production routes by actively harnessing the impurities of novel silane production methods. Danica Silicon is developing an inexpensive, small-scale silane production method. The Institute for Energy Technology has pilot-scale silane reactors to produce silicon composite nanoparticles for anodic material in lithium-ion batteries. In our collaboration, we use knowledge of each partner’s chemical and physical processes to cut out several steps in the traditional silicon-production value chain. To date, the two groups have shown good independent results. Current focus is on knitting these two technologies even tighter to reduce production and synthesis costs and to improve material performance.

Figure 1: Integrating raw-materials synthesis with nanoparticle production provides new route to local-scale fabrication of nanomaterials.

193 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 47 Erlangen, Germany

Synthesis and characterization of co-doped cerium gadolinium oxide nanoparticles employing novel sol-gel method

Rahayu, S.*; Kale, G.M. and Ghadiri, M.

School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK

*e-mail: [email protected]

Keywords: IT-SOFC, co-doped, nanoparticles, TEM

Cerium gadolinium oxide nanoparticles with co-doped rear earth (Dy, Er and Ho) materials as intermediate–temperature electrolyte solid–oxide fuel cells [IT-SOFC] have been synthesized by a novel sol-gel method. Sodium alginate is granuled and used to prepare the nanoparticle complex metal oxide by ion exchange and subsequent thermal oxidation. The method produces cubic single phase nanoparticle of cerium gadolinium oxide (Ce0.8Gd0.2O1.9), cerium dysprosium gadolinium oxide (Ce0.8Dy0.1Gd0.1O1.9), cerium erbium gadolinium oxide (Ce0.8Er0.1Gd0.1O1.9) and cerium holmium gadolinium oxide (Ce0.8Ho0.1Gd0.1O1.9) having homogeneous composition. The final crystalline size of nanoparticles is less than 10 nm calcined at 500oC; higher temperature calcination (700oC) produces bigger crystalline sizes. The mean crystalline size calculated with XRD Rietveld refinement have excellent agreement with the morphologies observed by Transmission Electron Microscopy (TEM). Hence, this novel sol-gel method is the promising processes to produce nanoparticles of complex metal oxide compounds.

Figure 1: TEM images of Ce0.8 Ho0.1Gd0.1O1.9 sample calcined at 700°C for 2 h References [1] Kilner, J.A.; Burriel, M. Annu. Rev. Mater. Res. 2014 44, 365-393. [2] Steele, B.C.H. Solid State Ionics. 2000 129, 95-110. [3] Wang, Z.; Kale, G.M.; Ghadiri, M. Chem. Eng. J. 2012 198-199, 149-153

194 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 23 Erlangen, Germany

Numerical simulations of fluidized bed behavior and heat transfer among the phases using hybrid Eulerian-Lagrangian approach Iqbal, N. 1,*, Muensch, M.1, Rauh, C.2 and Delgado, A1.

(1) Institute of Fluid mechanics, Friedrich-Alexander University Erlangen-Nuremberg, Germany, Cauer Str. 4, 91058 Erlangen, Germany

(2) Institute of Food Biotechnology and Food Process Engineering, Technical University of Berlin, Königin-Luise-Str. 22, 14195 Berlin, Germany

*e-mail: [email protected]

Keywords: CFD-DEM, Eulerian-Lagrangian, spout fluidization, multiphase flow.

Authors have developed a numerical model using hybrid Eulerian-Lagrangian approach. The validation of the model has been reported elsewhere [1, 2] using well known Ergun and Wen & Yu. This model is capable of simulating particulate flows with a broad range of particle volume fractions. Simulation of jet/spout fluidized bed [2, 3] shows a good agreement with the experimental results reported in the literature [4]. The model is extended to simulate the heat transfer among the both phases as well as between the phases. The coupled energy equation is solved along with mass and momentum equations. The temperature of gas entering through a jet is 400K to see the effects of heat transfer to the particles. The particles have an initial temperature of 300K. Due to bubble formation during the fluidization process, the particles encounter different residence time that results in non-uniform temperature distribution as shown in figure 1. The particles residing for longer time like on the top of bubble have higher temperature.

Figure 1: Temperature distribution at different times in a fluidized bed References [1] Iqbal, N. Rauh, C. and Delgado, PAMM. 2012 vol. 12, pp. 393-394. [2] Iqbal, N. Rauh, C. and Delgado, A. PROENG. 2015 vol. 102 pp. 867-876. [3] Iqbal, N. and Rauh, C. AMC. 2016 vol. 277, pp. 154-163. [4] J.M. Link, N.G. Deen, J.A.M. kuipers, X. Fan, A. Ingram, D.J. Parker, J. Wood, J.P.K. Seville, AIChE. 2008 vol. 54(5), pp. 1189-1202.

195 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 52 Erlangen, Germany

Mesoscopic simulations of electrokinetic phenomena.

1,* 1 Rivas, N. and Harting, J.

(1) Forschungszentrum Jülich GmbH, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IEK-11), Fürther Straße 248, 90429 Nürnberg.

* e-mail: [email protected]

Keywords: electrokinetics, mesoscale simulations

Electrokinetic effects play a crucial role in many natural and technological systems, from the biological to nano-fluidics. Numerical simulations of conducting fluids presents a significant challenge mainly due to the variety of length-scales involved, and the presence of two long- range interactions: hydrodynamic and electrostatic. We show an electrohydrodynamic mesoscopic model, discuss its validity, and present results of two model systems. The hydrodynamics of two fluids is solved using the lattice-Boltzmann method. Ions present in the solvents are considered at the level of the Nernst-Planck equation, which is solved via a finite- volume, finite-difference discretization, following the link-flux method [1]. Furthermore, colloids can be added provided that a novel discretization scheme is used to avoid large velocity fluctuations. We show that the simulation scheme is robust and remains valid in a wide range of parameters. The model is able to capture the electrowetting effect at the nanoscale, and provide insights into the dynamics of contact-angle saturation. Furthermore, it allows us to study the behaviour and interaction of particle-coated droplets under the effect of external electric fields.

Figure 1: Contour lines of the concentration field (left) and the ion concentration field (right) for a drop deformed under the effect of an external electric field Ez. References [1] B. Rotenberg, I. Pagonabarraga, and D. Frenkel, Faraday Discuss. 2010, 144, 223.

196 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 91 Erlangen, Germany

Computational homogenization accounting for size effects via interface elasticity Saeb, S. 1,*, Javili, A. 2 and Steinmann, P.1

(1) Chair of Applied Mechanics, University of Erlangen-Nuremberg, Egerlandstraße 5, 91058, Erlangen, Germany (2) Department of Mechanical Engineering, Bilkent University, 06800 Bilkent, Ankara, Turkey

*e-mail: [email protected]

Keywords: Interface elasticity, Multi-scale modeling, Random microstructures The objective of this presentation is to establish a computational homogenization framework to model the behavior of heterogeneous materials in which the influence of interfaces at the micro-scale is taken into account. The term “interface” refers to a zero thickness model that represents the finite thickness “interphase” between the different phases of the micro-structure. Therefore, the interface is essentially a two-dimensional manifold embedded in a three-dimensional space. The interface effect is particularly important at the microscopic level and often dominates the mechanics of nano-structures due to the increasing area-to-volume ratio at small scales. Hence, it is of significant importance to account for interfaces at the micro-scale. We show that an immediate consequence of including the interface at the micro-scale is the introduction of a length-scale into first-order computational homogenization. Therefore, the proposed interface-enhanced computational homogenization framework captures size effects in the material response that are missing in classical computational homogenization. In this contribution, the interface does not allow for a displacement jump across the interface and hence, is only valid for coherent interfaces. However, the traction jump, which is mainly due to the elasticity along the interface, is permitted. Central to computational homogenization is the Hill-Mandel condition which ensures the incremental energy equivalence between the macro- and the micro-scale. A generalized version of the Hill-Mandel condition is presented that accounts for the presence of the interface at the micro-scale. Accordingly, suitable boundary conditions to satisfy the Hill-Mandel condition are derived. Moreover, extended average theorems, in particular average deformation gradient and average stress theorems, are employed to relate the macroscopic quantities to their microscopic counterparts. The computational aspects of the proposed framework using the finite element method are detailed. Finally, the influence of different boundary conditions on the overall response of the micro-problem with different sizes, geometries and interface properties is discussed through presenting several numerical examples.

197 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 83 Erlangen, Germany

Optimization of nanoporous water oxidation electrodes based on an original iridium atomic layer deposition reaction

Schlicht S.;1* Haschke S.;1 Mikhailovskii V.;2 Manshina A.;3 and Bachmann J.1

(1) Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany. (2) Saint-Petersburg State University, Interdisciplinary Resource Center for Nanotechnology, Uljanovskaya 1, 198504 St. Petersburg, Russia (3) Saint-Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia

*e-mail: [email protected]

Keywords: Oxygen Evolution Reaction, Iridium, Porous Materials, Atomic Layer Deposition, Anodic Aluminum Oxide

Nanoporous iridium electrodes are prepared and electrochemically investigated towards the water oxidation (oxygen evolution) reaction. Due to its good electric conductivity and high catalytic activity, iridium is used as active surface for the four-electron water oxidation to oxygen, which represents the kinetic bottleneck of water splitting. The preparation bases on ‘anodic’ aluminum oxide templates which provide straight, cylindrical nanopores. Their walls are coated by atomic layer deposition (ALD) using a newly developed reaction from (1,3-cyclohexadiene)(ethylencyclopentadienyl)iridum and ozone, which results in a metallic iridium layer. The ALD film growth is quantified by spectroscopic ellipsometry and X-ray reflectometry. The morphology and composition of the nanostructured electrodes is characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Their catalytic activity is quantified by cyclic voltammetry, steady-state electrolysis and electrochemical impedance spectroscopy for various pore geometries in different pH. This platform is particularly competitive for achieving moderate current densities at very low overpotentials, that is, for a high degree of reversibility in energy storage.

Figure 1: Scanning electron micrograph of anodic aluminum oxide membranes coated with iridium. Dependence of the electrocatalytic current density J on the nanopores´ length L.

198 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 34 Erlangen, Germany

Structural characterization of organic nanoparticles produced by antisolvent precipitation

Schuldes, I.1,*,, Noll, D.1 , Unruh, T.1

(1) Friedrich-Alexander-Universität Erlangen-Nürnberg, Chair for Crystallography and Structural Physics, Staudtstraße 3, 91058 Erlangen

*e-mail: [email protected]

Keywords: organic nanoparticles, antisolvent precipitation, scattering methods, phase transition

The production of organic nanoparticles by means of antisolvent precipitation (AS) is a low-cost and less invasive alternative to top-down methods like high pressure homogenization (HPH) [1], and yields stable, small and narrowly size distributed nanoparticles even without the addition of stabilizers [2]. The combination of small-angle x-ray and neutron scattering (SAXS, SANS) proved suitable for the structural determination of the stabilizing layer of triglyceride nanoparticles produced by HPH [3]. Here we use this combined approach to characterize triglyceride and coenzyme Q10 nanodispersions produced by AS with special focus on the stabilization and the role of the residual solvent which are not yet understood. The organic nanodispersions produced by AS exhibit particular small sizes of about 20 nm in diameter. Moreover, the melting behavior of the nanodispersions differs significantly from the one of previously reported triglyceride nanodispersions.

Figure 1: Left: SAXS (blue circles) and SANS (red circles) data of a triglyceride nanoemulsion stabilized with sodium dodecyl sulfate (SDS). The simultaneous fits (black lines) reveal spherical shaped particles with a diameter of 17 nm and a SDS layer with a thickness of 0.8 nm. Right: DSC heating and cooling curves of triglyceride particles, which show a melting peak at untypical low temperatures.

References [1] Oliveira, D. INTECH Open Access Publisher 2011. [2] Botet, R. J. Phys. Conf. Ser. 2012 352, 0012047. [3] Schmiele, M. J. Chem. Phys. 2014 14, 214905.

199 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 39 Erlangen, Germany

Tribochemically induced optical Property Changes in MgO-Nanoparticle Powders

Schwab, T.; 1,*, Thomele, D.; 1 and Diwald, O.; 1

(1) Department of Chemistry and Physics of Materials, University of Salzburg, Jakob-Haringer-Straße 2a, A-5020 Salzburg/Austria

*e-mail: [email protected]

Keywords: Tribochemistry, Paramagnetic Oxygen Species, Solid-solid interfaces

As an insulator Magnesium Oxide does not show optical absorptions in the range of visible light. Moreover, with its cubic crystal structure this oxide is optically isotropic, non-birefringent which makes it suitable for translucent ceramics.[1] For the production of optical ceramics, particle powders are pressed and subsequently subjected to sintering. The pressure applied has an important effect on porosity and translucence of the pressed powders.

