Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms

Total Page:16

File Type:pdf, Size:1020Kb

Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln US Department of Energy Publications U.S. Department of Energy 1999 Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Gordon E. Brown Jr. Stanford University Victor Henrich Yale University William Casey University of California David Clark Los Alamos National Laboratory Carrick Eggleston University of Wyoming See next page for additional authors Follow this and additional works at: https://digitalcommons.unl.edu/usdoepub Part of the Bioresource and Agricultural Engineering Commons Brown, Gordon E. Jr.; Henrich, Victor; Casey, William; Clark, David; Eggleston, Carrick; Andrew Felmy, Andrew Felmy; Goodman, D. Wayne; Gratzel, Michael; Maciel, Gary; McCarthy, Maureen I.; Nealson, Kenneth H.; Sverjensky, Dimitri; Toney, Michael; and Zachara, John M., "Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms" (1999). US Department of Energy Publications. 197. https://digitalcommons.unl.edu/usdoepub/197 This Article is brought to you for free and open access by the U.S. Department of Energy at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in US Department of Energy Publications by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. Authors Gordon E. Brown Jr., Victor Henrich, William Casey, David Clark, Carrick Eggleston, Andrew Felmy Andrew Felmy, D. Wayne Goodman, Michael Gratzel, Gary Maciel, Maureen I. McCarthy, Kenneth H. Nealson, Dimitri Sverjensky, Michael Toney, and John M. Zachara This article is available at DigitalCommons@University of Nebraska - Lincoln: https://digitalcommons.unl.edu/ usdoepub/197 Chem. Rev. 1999, 99, 77−174 77 Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Gordon E. Brown, Jr.* Surface and Aqueous Geochemistry Group, Department of Geological & Environmental Sciences, Stanford University, Stanford, California 94305-2115 Victor E. Henrich* Surface Science Laboratory, Department of Applied Physics, Yale University, New Haven, Connecticut 06520 William H. Casey Department of Land, Air, and Water Resources, University of California, Davis, Davis, California 95616 David L. Clark G.T. Seaborg Institute for Transactinium Science, Nuclear Materials Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 Carrick Eggleston Department of Geology and Geophysics, University of Wyoming, Laramie, Wyoming 82071-3006 Andrew Felmy Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 D. Wayne Goodman Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255 Michael Gra¨tzel Institute of Chemical Physics, EÄ cole Polytechnique Fe´de´rale de Lausanne, CH-1015 Lausanne, Switzerland Gary Maciel Department of Chemistry, Colorado State University, Ft. Collins, Colorado 80523 Maureen I. McCarthy Theory, Modeling and Simulation Group, Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 Kenneth H. Nealson Jet Propulsion Laboratory-183-301, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, California 91109-8099 Dimitri A. Sverjensky Department of Earth and Planetary Sciences, The Johns Hopkins University, Baltimore, Maryland