In the present study, we investigated optical property (colour and translucence) of MgO particle ensembles during pressing and tracked at the same time the formation of paramagnetic species in the course of this transformation. For the nanocrystalline MgO powders we observed the following significant changes upon pressing: an absorption band in the range of visible light associated with a change of colour from white to yellow. Complementary measurements with electron paramagnetic resonance spectroscopy point to the pressure-induced emergence of oxygen radicals.[2] These radicals are stable in high vacuum conditions or in oxygen atmosphere but degrade by water absorption. Comparison of pressure and light induced radical formation [2] provides a base for the assignment of UV-Vis absorption features as well as EPR signals and point to a tribochemically induced reaction path that will be discussed in this presentation.

We believe that these findings will have an impact on the processing of MgO based nanocrystalline ceramics. Moreover, pressure induced radical formation is also relevant for heterogeneous catalysis and surface chemistry on oxides in general.

References [1] Krell, A. et al.; J. Eur. Ceram. Soc. 2009 29, 207 – 221. [2] Siedl, N. et al.; Phys. Chem. Chem. Phys. 2014 16, 8339 – 8345

200 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 51 Erlangen, Germany

Chemical Functionalization of Oxide Surfaces: Insights into the Mechanism of Molecular Adsorption at the Solid/Liquid Interface

Schwarz, P. 1*; Meyer, B.1

(1) Interdisciplinary Center for Molecular Materials and Computer Chemistry Center, Friedrich-Alexander-Universität Erlangen-Nürnberg

*e-mail: [email protected]

Keywords: Chemistry at the Solid/Liquid Interface, Simulation Self-assembled monolayers of functional organic molecules on oxide surfaces are utilized in dye-sensitized solar cells, molecular electronics or for tuning the optical and electronic properties of nanoparticles. The organic molecules are usually attached to the oxide surfaces via strongly interacting linker groups, for example, phosphonic acid or silanol units, employing wet-chemical processes. However, how molecules from a solution bind to oxide surfaces is basically unknown. To obtain a fundamental understanding of these chemical processes at the solid/liquid interface we performed ab initio molecular dynamics simulations to study the anchoring of methylsilanetriol (MST) linker units to aluminum oxide surfaces via condensation reactions in the presence of residual water and liquid isopropanol. While in vacuum MST molecules spontaneously coordinate to the surface Al ions via one of their oxygen atoms, adding residual water molecules and liquid isopropanol suppresses the direct approach of MST to the surface. By applying the metadynamics technique we were able to accelerate this activated process and to identify the mechanism of the subsequent condensation reaction. The simulations show a variety of reaction pathways that differ in how MST binds to the surface and how the condensation reaction proceeds. Several scenarios are competing with each other, differing in how and when the MST deprotonates, the surface OH captures a proton and the newly-formed water molecule leaves the surface. As key factor for spontaneous condensation reactions to occur, it was found that an intermediate six-membered ring between the surface Al atom, MST, and the leaving water group has to form. Solvent molecules that are capable to form strong hydrogen bonds, for example residual water, aggravate the formation of the intermediate six-membered ring by hydrogen bond interactions with MST, thereby making the condensation reaction an activated process.

Figure 1: Methylsilantriol binding to aluminum oxide in liquid isopropanol.

201 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 50 Erlangen, Germany

Theoretical study of intramolecular singlet fission

S. Rajagopala Reddy*, P. B. Coto, M. Thoss

Friedrich-Alexander-Universität Erlangen-Nürnberg, Interdisziplinäres Zentrum für Molekulare Materialien (ICMM) & Institut für Theoretische Physik, Staudtstrasse 7/B2, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Singlet fission, nuclear dynamics study, mediated mechanism Singlet fission (SF) [1] is a spin-allowed process in molecular materials, in which a singlet excited state spontaneously splits into a pair of triplet excited states. It holds great possibility to increase the efficiency of solar cells [2]. In collaboration with experimental groups, we have studied intramolecular singlet fission (iSF) in pentacene dimers, which are covalently bonded by suitable linkers to form conjugated, cross-conjugated and non-conjugated systems [3, 4, 5]. In this contribution, we present results of our theoretical study of iSF. Using a methodology that combines multi-reference perturbation theory methods [5], Truhlar’s fourfold diabatization scheme [6] and wave-packet propagation techniques (MCTDH) [7], we show that SF predominantly occurs via a mediated mechanism involving charge transfer states. The impact that the electronic structure of the linker and the conformation of the pentacenes in the dimer have in the process is also discussed.

References 1. M. B. Smith, J. Michl, Chem. Rev., 2010, 110, 6891; M. B. Smith, J. Michl, Annu. Rev. Phys. Chem., 2013, 64, 361. 2. M. C. Hanna, A. J. Nozik, J. Appl. Phys., 2006, 100, 074510. 3. J. Zirzlmeier, D. Lehnherr, P. B. Coto, E. T. Chernick, R. Casillas, B. S. Basel, M. Thoss, R. R. Tykwinski, and D. M. Guldi, Proc. Natl. Acad. Sci. USA 2015, 112, 5325. 4. J. Zirzlmeier, R. Casillas, S. R. Reddy, P. B. Coto, D. Lehnherr, E. T. Chernick, I. Papadopoulos, M. Thoss, R. R. Tykwinski, D. M. Guldi, Nanoscale 2016, 8, 10113. 5. B. Basel, J. Zirzlmeier, C. Hetzer, B. Phelan, M. Krzyaniak, S. R. Reddy, P.B. Coto, N. Horwitz, R. Young, F. White, F. Hampel, T. Clark, M. Thoss, R.R. Tykwinski, M. Wasielewski, and D.M. Guldi, Nature Communications (In Press). 6. A. A. Granovsky, J. Chem. Phys. 2011, 134, 214113. 7. H. Nakamura, D. G. Truhlar, J. Chem. Phys. 2001, 115, 10353; H. Nakamura, D. G. Truhlar, J. Chem. Phys. 2002, 117, 5576. 8. H. -D. Meyer, U. Manthe, and L. S. Cederbaum, Chem. Phys. Lett. 1990, 165, 73.

202 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 18 Erlangen, Germany

Magnetic nanoparticles improve cell adhesion to natural polymer-based hydrogels

Raminder Singh1, 2*, Anna Wieser1, Supachai Reakasame3, Barbara Dietel2, Rainer Detsch3, Aldo R. Boccaccini3, Christoph Alexiou1, Iwona Cicha1

1Section of Experimental Oncology and Nanomedicine (SEON), University Hospital Erlangen, Germany

2Department of Cardiology and Angiology, University Hospital Erlangen, Germany 3Institute of Biomaterials, University of Erlangen-Nuremberg, Erlangen, Germany *e-mail: [email protected]

Keywords: hydrogels, iron oxide nanoparticles, cell adhesion

INTRODUCTION: For the successful clinical applications of the natural material-based tissue engineered scaffolds, early cell adhesion and proliferation of cells is required. Magnetic nanoparticles are presently used for various biomedical purposes. In the present study, magnetic nanoparticles were used to enhance the cell adhesion to the hydrogel-based scaffolds, aiming at tissue-engineering applications. For this purpose, viability, proliferation, and morphology of fibroblasts magnetically seeded on different sodium alginate (Alg)-based hydrogels was investigated and compared to conventional seeding approach.

MATERIALS and METHODS: Alginate di-aldehyde (ADA) was covalently crosslinked with gelatin (G) to from ADA-G hydrogel film. In another formulation, silk fibroin (SF) was blended with sodium alginate (Alg). The weight ratio of ADA to G or Alg to SF in the final hydrogels was 50:50. Hydrogels were placed into 24-well plates. Fibroblast (NHDF, normal human dermal fibroblasts) were grown in the DMEM media supplemented with 10% (v/v) FCS and 1% (v/v) antibiotic-antimycotic, at 37°C, with a controlled atmosphere of 5% CO2 and 95% relative humidity. Cells with or without magnetic nanoparticles, were seeded on hydrogels (with or without magnetic field for initial 24 hours) and subsequently grown for 7 days. Cell viability and morphology using different seeding techniques were compared by fluorescent staining (calcein and phalloidin, respectively). WST-8 assay served to analyse the metabolic activity of the cells.

RESULTS: Compared with conventionally-seeded fibroblasts, magnetic cell seeding strongly enhanced the initial cell coverage of ADA-G at day 1. Moreover, in larger parts of ADA-G hydrogels, the formation of a dense cellular layer was observed. Correspondingly, the metabolic activity of magnetically-seeded fibroblasts was enhanced relative of conventional seeding method on day 1, and remained significantly increased on day 3 and day 7. Regarding cell morphology, formation of dense multilayer of axially aligned fibroblasts was observed from day 3 on. In contrast, the conventionally-seeded cells showed criss-crossed orientation.

In the case of Alg/SF, magnetic cell seeding dramatically enhanced the initial cell coverage of hydrogels, compared with conventionally-seeded fibroblasts. Similar to ADA-G, the formation of a dense cellular layer was observed already at day 1 on Alg/SF hydrogels, although axial orientation was not detectable at this stage yet. The metabolic activity of magnetically-seeded fibroblasts was increased 4-fold relative of conventional seeding method on day 1, and remained significantly, nearly 3-fold increased on day 3 and day 7.

203 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 18 Erlangen, Germany

DISCUSSION: Hydrogels provide cells with structural support and aqueous environment similar to the native extracellular matrix, but insufficient initial attachment of cells, and/or non-uniform seeding, are the main cause of graft failure. Our results demonstrated that magnetic cell seeding dramatically improves the strength and uniformity of initial cell attachment to hydrogel surface, which can shorten culture time and may thus play a decisive role for the regenerative outcomes.

OUTLOOK: These preliminary studies represent an important step towards successful fabrication of biocompatible, cell-growth-supporting vascular constructs based on natural hydrogels. In further studies we intendent to use 3D inkjet printing for the fabrication tubular constructs with different lumen diameters. Fibroblasts and endothelial cells will be seeded on the the lumen surface of vascular constructs by using layer-by-layer radial magnetic cell seeding technique (VascuCell endothelizer).

Acknowledgments: This project was supported by the DFG (SI 2093/2-1 and CI 162/2-1).

204 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 55 Erlangen, Germany

Synthesis of Intrinsically Conducting Polymers Directed to Applications at Electronic Area

Prediger, M.1, Santin, K.1 and Rocha, T.1*, Spohr, D.

(1) Universidade do Vale do Rio dos Sinos - UNISINOS, São Leopoldo – RS, Brasil. *e-mail: [email protected]

Keywords: Conducting Polymers, Polyaniline, PEDOT:PSS This study aims the chemical synthesis of intrinsically conducting polymers directed to application in electromagnetic shielding and Faraday Cage. The chemical synthesis of Polyaniline (PAni) was carried out through the mixture of dodecylbenzenesulfonic acid (DBSA), dopant agent, with the monomer aniline by magnetic stirring. A solution of ammonium persulfate was added dropwise into the reaction. After the dripping, the reaction was kept under constant stirring for more 2,5h at room temperature. The material was filtered, washed with water and dried at a desiccator. To obtain polyaniline nanoparticles, immediately after the chemical polymerization, the material was purificated by dialyzing against water and centrifugated to remove the impurities from the reaction. The chemical polymerization of PEDOT:PSS was conducted by the reaction between the poly(styrene sulfonate) (PSS), dopant agent, and the 3,4-ethylenedioxythiophene (EDOT), reaction’s monomer. After the mixture of the reagents, ammonium persulfate and ferric sulfate were added at the reaction, acting as oxidizing agent. The solution was kept under constant stirring for 24h at room temperature. The obtained materials were characterized by Uv-Vis and FT-IR Spectroscopy to examine the absorption bands of the conducting polymers, by the four point probe method to obtain the electric conductivity and by the scanning electron microscope (SEM) to investigate the particle size. PEDOT:PSS showed an electrical conductivity of 0,8S/cm. On the other hand, the PAni nano of 10-1 S/cm and the Polyaniline of 10-3 S/cm. The UV-Vis spectra of the polymers exhibit the band at about 350 nm relative to the transition π-π* present on the conjugated structure of the conducting polymers [1]. Moreover, it was possible to identify at polyaniline’s UV-Vis spectrum, the absorption peaks at about 400nm and 850nm, associated with the polarons [1]. The PAni nano FT-IR spectrum showed the main bands at 1120 cm-1, which was formed during the protonation and at 1242 cm-1, assigned with the formation of the conducting polyaniline[1]. And in the PEDOT:PSS, the spectrum exhibited a peak at 3100 cm-1, relative with PSS (agent dopant) connected at -CH[2]. The images of polyaniline’s particle size show that it belongs to the nanoscale. The intrinsically conducting polymers were obtained successfully and can be applied in the electronic area.

References [1] Han, M.G.; Cho, S.K.; Oh, S.G. T.; Im, S.S. Synth.Met. 2002,126, 53-60. [2] Wang, J.; Zhu, X; Zhou, X. Journal of Applied Polymer Science. 2012, 124, 109-115.

205 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 70 Erlangen, Germany

Shell-by-Shell coating of silver nanocrystals to provide a switchable dispersibility in polar, apolar, and fluorinated solvents

Stiegler, L.* and Hirsch, A.

(1) University of Erlangen-Nuermberg, Institute of Organic Chemistry II, Henkestraße 42, 91054 Erlangen, Germany

*e-mail: [email protected]

Keywords: fluoro-, lipo-, hydro-philic/phobic, shell-by-shell coating, amphiphiles

Interactions between materials and solvents are mostly governed by the surface properties of the material. By attaching organic self-assembled monolayers (SAMs) onto the surface of nanoparticles, colloidal dispersibility can be achieved in various solvents. Herein we describe a wet-chemical covalent functionalization approach using thiols resulting in stabilized silver nanoparticles[1] with hydrophilic, hydrophobic or fluorophilic surfaces. By employing a versatile bilayer coating concept this stable covalent functionalization sequence was extended towards a reversible noncovalent attachment of ionic and nonionic amphiphiles.[2] Thereby, the formation of a micellar arrangement of amphiphilic molecules around pristine coated nanoparticles via solvophobic (that is either hydrophobic, lipophobic, or fluorophobic) interactions led to an orthogonal reversion of the polarity of the surface of nanoparticles.[3]

O F O F F F FF F F F F F N F H F FF FF F F FF F Ag Ag self-assembly Ag

st nd 1st shell: dodecanthiol, 2nd shell:

lipophilic fluorophilic fl. solvent

Figure 1: General Shell-by-Shell coating concept of silver nanocrystals.

References

[1] H. Hiramatsu and F. E. Osterloh, Chem. Mater. 2004, 16, 2509-2511. [2] T. Pellegrino, L. Manna, S. Kudera, T. Liedl, D. Koktysh, A. L. Rogach, S. Keller, J. Rädler, G. Natile and W. J. Parak, J. Am. Chem. Soc. 2004, 4, 703-707. [3] L. Zeininger, S. Petzi, J. Schoenamsgruber, L. Portilla, M. Halik and A. Hirsch, Chem. Eur. J. 2015, 21, 14030-14035.

206 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 78 Erlangen, Germany

The size effect of Pt/Co3O4 nanoparticle model catalysts prepared in UHV for electrocatalytic CO oxidation studied by IRAS

Stumm C. *, Bertram M., Wähler T., Faisal A., Brummel O., Libuda J.

Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander Universität Erlangen-Nürnberg, Erlangen/Deutschland

*e-mail: [email protected]

Keywords: CO electrooxidation, Pt nanoparticles, cobalt oxide, model catalysts, electrochemical IRRAS We have studied the electrooxidation of CO by in-situ IR spectroscopy on a supported model catalyst, which was prepared and characterized by surface science methods in ultrahigh vacuum (UHV). The Pt/Co3O4 model catalysts were prepared UHV conditions by physical vapour deposition (PVD) of different amounts of Pt onto a well-ordered Co3O4(111) film grown on Ir(100). The samples were characterized by low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) before and after the electrochemical experiments. At low pH values the Pt/Co3O4 system dissolves rapidly during potential cycling, whereas at pH 10 at potentials from 0.33 VRHE to 1.03 VRHE the films are stable during potential cycling. Within this stability window, electrochemical IR spectroscopy shows the presence of a metallic Pt nanoparticles or partially oxidized nanoparticles at low Pt loading (see Figure 1). Comparison of the nanoparticle surfaces to a well-defined single crystalline Pt(111) surface shows a red-shift of the COt stretching frequency and suppression of the bridging CO for the Pt/Co3O4 system. With decreasing Pt coverage and nanoparticle size, the red-shift increases due to the decreasing coordination number of the Pt atoms. The integrals of the CO oxidation peak in CV and the peak integrals in EC-IRRAS show good agreement.

Figure 1: Surface structure of the Pt/Co3O4 catalysts upon different platinum loadings

207 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 4 Erlangen, Germany

Effective diffusion of tethers between functional surfaces

Stumpf, H. 1,*, Smith, A.-S. 1

(1) PULS Group at the Institute for Theoretical Physics I and EAM, FAU Erlangen-Nürnberg, Germany

*e-mail: [email protected]

Keywords: Multiscale Modeling and Simulations, Functional Surfaces

Molecular reactions of tethers, such as proteins, between fluctuating functional surfaces are strongly dependent on their dynamic properties. Furthermore, because tethers affect the thermal fluctuations, as well as deform the surface which they are confined to, surface-mediated interactions arise [1]. To study these effects, we analytically calculate the forces between tethers in thermal equilibrium [2]. These forces are repellent at high separations, attractive at intermediate ranges as well as entropically attractive in close proximity. Naturally, these interactions have a decisive influence on the dynamics in the system, which we investigate by analytical and numerical methods. For small diffusing clusters of tethers we use a Brownian dynamics simulation. As it turns out, the strong interactions make it possible to employ a simple analytical model of harmonic interactions, showing excellent agreement with simulations. For higher amounts of bonds we look at the diffusion of a single tether in a tether domain, which is treated by a multiscale approach, resulting in an effective diffusion coefficient as a function of tether density and surface parameters [3]. We find that the diffusion is greatly reduced depending on the tether density, where at low densities, only two tethers interacting at a time, the effect is strongest.

Figure 1: Diffusing tether (red) in affixed tether domain References [1] Fenz, S.; Smith, A.-S. Nat. Phys. 2017, accepted [2] Schmidt, D.; Smith, A.-S. EPL 2012 99.3, 38003. [3] Pavliotis, G.A.; Vogiannou, A. FNL 2008 8, L155-L173

208 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 33 Erlangen, Germany

Classification of nanoparticles smaller than 50 nm

Süß, S.; 1,2,* Segets, D.; 1,2 and Peukert, W. 1,2

(1) Institute of Particle Technology (LFG), FAU Erlangen-Nürnberg, Germany (2) Interdisciplinary Center for Functional Particle Systems (FPS), FAU Erlangen-Nürnberg, Germany

*e-mail: [email protected]

Keywords: Classification of Nanoparticles, Size-exclusion chromatography, Size-selective precipitation Nanoparticles (NPs) like ZnS and Au NPs are widely used in a lot of applications such as electronics or medicine due to their size-dependent optical properties. However, even when the synthesis step is optimized, the obtained small but non-negligible dispersity in the particle size distribution (PSD) leads to a reduced product quality. Thus, methods for the post-synthetic classification of NPs, e.g. by size-exclusion chromatography (SEC), need to be developed.

First, as reference process, the size-selective precipitation (SSP) of ZnS NPs (x1.3 = 1.8 nm) was developed. Therefore an anti-solvent is added to the suspension, whereas the larger NPs flocculate first. We showed how SSP depends on the relative permittivity of the solvent mixture and how excellent results for the classification sharpness κ even beyond 0.7 and thus close to analytical separation are achieved. For chromatographic separation, SEC is using a porous stationary phase, whereat the separation effect is based on the size-dependent diffusion of NPs into the porous material. Thus, for tailored separation, many parameters need to be taken into account. Therefore, the interactions of the NPs with a suitable stationary phase are of major importance for the feasibility of SEC. In preliminary standardized shaking experiments for the identification of appropriate stationary phases, we developed a routine to investigate the adsorption of gold NPs (xmod.3 = 20.3 – 54.8 nm) as well as ZnS NPs on several commercially available stationary phases. Knowledge of these interactions is absolutely mandatory because unwanted adsorption of NPs will block the pores of the column making the separation of particles by SEC impossible. By performing SEC experiments, we obtained different retention times with high reproducibility according to the underlying PSDs. Furthermore, we systematically varied the process parameters, e.g. flow rate in order to improve the separation performance. With these, we were able to separate two species of a bimodal sample (Au NPs) into two discrete peaks. A fraction collector after the SEC was used to collect differently sized NPs and allowing the derivation of separation efficiencies that are finally compared to former SSP results. In conclusion, we developed a reasonable approach to describe and execute the separation of NPs using SSP and SEC. This paves the way to continuous and knowledge-based separation of NPs below 50 nm based on tailored particle-particle interactions. References [1] Segets, D.; Komada, S.; Butz, B.; Spieker, E.; Mori, Y.; Peukert, W. J. Nanopart. Res. 2013 15, 1486. [2] Segets, D.; Lutz, C.; Yamamoto, K.; Komada, S.; Süß,S.; Mori, Y.; Peukert, W. J. Phys. Chem. C, 2015 119, 4009-4022. [3] Süß, S.; Sobisch, T.; Lerche, D.; Mori, Y.; Peukert, W.; Segets, D. Chem. Ing. Tech. 2016 88, 1298.

209 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 61 Erlangen, Germany

Atomic Layer Deposition for Building Ultrathin Amorphous Silicon Solar Cells with Nano-pore Array Structure

Sun H 1,*, Julien B1

1 Department of Chemistry and Pharmacy, Friedrich -Alexander University of Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany *e-mail: [email protected]

Keywords: atomic layer deposition, Amorphous Si solar cell, nano-pore array structure Applications of silicon solar cells are limited by their cost and/or efficiency. Amorphous silicon (a-Si) cells provide cost reductions but their planar geometry limits their performance. In the present work, nanopore arrays are used as a template to structure a-Si junctions to address this issue. Nanopore arrays can display excellent antireflection characteristics, efficient light trapping, and improve the efficient charge carrier diffusion and collection in thin coatings due to the short collection length of photogenerated carriers. This offers opportunities for improving solar cell efficiency and reducing material consumption[1]. Here, 'anodic' aluminum oxide is produced as a nanoporous template, then coated with SiO2 by atomic layer deposition. After growing SiO2 doped with either Sb (n) or Al (p) as thin layers on the pore walls, Li is used to reduce SiO2 into Si thermally. Finally, electrical contacts are sputter-coated on both sides of the template to contact each side of the Si homojunction, and fabricate it into a solar cell. This preparative strategy offers a model system in which to investigate systematically how geometry and doping levels can be exploited to optimize the solar cell’s performance. References [1] Diedenhofen, S. L.; Janssen, O. T. A. ACS Nano. 2011 5, 2316−2323.

210 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 48 Erlangen, Germany

Adsorption of ionomers on carbon black dispersions

Thoma, M. 1,*, Hoffmann, E. 1, Lin, W. 1, Damm, C. 1 and Peukert, W. 1

(1) Institute of Particle Technology, FAU Erlangen-Nürnberg, Germany

*e-mail: [email protected]

Keywords: PEM fuel cell, adsorption isotherm, PFSA ionomer Proton exchange membrane fuel cells (PEMFCs) are of great interest for environmental-friendly conversion of chemical energy into electricity. The electrodes consist of catalyst particles precipitated on carbon black (CB) embedded in a matrix of perfluorinated sulfonic acid (PFSA) ionomer. For electrode layer production the pristine materials are dispersed in a solvent prior to layer formation. The interactions between catalyst particles, ionomer and solvent are defining the colloidal stability and properties of the catalyst-ink and therewith the structure and effectivity of the MEA. An understanding of the influence of catalyst-ionomer interactions on the ink properties is indispensable to customize catalyst-inks and optimize MEAs. In this work we present a simple and fast method to estimate adsorption isotherms of ionomers on CB. The equilibrium of the PFSA ionomer concentration is determined by measuring the dispersion density using a u-tube oscillator after separating the CB particles. The adsorption isotherms are fitted with a Langmuir model followed by multilayer adsorption at higher ionomer concentrations.[1] The method was validated by comparing the results with adsorption isotherms measured by isothermal titration calorimetry showing e.g. similar surface coverage concentrations. Moreover, the influence of material properties on the adsorption isotherms was investigated. It was found that a larger amount of ionic side chains (given as equivalent weight (EW) in g/mol

SO3H) as well as a larger number of hydrophilic functional groups on the CB surface lead to a reduction of the maximum ionomer coverage on the CB surface (Figure 1).

Figure 1 Dependence of the saturation surface coverage of CB on the EW of the PFSA ionomer References [1] Ma, S.; Chen, Q.; Jøgensen, F.; Stein P.; Skou, E., Solid State Ionics 2007 178, 1568-1575.

211 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 22 Erlangen, Germany

Micro-Swimming with Inertia

Trosman,Oleg 1,2 *, Pande, Jayant 1,2 and Smith, Ana-Sunčana 1,2,3

(1) PULS group, Department of Physics, Friedrich-Alexander-University of Erlangen-Nuremberg, Germany (2) Cluster of Excellence: Engineering of Advanced Materials, Friedrich-Alexander-University of Erlangen-Nuremberg, Germany (3) Division of Physical Chemistry, Ruđer Bošković Institute, Zagreb, Croatia

*e-mail: [email protected]

Keywords: Three bead microswimmer, Inertial effects beyond the pure Stokes regime.

Increased theoretical study in the past few decades has enabled scientists to gain a deeper insight into the motion of micro-swimmers, yet most theoretical approaches addressed the domain of negligible Reynolds number Re, ignoring inertia. In nature, however, in an intermediate range of Re, before turbulences arise, the inertial effects become important. In this work we conduct a theoretical study of how this regime emerges. For this we extend the swimmer model by Golestanian and Najafi [1], which has three beads attached in series in a fluid and moving along the axis of the swimmer, by inclusion of the beads’ masses. We do this by combining the Oseen-Stokes equations for the coupled motion of distant spheres in a fluid with Newton’s force-mass relations and obtain a coupled system of first-order differential equations. Solving these equations allows us to derive a closed-form expression for the velocity of the swimmer which explicitly takes inertia into account. This velocity expression compares considerably better to results obtained from lattice-Boltzmann simulations of the swimmer, for intermediately high bead masses or driving forces, than the inertia-free model of Golestanian and Najafi.

References [1] R. Golestanian and A. Ajdari, Analytic results for the three-sphere swimmer at low Reynoldsnumber , Physical Review E - Statistical, Nonlinear and Soft Matter Physics , 77(3):1, 2008. ISSN 15393755. doi: 10.1103/PhysRevE.77.0363

212 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 14 Erlangen, Germany

Investigating the influence of intermolecular interactions between Naproxen and stabilizers on the morphology of spray-dried dispersions at various process times

Trzenschiok H.1,*, Sterzinger M.1 and Peukert W.1

(1) Institute of Particle Technology, Friedrich-Alexander-University Erlangen-Nürnberg(FAU), Erlangen, Germany

*e-mail: [email protected]

Keywords: precipitation, stabilization, poorly water soluble drugs Due to their molecular structure, many commonly used or new developed drugs are poorly water soluble leading to a decreased bioavailability. One possibility to improve drug delivery to the patient is to reduce the size of drug particles. The minimized size of the particles leads to an improved dissolution rate but also to an increase of the Gibbs free energy hence promoting ripening and agglomeration. Therefore stabilizers like polymers or surfactants are commonly used. Besides the interaction between the stabilizers and the drug-particles another important but in the literature not well-covered influencing parameter on the crystallinity and morphology of the drug particles is the residence time in dispersion. To investigate the stabilizers influence as a function of time Naproxen particles were precipitated by pH-shift and the time between precipitation and drying was varied systematically by direct coupling of a T-mixer to a laboratory scale spray dryer. By this approach, different residence times between 3 and 1800 seconds could be analysed. The influence of different intermolecular interactions was investigated using two polymers with different functional groups. The morphology, crystallinity and the interaction between the drug and the polymers were studied by X-ray diffraction, Fourier transformed infrared spectroscopy and differential scanning calorimetry. Depending on the polymer type used for stabilization clear differences in the evolution of the particle properties were observed. This effect was correlated to hydrogen bonding between drug molecules and polymer chains which were identified by vibrational spectroscopy. For both polymers the observed changes of the particles morphology were verified by scanning electron microscopy. The effects of the particles residence time in dispersion were investigated by analytical centrifugation of redispersed powders. In summary, the influence of the drug-polymer interactions on the crystalline state of the particles at different process-times were investigated and it was shown, that a simple reduction of the particles residence-time in dispersion does not result in the formation of redispersible sub-micron particles.

213 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 96 Erlangen, Germany

Correlative probe and electron microscopy of GaN and AlN films on Si {111} substrate

Vacek, P.; 1,2,*, Nováček, Z.; 3 ,Dluhoš, J.; 4 and Gröger, R.;2

(1) Academy of Sciences of the Czech Republic: CEITEC IPM, Žižkova 22, 616 62 Brno, Czech Republic (2) Brno University of Technology: Central European Institute of Technology, Purkyňova 123, 612 00 Brno, Czech Republic (3) NenoVision: Purkyňova 127, 612 00 Brno, Czech Republic (4) Tescan Brno: Libušina tř. 1, 632 00 Brno, Czech Republic

*e-mail: [email protected]

Keywords: Scanning probe microscopy, Scanning electron microscopy, Correlative imaging

III-nitrides (AlN, GaN, InN) are promising materials for optoelectronic applications, high-frequency short-wavelength UV devices for water purification and long lifetime lasers for high-density data storage. The internal quantum efficiency of these devices is negatively affected by high density of threading dislocations emanating on the surface of the III-nitride film. Further progress in reducing the density of these defects is not possible without detailed understanding the mechanism of their nucleation. To target this objective, we employ a newly established correlative probe and electron microscopy to establish direct link between surface topography of GaN and AlN films on Si {111} substrate obtained by AFM and spatial variation of electrical and optical properties acquired using the SEM/EBIC and SEM/CL detectors, respectively. The simultaneous capture of signals from the probes separated only 100 nm allows us to discriminate threading dislocations in these materials according to changes of electrical and optical properties of the film in their vicinity.

214 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 6 Erlangen, Germany

Adhesion of deformable fluctuating interfaces by multiple types of functional complexes

Vlajčević, J.; 1,* and Smith, A.; 1,2

(1) Division of Physical Chemistry, Ruđer Bošković Institute, Zagreb (2) PULS Group, Institut für Theoretische Physik, Univesität Erlangen-Nürnberg

*e-mail: [email protected]

Keywords: membranes, adhesion, complexation, simulation

We present a model for the adhesion of flexible fluid membranes to a flat substrate by functional molecules (ligand-receptor pairs) which are freely diffusing on the adherent interfaces. In the absence of molecular complexation, the membrane resides close to a flat surface in a nonspecific potential that originates from van der Waals interactions and the steric repulsion associated with thermal fluctuations. Upon molecular complexation, the interface is deformed introducing cooperative effects for further specific molecular binding. While the system containing only one type functional pairs has been intensively studied in the past [1], the phase behavior and the dynamics of adhesion mediated by multiple functional pairs is poorly understood [2].

Figure 1: Model of adhesion of flexible membranes mediated by Figure 2: Separation of complexation of diffusing ligands and receptors of multiple types. adhesion domains.

To rectify this issue we construct a Monte Carlo scheme that appropriately accounts for the described adhesion process. We study the organization of functional pairs into domains as a function of the molecular flexibility, length, binding energies and other properties of the system, and find a very rich phase diagram as a function of these parameters. Furthermore, we apply this model to the adhesion of T-lymphocyte cells, by binding of TCR to pMHC and LFA-1 to ICAM-1 proteins, to explain the fundamental processes in the formation of the immune synapse. Acknowledgements: We thank ERCStg 337283 MEMBRANESACT for support.

References [1] Bihr, T.; Seifert, U.; Smith, A. S. New J. Phys. 2015 17, 083016. [2] Weikl, T. R.; Lipowsky, R. Adv. Planar Lipid Bilayers Liposomes. 2007 5, 64-129.

215 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 21 Erlangen, Germany

Wetting and Contact Angle of the [C2Mim][NTf2] Ionic Liquid

at the Neutral Sapphire Interface

Vučemilović-Alagić N.;1,2,* Smith D.M.;1,2 Smith A-S.1,2,3

1EAM, Cluster of Excellence, Erlangen, Germany, 2Ruđer Bošković Institute, Zagreb, Croatia, 3Institute for Theoretical Physics I, Friedrich-Alexander University, Erlangen, Germany

*e-mail: [email protected]

Keywords:ionic liquid, wetting, contact angle

Room Temperature Ionic Liquids (RTILs) have found a vast range of applicability in research and development.1 For applications in heterogeneous and transport systems, as well as porous environments, knowledge of the wettability of RTILs is required.2 Using extensive molecular dynamics (MD) simulations, we have investigated the surface-wetting properties of a model 3 RTIL [C2Mim][NTf2] by employing cylindrically shaped nanodroplets with 2 different radii (with the longitudinal axis oriented along the x direction).

Figure 1: Scheme of cylindrically shaped Figure 2: Simulation of wetting process (ionic liquid at nanodroplet the neutral sapphire interface)

Analysis of our MD simulations allows, for example, the evaluation of the contact angle between the RTIL and the sapphire surface. Additional important properties that are accessible in this way include spreading velocity, film thickness, precursor film and surface tension, all of which are analyzed and described in appreciable detail.

References:

[1] Ionic Liquids in Synthesis; Wasserscheid, P., Welton, T. Eds.;Wiley-VCH: Weinheim, Germany, 2008.

[2] Plechkova N, Seddon K. Applications of ionic liquids in the chemical industry. Chem. Soc. Rev. 2008; 37:123-50

[3] Driskill J, Vanzo D, Bratko D, Luzar A. Wetting transparency of graphene in water. J. Chem. Phys. 2014;141;18C517.

216 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 12 Erlangen, Germany

Coupling of cell density fluctuations and multicellular motion on active interfaces

Vurnek D.; 1,*, Kaliman S.; 1, Aliee M.; 1, Wollnik C.; 2, Rehfeldt F.; 2, Dudziak D.; 3 and Smith A-S.; 1,4

(1) PULS Group at the Institute for Theoretical Physics and EAM, FAU Erlangen-Nürnberg, Germany (2) Biologie Dentritischer Zellen, Hautklinik, Universitätsklinik Erlangen, Germany (3) Third institute of Physics - Biophysics, GAU Göttingen, Germany (4) Division of Physical Chemistry, Ruđer Bošković Institute Zagreb, Croatia

*e-mail: [email protected]

Functional Particle Systems, Multi-cellular Systems, Particle Image Velocimetry

Collective cell migration is triggered by chemical and physical cues that cells find in their environment. These stimuli can be varied by modulating the interface on which cells adhere. Using MDCK II model epithelium grown on collagen I coated glass substrates we look at the global development of an initially droplet seeded system of cells. Allowed to expand freely over time cells grow in a circular fashion. Large scale experiments of live fluorescent samples are preformed spanning days, and having multiple connected fields of view. Subsequently, velocities are extracted with the help of particle image velocimetry. Such multi-scale approach allows for both microscopic (µm) and macroscopic (cm) scales as cell clusters are investigated all the way from the contact inhibited centre up to the colony border which surprisingly shows perpetually changing speeds. Average radial and tangential velocity components as well as velocity correlations in space and time are calculated. Our recent findings show the coupling between the accelerating/decelerating border and the density fluctuations in the bulk of the model tissue as cells that face open space coordinate layer expansion with the ones in the locomotion inhibited centre. [1]

References [1] Vurnek, D.; et. al, In Preparation

217 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 19 Erlangen, Germany

Electrostatically Self-Assembled Multi-Switchable Functional Nanoparticles

Wagner, M. 1,*, Zika, A. 1*, Gröhn F.1

Department Chemistry and Pharmacy, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3 91058 Erlangen

[email protected]

Keywords: Electrostatic Self-Assembly, Functional Nanomaterials, Switchable Nanoparticles

The field of functional nanoparticles is vast and highly inspired by nature. Nanoparticles can be functionalized for medical applications as well as for optical properties. A promising field for biomedical applications are stimuli responsive systems, which bear great potential as drug carriers. As such systems become more and more complex their synthesis can be hard to achieve, which makes the development of facile ways for their preparation inevitable. Supramolecular interactions such as hydrogen bonds or π-π-interactions can be exploited for expanding the scope of a system. Beside the routinely discussed interactions, electrostatic interactions of individual building blocks can also be applied for the organization of complex architectures.

O O O O

S S S S

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O O O

O S SH S O SH O O O

Figure 1: Light and ultrasound cleavable polymers in combination with cationic porphyrin and dendrimer-photoacid assembly with altering aggregation induced by light Polyelectrolytes with respective counter-ions self-assemble to aggregates, which can be controlled by the charge ratio. We focus on both approaches, functional switchable dendritic polyelectrolytes in combination with a non-switchable dye and dendritic non-functional polymers with a photoactive counter ion. The key functional group for the switchable polymer is the disulfide bond, which can be split either with light, ultrasound or via exchange with another thiol group.1 As the synthesis of the disulfide polymer does not require great effort, the desired functional groups can be adjusted in a single step resulting in a highly versatile polymer. In case of the photoacid, the electronic excited state undergoes a short-lived increase in acidity, which can alter the properties due to higher charge density.2 The broad variety of available molecules bears great potential for switches operating at desired pH values. References [1] Wagner, M.; Krieger, A.; Bernhardt, S.; Minameyer, M.; Drewello, T.: Gröhn, F. in preparation [2] Cardenas-Daw, C.; Gröhn, F., J. Am. Chem. Soc., 2015, 137, 8660–8663.

218 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 64 Erlangen, Germany

Photochemical Energy Storage and Electrochemically Triggered Energy Release in the Norbornadiene-Quadricyclane System: UV-Photochemistry and IR-Spectroelectrochemistry in a Combined Experiment

Waidhas, F.;1,* Brummel, O.;1 Bauer, U.;1 Wu, Y.;2 Bochmann, S.;2 Bachmann, J.;2 Papp, C.;1 Steinrück, H.P.;1 Libuda, J.;1 (1) Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, 91058 (Germany); (2) Lehrstuhl für Anorganische und Allgemeine Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, 91058 (Germany) *e-mail: [email protected]

Keywords: norbornadiene, infrared reflection absorption spectroscopy, solar energy conversion

The two isomers norbornadiene (NBD) and quadricyclane (QC) comprise a promising system for solar energy storage in form of a strained organic molecule. In our previous research, we investigated the electrochemically triggered back-conversion of the energy-rich QC to the energy-lean NBD using cyclic voltammetry and electrochemical IR spectroscopy.[1] Characte- ristic vibrational modes of both pure compounds were identified, redox potentials were determined, and procedures were established to follow the electrochemically-triggered back conversion in-situ by means of electrochemical IR reflection absorption spectroscopy (EC-IRRAS). In this contribution, we describe a new photoelectrochemical PEC-IRRAS experiment which allows us to perform in-situ studies of the full storage cycle in the NBD-QC system. Both the photochemically triggered conversion from NBD to QC and the electrochemically triggered back-conversion from QC to NBD are monitored in-situ in thin film configuration under potential control. Careful calibrations were performed to determine concentrations and external quantum efficiencies, and the operation conditions (concentrations, irradiation time, electrode potentials) were varied systematically. Experiments using 4,4′-Bis(dimethylamino)- benzophenone (Michler’s ketone) as photosensitizer and Pt(111) single crystal electrodes revealed that the photochemical and electrochemically triggered conversion between NBD and QC is largely reversible under suitable conditions. In addition to that, we determined selectivities for both the photochemical conversion and the electrochemical back-conversion and identified the critical steps that limit the reversibility of the storage cycle.

Figure 1: Schematic representation of the combined PEC-IRRAS experiment (a) and concentrations NBD and QC measured in-situ in a combined photo and electrochemical experiment.

References: [1] Brummel, O., et al. ChemSusChem. 2016 9(12), 1424-1432.

219 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 29 Erlangen, Germany

Angle-dependent Coloration of Colloid Clusters in Confinement

Wang, J.W.1*, Mbah, C.F.2, Przybilla, T.3, Spiecker, E.3, Engel, M.2, Vogel, N.1

(1) Institute of Particle Technology, FAU, Cauerstr. 6, Erlangen (3) Institute of Micro- and Nanostructure Research, FAU, Cauerstr. 6, Erlangen

*e-mail: [email protected]

Keywords: self-assembly, confinement, photonic color Colloids assemble into crystals upon increase of volume fraction. Complex structures have been achieved by varying composition, interaction, or shape of the constituent colloidal particles [1]. Another method to modify the crystallization process is to utilize interfacial effects by the application of confinement [2]. Recently it has been shown that entropy favors icosahedral symmetry for colloids assembling in spherical confinement [3]. Here we use droplet-based microfluidics to create homogeneous emulsion droplets as sources for defined spherical confinement. This allows systematically investigation of assembly behavior of near- monodisperse colloidal spheres into colloid clusters. We observe a discrete series of colloid clusters with icosahedral symmetry. To understand and explain the formation of the colloidal clusters, we propose a geometric model and extract extremal principles. We also study the angle-dependent photonic color arising from icosahedral arrangement of colloidal particles. Our colloid clusters may find use as templates, photonic materials and building blocks for hierarchical assemblies.

Figure 1: Icosahedral colloid cluster assembled in emulsion droplets.

References [1] P.F. Damasceno, M. Engel, S.C. Glotzer, Science, 2012, 337, 453. [2] N. Vogel, S. Utech, G.T. England, T. Shirman, K.R. Phillips, N. Koay, I.B. Burgess, M. Kolle, D.A. Weitz, J. Aizenberg, PNAS, 2015, 112, 0845. [3] B. de Nijs, S. Dussi, F. Smallenburg, J.D. Meeldijk, D.J. Groenendijk, K. Filion, A. Imhof, A. van Blaaderen, M. Dijkstra, Nature Materials, 2015, 14, 56.

220 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 93 Erlangen, Germany

Multidimensional Characterization of Nanoparticle by Means of Analytical Ultracentrifugation

Wawra, S. 1,*, Walter, J. 1, Nacken, T.1, Halbig, C. 2, Thajudeen T.1, Eigler S.2, Peukert, W. 1 (1) Institute of Particle Technology (LFG), FAU Erlangen-Nürnberg, Cauerstraße 4, 91058 Erlangen, Germany (2) Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany

*e-mail: [email protected]

Keywords: Analytical Ultracentrifugation, particle size characterization, scanning mobility particle sizer Since nanoparticles (NPs) exhibit a large variety of properties, the analysis of shape, size and density is essential. However, the combined analysis of these parameters is a major challenge. Scattering or microscopic techniques are often limited by statistics, resolution and applicability to broad particle size distributions (PSDs). We will demonstrate that analytical ultracentrifugation equipped with an UV-Vis multiwavelength detector (MWL-AUC) is a powerful and highly accurate tool for the multidimensional analysis of NPs. MWL-AUC combines the fractionation of particles in a centrifugal field with in-situ UV-Vis spectroscopy. Our recent developments on the instrumentation, data acquisition and evaluation allow us to largely extend the possibilities of AUC. For platelets such as graphene oxide (GO), a methodology was developed to determine the lateral size distribution directly in solution using AUC.[1] Adopting this procedure to ultrasonication of GO allowed us studying the size evolution of nanoplatelets.[2] Additional Raman- and NMR- information enabled us to identify relevant parameters including the chemical GO-functionalization for a controlled and scalable production of nanoplatelets. AUC can be combined with the scanning mobility particle sizer (SMPS), where particles are classified according to their mobility diameter in the gas phase. Apart from validating the colloidal stability of ionomer particles in solution by comparing results from AUC and SMPS, we used a combination of both methods to determine the average length and diameters of nanorods. MWL-AUC is a powerful technique providing multidimensional access to NPs not accessible so far by any other technique. The direct correlation of size, shape and optical properties of NPs in the range between less than 1 nm and up to 1 µm is highly relevant for a variety of new applications. References [1]. J. Walter, T. J. Nacken, C. Damm, et al., Small, 2015, 11, 814-825. [2]. C. E. Halbig, T. J. Nacken, J. Walter, et al., Carbon, 2016, 96, 897-903.

221 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 1 Erlangen, Germany

Densest Local Structures and Packing Properties of Uniaxial Ellipsoids

Schaller, F.; 1, Weigel, R.; 1,* and Kapfer, S.; 1

(1) Institut für Theoretische Physik, FAU Erlangen-Nürnberg, Staudtstraße 7, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: Granular matter, packing problems, ellipsoid

The relationship between local structure and macroscopic properties is a current research focus in granular matter. We study the distribution of local packing fractions (defined via Voronoi cell volumina) which is a sensitive observable for characterizing these systems. Previously, mainly packings of spherical particles were considered. Here, we focus on packings of uniaxial ellipsoids as an instance of aspherical particles [1]. In particular, we generalize the famous “kissing problem” and report numerical results on the densest local structures of ellipsoids with aspect ratio between 0.7 (oblate) and 1.4 (prolate). Like in the spherical case, these packings locally exceed the density of known ellipsoid crystals. Analogous to results for lattice packings [2], we find that ellipsoids pack denser than spheres, and with more neighbors. In dense disordered packings of ellipsoids, distorted variations of some of our densest packing motifs can be identified. Our results permit us to generalize and test the k-Gamma model for local packing fraction distributions, previously only applicable to spherical particles [3]. References [1] Fabian Schaller et al., Phys. Rev. X 2016 6, 041032 [2] Yoav Kallus, Adv. Math. 2014 264, 355–370 [3] Tomaso Aste et al., Europhys. Lett. 2007 79, 24003

222 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 38 Erlangen, Germany

Confined Etching within 2D and 3D Colloidal Crystals for Tunable Nanostructured Templates: Local Environment Matters

Fedja J. Wendisch, 1,* Richard Oberreiter, 1 Miralem Salihovic, 1 Michael Elsaesser, 1 and Gilles R. Bourret1

(1) Chemistry and Physics, Paris-Lodron University Salzburg, Austria

*e-mail: [email protected]

Keywords: colloidal crystal; metal-assisted chemical etching; nanosphere lithography; Si nanowires; template

We report the isotropic etching of 2D and 3D polystyrene (PS) nanosphere hcp arrays using a 1 benchtop O2 RF plasma cleaner. Unexpectedly, this slow isotropic etching allows tuning both particle diameter and shape. Due a suppressed etching rate at the point of contact between the PS particles originating from their arrangement in 2D and 3D crystals, the spherical PS templates are converted into polyhedral structures with well-defined hexagonal cross-sections in directions parallel and normal to the crystal c-axis. Additionally, we found that particles located at the edge (surface) of the hcp 2D (3D) crystals showed increased etch rates compared to the particles within the crystals. This indicates that 2D and 3D order affect how nanostructures chemically interact with their surroundings. This work also shows that the morphology of nanostructures periodically arranged in 2D and 3D supercrystals can be modified via gas-phase etching, and programmed by the superlattice symmetry. To show the potential applications of this approach, we demonstrate the lithographic transfer of the PS template hexagonal cross-section into Si substrates to generate Si nanowires with well-defined hexagonal cross-sections using a combination of nanosphere lithography and metal-assisted chemical etching.

References [1] Fedja J. Wendisch, Richard Oberreiter, Miralem Salihovic, Michael S. Elsaesser, and Gilles R. Bourret

ACS Appl. Mater. Interfaces 2017, 9, 3931–3939

223 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 57 Erlangen, Germany

Synthesis and modification of silicon/germanium nanoparticles in the gas phase

Wergen, L.1,*, Mehringer, C.1 and Peukert, W.1

(1) Institute of Particle Technology, Friedrich-Alexander-University Erlangen-Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany

*e-mail: [email protected]

Keywords: silicon, germanium, nanoparticles, doping, gas phase synthesis

Semiconducting nanoparticles (NPs) from e.g. germanium or silicon are promising materials in the field of printable electronics. Dispersed in organic liquids and deposited as thin functional film the NPs can be utilized in electronics, optoelectronics or photovoltaics. The NPs are synthesized through SiH4 and GeH4 pyrolysis in a reactor system utilizing two consecutive hot-wall reactors. This 2-stage setup allows besides from the production of pure silicon NPs or germanium NPs also the combination of these materials like GeSi alloy NPs or anisotropic hybrid particles from Ge and Si.[1,2] The particles in general show a well-defined morphology and a narrow size distribution. Through different growth regimes patchy or Janus-like particles (Ge@Si NPs) can be synthesized. Also alloying Si and Ge to yield GexSi1-x particles with controllable composition is possible. Through addition of phosphine or diborane during synthesis n- or p-doping of NPs in a wide range is achievable dependent on process parameters e.g. temperature.

Figure 1: a) SEM/TEM image of Si NPs, b) Growth diagram for anisotropically coated particles, c) Measured doping concentration compared to nominal doping concentration for phosphorus and boron doped Si NPs

The progress on the synthesis of Si and GeSi NCs will be demonstrated, regarding the influence of the process parameters on their morphology, composition and growth. Furthermore the in-situ modification of NCs through impurity doping as a function of process parameters will be discussed. References [1] Mehringer, C. et al. J. Aerosol Sci. 2014 67, S. 119–130. [2] Mehringer, C. et al. Nanoscale 2015 7 (12), S. 5186–5196.

224 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 11 Erlangen, Germany

Modelling the reactions catalysed by coenzyme B12-dependent enzymes: Accuracy and cost-quality balance

Wick, C. R. 1,2,* and Smith, D. M. 1,2

(1) Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, 1000 Zagreb, Croatia (2) PULS Group, FAU Erlangen-Nürnberg, Nägelsbachstraße 49b, 91052 Erlangen, Germany

*e-mail: [email protected]

Keywords: Multiscale Modelling and Simulation, Catalysis, radical reactions

Coenzyme B12 (5’-deoxyadenosylcob(III)alamin, dAdoCbl) is one of the most prominent organometallic cofactors due to the presence of a carbon-cobalt (Co-C) bond, which is the key to enzymatic reactions utilizing coenzyme B12 as a cofactor: The homolytic cleavage of the Co-C bond is highly encouraged compared to the nonenzymatic reaction and leads to the formation of a 5’-dAdo radical. In the (subsequent or concerted) second step, the 5’-dAdo radical is involved in an H-atom transfer reaction, generating a substrate radical and 5’-dAdo. The two reactions have been subject to many theoretical investigations. Recently, two studies[1,2] have elucidated the importance of the model system design and the inclusion of dispersion and solvent corrections for the Co-C breaking step. Concomitantly, the accurate description of the H-atom transfer reaction is known to be very sensitive to the level of theory applied.[3–5] Our goal is to find a level of theory that ensures an accurate description of both reactions, Co-C cleavage and H-atom transfer. We present an ONIOM(QM/MM) setup that simultaneously reduces the computational costs and retains the accuracy of non-approximate calculations on the full coenzyme system. This enables us to accurately simulate the full catalytic reaction within the enzyme by means of a cross-validated, QM/MM-based approach, while tremendously increasing the accessible timescales compared to other high-level model chemistries.

Figure 1: Minimal mechanism for the reactions catalyzed by dAdoCbl-dependent enzymes. References [1] Qu, Z.; Hansen, A.; Grimme S. J. Chem. Theory Comput. 2015, 11, 1037–1045. [2] Kepp, K. P. J. Phys. Chem. A 2014, 118, 7104–7117. [3] Henry, D. J.; Parkinson, C. J.; Mayer, P. M.; Radom, L. J. Phys. Chem. A 2001, 105, 6750–6756. [4] Coote, M. L. J. Phys. Chem. A 2004, 108, 3865–3872. [5] Durbeej, B.; Sandala, G. M.; Bucher, D.; Smith, D. M.; Radom, L. Chemistry 2009, 15, 8578–85.

225 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 95 Erlangen, Germany

Determination of nanoscale 3D electrostatic field at electron field emitter

Wu, M.1*, Tafel, A.2, Hommelhoff, P.2 and Spiecker, E.1

(1) Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), Department of Materials Science, Univ. of Erlangen-Nürnberg, Cauerstr. 6, 91058 Erlangen (2) Chair of Laser Physics, Department of Physics, Univ. of Erlangen-Nürnberg, Staudstr. 1, 91058 Erlangen

*e-mail: [email protected]

Keywords: field emission, electrostatic field, tomography

Revealing the local electrostatic field of cold electron field emission tips in working condition is the key to answer the fundamental question of how the field interacts with the sharp tip, which has not yet been adequately addressed despite its long history [1]. Furthermore, the knowledge of electrostatic field topography around the tip apex may form the basis of an aberration correction scheme for atom probe tomography [2]. Here, we determine the 3D electrostatic field in nanoscale around an axially symmetric electron field emitter during in situ biasing the tip to field emission condition. The corresponding emission current is logged simultaneously. The (projected) field is determined by accurate measurement of the electron beam deflection while it propagates through the sample area by differential phase contrast in scanning transmission electron microscopy (DPC-STEM, cf. Fig. 1). Assuming axial symmetry of the setup, the axial slice of the field (and thus also the 3D field) can be reconstructed via suitable tomographic reconstruction (here we applied the inverse Abel transform) from the single projection measurement. The experimental results are compared with modeling based on finite element calculations. The results show very good agreement. This study will find interest in the broad community of field emission and atom probe tomography research.

Figure 1: Scheme (left) of DPC-STEM, in-situ biasing setup (middle) and reconstructed axis slice of electrostatic field (in tip normal direction) at field emission condition (bias -140V).

References [1] Forbes, R.; Deane, J. P. Roy. Soc. A. 2007 463, 2907. [2] Kelly, T., Microsc. Microanal. 2017 23, 34.

226 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 25 Erlangen, Germany

Shaping particles by reaction and diffusion Yang, T. 1,*; Segets, D. 2,3; Peukert, W. 2,3; and Han, Y 1 (1) State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, 100190 Beijing, China (2) Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Cauerstraße 4, 91058 Erlangen, Germany (3) Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Haberstraße 9a, 91058 Erlangen, Germany *e-mail: [email protected]

Keywords: reaction, diffusion, mixing, particle shape, concentration gradient It’s widely known that the particle morphologies are dominated by both kinetics and thermodynamics. Under the actual conditions far away from equilibrium, the kinetic processes play a major role in the evolution of particle shapes. From a point of view of chemical engineering, the reaction and diffusion of chemicals, as two general kinetic factors in particle growth, are put forward to be a strategy for regulating particle shapes. Generally, taking silver as an example, reaction-limited situations produce compact shapes, while diffusion-controlled conditions account for dendritic ones or even tiny crystals 1,2. This morphological evolution is attributed to the concentration gradient surrounding the growing particles, which depends on reaction-diffusion conditions 3. After establishing quantitative methods for particle shape characterization by optical spectroscopy and analytical centrifugation (AC), mixing effects are investigated by a T-mixer. Poor mixing results in less contact of reactants so as to low apparent reaction rate, which together with the preferential growth of high-energy facets leads to sheet-like products. In contrast, good mixing gives a fast reaction and relatively limited diffusion, which generates dendritic particles.

Figure 1: An illustration of the concentration gradient mechanism. (a) Completely limited reaction accounts for compact particles. (b) Purely diffusive transport dominated, the appropriate concentration gradient around nuclei inducing interface instability leads to dendrites. (c) Extremely limited diffusion results in tiny crystals. References (1) Yang, T.; Han, Y. Cryst. Growth Des. 2016 16, 2850–2859. (2) Yang, T.; Han, Y.; Li, J. Chem. Eng. Sci. 2015 138, 457–464. (3) Yang, T.; Liu, J.; Dai, J.; Han, Y. CrystEngComm 2017 19, 72–79.

227 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 80 Erlangen, Germany

Photocatalytic H2 generation using dewetted noble metal decorated TiO2 nanotubes

Yoo, J. E.1, and Schmuki, P1,2,3*

(1) Department of Material Science and Engineering, WW4-LKO, University of Erlangen-Nuremberg, Martensstrasse 7, D-91058 Erlangen (2) Chemistry Department, Faculty of Sciences, King Abdulaziz University, 80203 Jeddah, Saudi Arabia Kingdom (3) Regional Center of Advanced Technologies and Materials, Faculty of Scinece, Palacky University, 17.Listopadu 1192/12, 771 46 Olomouc, Czech Republic

*e-mail: [email protected]

Keywords:TiO2, H2 generation, Co-catalysts

In present work, we discuss an approach to produce highly defined optimized noble metal nanoparticle decorated TiO2 nanotube. A key feature is to deposit after thin metal layers on the NT surface of the nanotubes and to transform into noble metal nanoparticles by thermal dewetting. For perfect metal particles-ordering, extremely well ordered TiO2 NT layers are required. Theses are produced by self-organizing electrochemistry.

We investigate these Me@TiO2-NT substrates for the photocatalytic production of H2 from ethanol solution. Dependent on the metal particles loading, and the annealing condition, highly optimized catalyst geometries can be formed. These Me@TiO2 NTs exhibited a H2 production rate ca. 13 or 20 times higher than that of Me NPs-decorated compact TiO2 films. These results show that the geometrical features of our new photocatalytic platform can largely enhance the

H2 production ability of photocatalytic systems.

Figure 1: SEM images of Me@TiO2 nanotube arrays after thermal dewetting. References [1] Fujishima, A.; Honda, K. Nature 1972 23, 837. [2] Albu, S. P.; Ghicov, A.; Aldabergenova, S.; Drechsel, P.; Leclere, D.; Thompson, G. E.; Macak, J. M.; Schmuki, P. Adv. Mater. 2008 20, 4135. [3] Yoo, J. E.; Lee, K.; Altomare, M.; Selli, E.; Schmuki, P. Angew. Chem. Int. Ed. 2013 52, 7514. [4] Yoo, J. E.; Altomare, M.; Mokhtar, M.; Alshehri, A.; Al-Thabaiti, S. A.; Mazare, A.; Schmuki, P. J. Phys. Chem. C 2016 120, 15884.

228 International Congress Engineering of Advanced Materials ICEAM2017 Postersession 10 - 12 October 2017 Posternr. 67 Erlangen, Germany

Ordered, tunable silicon nanotube arrays as a lithium ion battery material

Zhuo, Y.1,*, and Bachmann, J.1

(1) Department Chemie und Pharmazie, Friedrich Alexander Universität Erlangen Nürnberg, Egerlandstraße 1, 91058 Erlangen

*e-mail: [email protected]

Keywords: lithium ion battery, Si, negative electrode, nanotube

Lithium ion batteries (LIBs) represent an attractive energy storage technology, especially for mobile applications such as personal electronics and electric vehicles. Compared to graphite, which is used as the negative electrode in commercial LIBs, silicon has a theoretical highest lithium storage capacity 8 to 10 times larger, 4,200 mAh g-1 approximately. However, the use of Si in LIBs has been limited due to the large volume change (>300%) that occurs during charging and discharging, which causes electrode fracture and pulverization, and thereby, a drastic loss of capacity. We present ordered arrays of parallel silicon nanotubes as a novel LIB platform. The tubular shape is designed to allow for volume expansion without damage, and thereby, to minimize electrode pulverization and prevent capacity loss in silicon anodes. Our silicon nanotubes are manufactured by a thermal reduction of silicon oxide nanotubes, generated by atomic layer deposition (ALD) onto the walls of the deep, straight, cylindrical pores of anodic aluminum oxide membranes serving as the matrix. Afterwards, the samples are treated with acid to remove the by-product. After sputtering an electrical contact made of gold, the electrodes are assembled into full lithium ion batteries for electrochemical characterization by cyclic voltammetry, charge-discharge, and electrochemical impedance spectroscopy. The performance of the samples can be optimized based on the tubes' geometry.

229

List of Participants in alphabetical order – FAU Erlangen-Nürnberg is located in Erlangen/Fürth/Nürnberg, Germany

Surname First- Contri- Institution Location Email name bution Mr. Abouserie Ahed University of Potsdam Potsdam [email protected] Laboratory of Supramolecular & Germany Materials Chemistry Dr. Albert Jakob Talk 41 FAU Erlangen-Nürnberg [email protected] Institute of Chemical Reaction Engineering Prof Alexiou Christoph University Hospital Erlangen Erlangen christoph.alexiou@uk- Section of Experimental Germany erlangen.de Oncology and Nanomedicine (SEON) Mr. Ali Muhamm Poster 36 FAU Erlangen-Nürnberg [email protected] ad Chair of Organic Chemistry II

Dr. Aliee Maryam Poster 10 FAU Erlangen-Nürnberg [email protected] PULS Group

Dr. Altomare Marco Poster 82 FAU Erlangen-Nürnberg [email protected] WW4: Surface Science and Corrosion Dr. Ameri Tayebeh FAU Erlangen-Nürnberg [email protected] WW6: Materials for Electronics and Energy Technology Dr. Aouane Othmane Poster 26 Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Prof Aspuru- Alán Keynote Harvard University Cambridge [email protected] Guzik 6 Department of Chemistry and USA Chemical Biology Prof Bachmann Julien FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Mr. Bachmann Philipp Poster 81 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Mr. Baer Andreas Poster 8 FAU Erlangen-Nürnberg [email protected] PULS Group

Mr. Bahr Leo Talk 1 FAU Erlangen-Nürnberg [email protected] Alexander Institute of Engineering Thermodynamics Dr. BARR Maïssa FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Ms. Bauer Tanja Talk 74 FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Mr. Bauer Udo Talk 26 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Mr. Bean Jonathan University of York York [email protected] Department of Physics Great Britain

Dr. Berger Daniel Talk 76 Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany 230

Dr. Berkes Balazs B. Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Mr. Berlinghof Marvin Poster 68 FAU Erlangen-Nürnberg [email protected] Nanomaterials Characterization

Ms. Bernhardt Sarah FAU Erlangen-Nürnberg [email protected] Professorship of Molecular Nanostructures Prof Beyerlein Irene Keynote University of California, Santa Santa Barbara [email protected] 1 Barbara (UCSB) USA b.edu

Dr. Bhuin Radha Poster 54 FAU Erlangen-Nürnberg [email protected] Gobinda Chair of Physical Chemistry II

Mr. Bilić Luka Poster 15 Ruder Boskovic Institute Zagreb [email protected] Group for Computational Life Croatia Sciences Ms. Birang Seydeh FAU Erlangen-Nürnberg [email protected] Oskouei Elmira Computational Engineering / Solid Mechanics and Dynamics Prof Bitzek Erik FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Dr. Blackwell Robert Talk 72 FAU Erlangen-Nürnberg [email protected] PULS Group

Dr. Bley Karina Talk 32 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Bochmann Sebastian FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film e materials Ms. Böhm Corinna Poster 89 FAU Erlangen-Nürnberg [email protected] WW3: Glass and Ceramics

Dr. Both Engel Adriana Poster 59 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Dr. Bourret Gilles Talk 47 University of Salzburg Salzburg [email protected] Chemistry and Physics of Austria Materials Prof Brabec Christoph FAU Erlangen-Nürnberg [email protected] WW6: Materials for Electronics and Energy Technology Mr. Brummel Olaf FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Prof Bück Andreas FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Ms. Bukowski Anna Talk 42 FAU Erlangen-Nürnberg [email protected] Poster 75 Institute of Chemical Reaction Engineering Mr. Büttner Pascal Poster 60 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Mr. Chen Nan Poster 24 FAU Erlangen-Nürnberg [email protected] Institute of Fluid Mechanics

Dr. Cherevko Serhiy Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Prof Clark Tim FAU Erlangen-Nürnberg [email protected] Computer Chemistry Center (CCC)

231

Prof Cölfen Helmut Keynote Universität Konstanz Konstanz helmut.coelfen@uni- 14 Germany konstanz.de

Prof Curtin William Keynote École polytechnique fédérale de Lausanne [email protected] 7 Lausanne (EPFL) Switzerland

Ms. Cvitkovic Mislav Talk 19 FAU Erlangen-Nürnberg and [email protected] Ruder Boskovic Institute PULS Group Dr. Damm Cornelia FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Dechet Maximi- FAU Erlangen-Nürnberg [email protected] lian A. Institute of Particle Technology

Mr. Decker Benedikt Talk 62 FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Mr. Demmert Benedikt Poster 16 FAU Erlangen-Nürnberg benedikt.bd.demmert@fau. WW3: Glass and Ceramics de

Mr. Diepold Benedikt Poster 84 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Ms. Dinkel Rebecca Talk 50 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Distaso Monica Talk 60 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Prof Diwald Oliver Talk 49 University of Salzburg Salzburg [email protected] Chemistry and Physics of Austria Materials Mr. Döhler Dirk Talk 51 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Ms. Donhauser Anna FAU Erlangen-Nürnberg [email protected] Physics Education

Dr. Du Xiaoyan FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Mr. Dufond Maxime Talk 67 Aix-Marseille Université Marseille [email protected] Centre Interdisciplinaire de France Nanoscience de Marseille Mr. Düll Fabian Poster 79 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Ms. Embrechts Heide- Poster 77 FAU Erlangen-Nürnberg heidemarie.embrechts@fau. marie Institute of Particle Technology de

Prof Engel Michael Keynote FAU Erlangen-Nürnberg [email protected] 12 Institute of Multiscale Simulation

Dr. Engel Jens Talk 79 Fraunhofer-Institute for Fürth/ [email protected] Integrated Circuits IIS Würzburg e Fraunhofer-Entwicklungszentrum Germany Röntgentechnik EZRT Prof Falqui Andrea Talk 55 King Abdullah University of Thuwal [email protected] Science and Technology Saudi Arabia (KAUST) Biological and Environmental Science and Engineering Division Prof Felfer Peter Talk 56 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Mr. Fey Sebastian FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

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Prof Freund Hannsjörg Keynote FAU Erlangen-Nürnberg [email protected] 3 Institute of Chemical Reaction Engineering Prof Frey Lothar FAU Erlangen-Nürnberg [email protected] Chair of Electron Devices erlangen.de

Prof Friend Cynthia Plenary Harvard University Cambridge [email protected] Talk 1 Department of Chemistry and USA Chemical Biology Mr. Galgon Florian Poster 88 FAU Erlangen-Nürnberg [email protected] WW2: Materials Science and Engineering for Metals Ms. Gehrer Simone Poster 13 FAU Erlangen-Nürnberg [email protected] PULS Group

Dr. Gillen Roland Poster 43 FAU Erlangen-Nürnberg [email protected] Chair of Experimental Physics (Superconductivity) Prof Göken Mathias FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Mr. Gotterbarm Martin Talk 24 FAU Erlangen-Nürnberg [email protected] Joint Institute of Advanced Materials and Processes Mr. Grabau Mathias Talk 25 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Ms. Grochowska Katarzyna Talk 28 The Szewalski Institute of Fluid- Gdansk [email protected] Flow Machinery Polish Academy Poland of Sciences Prof Gröhn Franziska FAU Erlangen-Nürnberg [email protected] Professorship of Molecular Nanostructures Mr. Guess Thomas Poster 90 FAU Erlangen-Nürnberg [email protected] Applied Mathematics 2

Mr. Gülden- Andreas Talk 44 FAU Erlangen-Nürnberg andreas.gueldenpfennig@fa pfennig Poster 2 Institute of Particle Technology u.de

Mr. Hadjab Moufdi Poster 44 Research Center in Industrial Algiers [email protected] Technologies CRTI Algeria

Prof Halik Marcus FAU Erlangen-Nürnberg [email protected] WW5: Polymer Materials

Mr. Hanževački Marko Poster 9 Ruder Boskovic Institute Zagreb [email protected] Group for Computational Life Croatia Sciences Ms. Harreiß Christina Poster 63 FAU Erlangen-Nürnberg [email protected] Chair of Micro- and Nanostructure Research Dr. Harris Joe Talk 39 FAU Erlangen-Nürnberg [email protected] WW3: Glass and Ceramics

Prof Harting Jens Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Prof Hartmann Martin FAU Erlangen-Nürnberg [email protected] Erlangen Catalysis Resource Center (ECRC) Ms. Haschke Sandra Talk 27 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials PD Haumann Marco Keynote FAU Erlangen-Nürnberg [email protected] Dr. 4 Institute of Chemical Reaction Engineering

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Mr. Herrmann Jürgen Talk 6 FAU Erlangen-Nürnberg [email protected] Institute of Manufacturing Technology Mr. Hielscher Johannes Poster 31 FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

PD Hieringer Wolfgang Keynote FAU Erlangen-Nürnberg [email protected] Dr. 4 Chair of Theoretical Chemistry

Ms. Hiltl Pia- Poster 17 FAU Erlangen-Nürnberg [email protected] Theresa Division of Pharmaceutics

Prof Hirsch Andreas EAM FAU Erlangen-Nürnberg [email protected] Talk 5 Chair of Organic Chemistry II

Ms. Hoffmann Eva Poster 69 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Höppel Heinz FAU Erlangen-Nürnberg [email protected] Werner WW1: General Materials Properties Dr. Horneber Tobias Talk 17 Technische Universität Berlin Berlin tobias.horneber@tu- Department of Food Germany berlin.de Biotechnology and Food Process Engineering Mr. Hübner Daniel Talk 40 FAU Erlangen-Nürnberg [email protected] Applied Mathematics 2

Mr. Janeš Josip Poster 5 Ruder Boskovic Institute Zagreb [email protected] Augustin Group for Computational Life Croatia Sciences Dr. Jank Michael Poster 49 Fraunhofer Institute for Integrated Erlangen [email protected] Systems and Device Technology Germany er.de IISB Thin-Film Systems Dr. Janko Christina Talk 70 University Hospital Erlangen Erlangen christina.janko@uk- Section of Experimental Germany erlangen.de Oncology and Nanomedicine (SEON) Ms. Johnson Kayla Poster 46 FAU Erlangen-Nürnberg [email protected] WW1: General Materials du Properties Mr. Josten Jan Paul Poster 94 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Mr. Jung David Poster 3 FAU Erlangen-Nürnberg [email protected] PULS Group

Ms. Kaliman Sara Poster 7 FAU Erlangen-Nürnberg [email protected] PULS Group

Dr. Kapfer Sebastian FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Dr. Katsouna- Ioannis Talk 12 Helmholtz-Institute Erlangen- Erlangen/ [email protected] ros Nürnberg for Renewable Energy Nürnberg Germany Dr. Killian Manuela Poster 56 FAU Erlangen-Nürnberg [email protected] S. WW4: Surface Science and Corrosion Mr. Killilea Niall FAU Erlangen-Nürnberg [email protected] WW6: Materials for Electronics and Energy Technology Ms. Kizaloglu Melek Poster 20 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry I

Mr. Klement Marco FAU Erlangen-Nürnberg marco-klement- Institute of Multiscale Simulation [email protected] 234

Prof Klupp Robin EAM FAU Erlangen-Nürnberg [email protected] Taylor Talk 4 Institute of Particle Technology

Prof Koch Norbert Keynote Humboldt-Universität zu Berlin Berlin [email protected] 11 Integrative Research Institute for Germany the Sciences (IRIS) Ms. Kocsis Krisztina Talk 4 University of Salzburg Salzburg [email protected] Chemistry and Physics of Austria Materials Mr. Kollhoff Fabian Poster 53 FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Dr. König Tobias Talk 48 Leibniz-Institut für Dresden [email protected] A.F. Polymerforschung Dresden e. V. Germany Institute of Physical Chemistry and Polymer Physics Mr. Konnerth Christoph Talk 14 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Prof Körner Carolin EAM FAU Erlangen-Nürnberg [email protected] Talk 6 WW2: Materials Science and Keynote Engineering for Metals 3 Ms. Krieger Anja Talk 52 FAU Erlangen-Nürnberg [email protected] Professorship of Molecular Nanostructures Mr. Kümmel Frank Talk 5 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Ms. Kumpidet Chiraphat Poster 76 FAU Erlangen-Nürnberg [email protected] Institute of Chemical Reaction Engineering Mr. Kunzmann Andreas Talk 66 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry I

Mr. Lamm Steffen Poster 87 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Mr. Langmar Oliver Poster 58 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry I

Dr. Leal-Egana Aldo Talk 71 FAU Erlangen-Nürnberg [email protected] Institute of Biomaterials

Mr. Leber Andreas Poster 37 FAU Erlangen-Nürnberg [email protected] Advanced Materials and Processes (MAP) Ms. Lennert Annkatrin Poster 62 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry I

Dr. Leonardi Alberto Poster 74 FAU Erlangen-Nürnberg [email protected] Institute of Multiscale Simulation

Prof Leugering Günter EAM FAU Erlangen-Nürnberg [email protected] Talk 2 Chair of Applied Mathematics

Mr. Lexow Matthias Talk 75 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Dr. Li Ning Keynote FAU Erlangen-Nürnberg [email protected] 15 WW6: Materials for Electronics and Energy Technology Dr. Li Qianqian Talk 7 Imperial College London London [email protected] Department of Aeronautics Great Britain

Dr. Lim Joohyun Max-Planck-Institut für Düsseldorf [email protected] Eisenforschung GmbH Germany Nanoanalytics and Interfaces 235

Mr. Lin Wei Poster 72 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Liu Ning Talk 11 FAU Erlangen-Nürnberg [email protected] WW4: Surface Science and erlangen.de Corrosion Mr. Liu Xin FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Mr. Lovrić Jakov Talk 64 Ruder Boskovic Institute Zagreb [email protected] Group for Computational Life Croatia Sciences Mr. Luchs Tobias Poster 71 FAU Erlangen-Nürnberg [email protected] Chair of Organic Chemistry II

Dr. Macauley Chandra Talk 78 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Prof Madix Robert J. Talk 9 Harvard University Cambridge [email protected] Harvard John A. Paulson School USA of Engineering and Applied Sciences Ms. Maffeis Viviana Talk 69 Istituto Italiano di Tecnologia Genova [email protected] Nanochemistry Italy

Mr. Mahmoud Ahmed Poster 92 FAU Erlangen-Nürnberg [email protected] Salaheldin Institute of Particle Technology

Prof Maier Sabine Talk 33 FAU Erlangen-Nürnberg [email protected] Poster 35 SPM Group

Dr. Maiti Moumita Talk 20 FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Dr. Makaya Advenit Keynote European Space Agency (ESA) Noordwijk [email protected] 5 The Netherlands Dr. Mandel Karl Talk 46 Julius-Maximilians- Würzburg [email protected] Universität (JMU) Germany .de Fraunhofer ISC Ms. Martinsons Miriam Poster 32 FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Mr. Mashkov Oleksandr FAU Erlangen-Nürnberg [email protected] WW6: Materials for Electronics and Energy Technology Mr. Mateus Giovanny FAU Erlangen-Nürnberg [email protected] Department of Chemical and Bioengineering Prof Maultzsch Janina FAU Erlangen-Nürnberg [email protected] Chair of Experimental Physics (Superconductivity) Mr. May Benjamin Poster 42 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry II

Prof Mayrhofer Karl Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Dr. Mazare Anca Poster 28 FAU Erlangen-Nürnberg [email protected] WW4: Surface Science and Corrosion Mr. Mbah Fru Poster 30 FAU Erlangen-Nürnberg [email protected] Chrameh Institute of Multiscale Simulation

Prof Mecke Klaus FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I erlangen.de

236

Prof Merklein Marion FAU Erlangen-Nürnberg [email protected] Institute of Manufacturing Technology Dr. Merle Benoit Talk 37 FAU Erlangen-Nürnberg [email protected] WW1: General Materials Properties Prof Meyer Bernd Keynote FAU Erlangen-Nürnberg [email protected] 16 Professor of Computational erlangen.de Chemistry Mr. Michaud Mark Poster 41 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Mínguez Ignacio Poster 65 FAU Erlangen-Nürnberg [email protected] Bacho Chair of Chemistry of thin film materials Mr. Mühlbauer Sebastian Poster 27 FAU Erlangen-Nürnberg sebastian.muehlbauer@fau. Institute of Multiscale Simulation de

Dr. Müller Patric FAU Erlangen-Nürnberg [email protected] Institute of Multiscale Simulation

Ms. Münsterjoh Bettina Talk 2 FAU Erlangen-Nürnberg bettina.muensterjohann@fa ann Institute of Engineering u.de Thermodynamics Dr. Nezzari Hassene Poster 45 Research Center in Industrial Algiers [email protected] Technologies CRTI Algeria Institute of Engineering Thermodynamics Mr. Nguyen Nhat Talk 59 FAU Erlangen-Nürnberg [email protected] Truong WW4: Surface Science and Corrosion Mr. Niedermaier Matthias Poster 40 University of Salzburg Salzburg matthias.niedermaier2@sbg Chemistry and Physics of Austria .ac.at Materials Mr. Noll Dennis M. Talk 13 FAU Erlangen-Nürnberg [email protected] Nanomaterials Characterization

Ms. Ozkan Selda Poster 73 FAU Erlangen-Nürnberg [email protected] WW4: Surface Science and Corrosion Prof Palkovits Regina Keynote Rheinisch-Westfälische Aachen [email protected] 10 Technische Hochschule Aachen Germany aachen.de (RWTH) Mr. Park Hyoung- FAU Erlangen-Nürnberg [email protected] won WW5: Polymer Materials

Prof Peukert Wolfgang EAM FAU Erlangen-Nürnberg [email protected] Talk 1 Institute of Particle Technology

Mr. Pflug Lukas Talk 29 FAU Erlangen-Nürnberg [email protected] Applied Mathematics 2

Mr. Plötz Steven Poster 86 FAU Erlangen-Nürnberg [email protected] Joint Institute of Advanced Materials and Processes Mr. Pohl Philip Poster 85 FAU Erlangen-Nürnberg [email protected] Manuel WW1: General Materials Properties Prof Pöschel Thorsten FAU Erlangen-Nürnberg [email protected] Institute of Multiscale Simulation

Dr. Preston Thomas Poster 66 Institute for Energy Technology Kjeller [email protected] Solar Energy Norway

Ms. Puscher Bianka Talk 68 FAU Erlangen-Nürnberg [email protected] Chair of Physical Chemistry I

237

Ms. Rahayu Sri Poster 47 University of Leeds Leeds [email protected] School of chemical and process Great Britain engineering Prof Rauh Cornelia Poster 23 Technische Universität Berlin Berlin [email protected] Fakultät III Germany Prozesswissenschaften Dr. Rechberger Stefanie Keynote FAU Erlangen-Nürnberg [email protected] 15 Chair of Micro- and Nanostructure Research Mr. Rejek Tobias FAU Erlangen-Nürnberg [email protected] WW5: Polymer Materials

Mr. Rey Marcel Talk 61 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Rivas Nicolas Poster 52 Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Dr. Rosemeyer Michael Auer Lighting GmbH Bad michael.rosemeyer@auer- Research & Development Gendersheim lighting.com Germany Mr. Saeb Saba Poster 91 FAU Erlangen-Nürnberg [email protected] Chair of Applied Mechanics

Prof Samori Paolo Plenary Université de Strasbourg & Strasbourg [email protected] Talk 4 CNRS France Institut de Science et d'Ingénierie Supramoléculaires (I.S.I.S.) Dr. Santinacci Lionel Talk 43 Aix-Marseille Université Marseille lionel.santinacci@univ- Centre Interdisciplinaire de France amu.fr Nanoscience de Marseille Mr. Sarcletti Marco FAU Erlangen-Nürnberg [email protected] WW5: Polymer Materials

Ms. Sardar Suneela Talk 36 University of Leeds Leeds [email protected] School of Chemical and Process Great Britain Engineering Mr. Schikarski Tobias Talk 15 FAU Erlangen-Nürnberg [email protected] Institute of Fluid Mechanics

Mr. Schindler Thomas FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Ms. Schlicht Stefanie Poster 83 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Prof Schmidt Kai FAU Erlangen-Nürnberg [email protected] Phillip Institute for Theoretical Physics I

Mr. Schmidt Hans Neue Materialien Fürth GmbH Fürth [email protected] Germany

Prof Schmidt Markus Keynote Leibniz-Institut für Photonische Jena markus.schmidt@leibniz- 8 Technologien Jena (IPHT) Germany ipht.de

Prof Schmiede- Michael Talk 63 FAU Erlangen-Nürnberg michael.schmiedeberg@fau berg Institute for Theoretical Physics I .de

Mr. Schmutzler Tilo Talk 3 FAU Erlangen-Nürnberg [email protected] Nanomaterials Characterization

Mr. Schneider Johannes Talk 53 University of Salzburg Salzburg [email protected]. Chemistry and Physics of Austria at Materials Prof Schreyer Andreas Plenary European Spallation Source ESS Lund [email protected] Talk 5 ERIC Sweden

238

Ms. Schuldes Isabel Poster 34 FAU Erlangen-Nürnberg [email protected] Nanomaterials Characterization

Mr. Schuschke Christian FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Ms. Schüßler Martina Talk 16 FAU Erlangen-Nürnberg [email protected] WW3: Glass and Ceramics

Mr. Schwab Thomas Poster 39 University of Salzburg Salzburg [email protected] Chemistry and Physics of Austria Materials Mr. Schwarz Paul Poster 51 FAU Erlangen-Nürnberg [email protected] Professorship of Computational Chemistry Mr. Schwarz Matthias Talk 10 FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Prof Schwieger Wilhelm Talk 57 FAU Erlangen-Nürnberg [email protected] Institute of Chemical Reaction Engineering Dr. Seelam Rajagopal Poster 50 FAU Erlangen-Nürnberg [email protected] a Reddy Research Group of Prof. Michael Thoss Dr. Segets Doris Talk 35 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Shakeri Ali FAU Erlangen-Nürnberg [email protected] Institute of Multiscale Simulation

Prof Sigmund Ole Plenary Technical University of Denmark Kgs. Lyngby [email protected] Talk 2 Department of Mechanical Denmark Engineering Dr. Singh Raminder Poster 18 University Hospital Erlangen raminder.singh@uk- Section of Experimental erlangen.de Oncology and Nanomedicine (SEON) Prof Smith Ana FAU Erlangen-Nürnberg [email protected] PULS Group erlangen.de

Prof Smith David FAU Erlangen-Nürnberg and [email protected] Ruder Boskovic Institute

Dr. Späth Andreas FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Prof Spiecker Erdmann EAM FAU Erlangen-Nürnberg [email protected] Talk 7 Chair of Micro- and Nanostructure Research Mr. Spohr Daniel Poster 55 Vale do Rio do Sinos University São Leopoldo [email protected] Lauxen Material Engineering Brasil

Prof Stein Andreas Plenary University of Minnesota Minneapolis [email protected] Talk 3 Department of Chemistry USA

Prof Steinmann Paul FAU Erlangen-Nürnberg [email protected] Chair of Applied Mechanics

Prof Steinrück Hans- FAU Erlangen-Nürnberg hans- Peter Chair of Physical Chemistry II [email protected]

Mr. Stepic Robert Talk 73 FAU Erlangen-Nürnberg [email protected] PULS Group

Ms. Stiegler Lisa Poster 70 FAU Erlangen-Nürnberg [email protected] Maria Chair of Organic Chemistry II Sophia

239

Prof Stingl Michael Talk 31 FAU Erlangen-Nürnberg [email protected] Applied Mathematics 2

Mr. Strobel Alexander FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Ms. Stumm Corinna Poster 78 FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry Prof Stummer Wolfgang Talk 77 FAU Erlangen-Nürnberg [email protected] Professorship for Mathematics

Mr. Stumpf B. Poster 4 FAU Erlangen-Nürnberg [email protected] Henning PULS Group

Prof Subramani- Bala Keynote University of Kansas Lawrence [email protected] am 2 Center for Environmentally USA Beneficial Catalysis (CEBC) Dr. Sukhov Alexander Talk 18 Helmholtz-Institute Erlangen- Erlangen/ [email protected] Nürnberg for Renewable Energy Nürnberg Germany Dr. Sun Hong Poster 61 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Mr. Süß Sebastian Poster 33 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Thajudeen Thaseem Talk 80 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Thoma Martin Poster 48 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Tornatzky Hans Talk 34 Technische Universität Berlin Berlin [email protected] Institute of Solid State Physics Germany

Mr. Trosmann Oleg Poster 22 FAU Erlangen-Nürnberg [email protected] PULS Group

Mr. Trzenschiok Holger Poster 14 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Prof Unruh Tobias Keynote FAU Erlangen-Nürnberg [email protected] 15 Nanomaterials Characterization

Mr. Vacek Petr Poster Institute of Physics of Materials Brno [email protected] 96 ASCR Czech Republic Mr. Vlajčević Josip Poster 6 Ruder Boskovic Institute Zagreb [email protected] Group for Computational Life Croatia Sciences Prof Vogel Nicolas Keynote FAU Erlangen-Nürnberg [email protected] 12 Institute of Particle Technology

Ms. Vu Bich Talk 38 FAU Erlangen-Nürnberg [email protected] Ngoc Applied Mathematics 2

Ms. Vučemilović Nataša Poster 21 Ruder Boskovic Institute Zagreb natasa.vucemilovic.alagic@ -Alagić Group for Computational Life Croatia gmail.com Sciences Mr. Vurnek Damir Poster 12 FAU Erlangen-Nürnberg [email protected] PULS Group

Mr. Wagner Maximilia Poster 19 FAU Erlangen-Nürnberg Maximilian.m.wagner@fau. n Professorship of Molecular de Nanostructures Mr. Waidhas Fabian Poster 64 FAU Erlangen-Nürnberg [email protected] Professorship of Physical Chemistry 240

Dr. Wang Fengwen Talk 30 Technical University of Denmark Kgs. Lyngby [email protected] Department of Mechanical Denmark Engineering Mr. Wang Junwei Poster 29 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Prof Wasser- Peter EAM FAU Erlangen-Nürnberg [email protected] scheid Talk 3 Institute of Chemical Reaction Engineering Mr. Wawra Simon E. Poster 93 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Mr. Weigel Robert Poster 1 FAU Erlangen-Nürnberg [email protected] Institute for Theoretical Physics I

Prof Weil Tanja Keynote Max-Planck-Institut für Mainz [email protected] 13 Polymerforschung, Mainz Germany

Dr. Wein Fabian Talk 22 FAU Erlangen-Nürnberg [email protected] Applied Mathematics 2

Mr. Weissen- Tobias Talk 58 FAU Erlangen-Nürnberg [email protected] berger Institute of Chemical Reaction e Engineering Mr. Wendisch Jan-Fedja Poster 38 University of Salzburg Salzburg [email protected] Department Chemistry and Austria t Physics of Materials Mr. Wergen Lukas Poster 57 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology

Dr. Wick Christian Poster 11 Ruder Boskovic Institute Zagreb [email protected] Rainer Group for Computational Life Croatia Sciences Mr. Wildner Wolfgang Talk 8 FAU Erlangen-Nürnberg [email protected] Institute of Polymer Technology erlangen.de

Dr. Will Johannes Talk 54 FAU Erlangen-Nürnberg [email protected] Nanomaterials Characterization

Prof Will Stefan FAU Erlangen-Nürnberg [email protected] Institute of Engineering Thermodynamics Prof Willen- Norbert Talk 65 Karlsruher Institut für Karlsruhe [email protected] bacher Technologie Germany du MVM - Angewandte Mechanik Prof Winnacker Albrecht FAU Erlangen-Nürnberg and [email protected] Centre for Advanced Materials i-erlangen.de Uni Heidelberg Mr. Winterhal- Felix FAU Erlangen-Nürnberg [email protected] ter Institute for Theoretical Physics I

Prof Witte Gregor Keynote Philipps-Universität Marburg Marburg [email protected] 16 Germany marburg.de

Ms. Wittmann Judith FAU Erlangen-Nürnberg [email protected] WW5: Polymer Materials

Mr. Wolf Torsten Talk 21 FAU Erlangen-Nürnberg [email protected] Joint Institute of Advanced Materials and Processes Mr. Wormser Maximi- Talk 23 FAU Erlangen-Nürnberg [email protected] lian Joint Institute of Advanced e Materials and Processes Dr. Wu Mingjian Poster 95 FAU Erlangen-Nürnberg [email protected] Chair of Micro- and Nanostructure Research Mr. Yang Tao Poster 25 FAU Erlangen-Nürnberg [email protected] Institute of Particle Technology 241

Ms. Yoo JeongEun Poster 80 FAU Erlangen-Nürnberg [email protected] WW4: Surface Science and Corrosion Prof Zaumseil Jana Keynote Universität Heidelberg Heidelberg zaumseil@uni- 9 Applied Physical Chemistry Germany heidelberg.de

Mr. Zeltner Richard Talk 45 Max Planck Institute for the Erlangen [email protected] Science of Light Germany e Photonic Chrystal Fibre Division Ms. Zhuo Ying Poster 67 FAU Erlangen-Nürnberg [email protected] Chair of Chemistry of thin film materials Mr. Zika Alexander FAU Erlangen-Nürnberg [email protected] Professorship of Molecular Nanostructures

242 International Congress Engineering of Advanced Materials ICEAM2017 10 – 12 October 2017 · Erlangen · Germany International Congress Engineering of Advanced Materials ICEAM2017

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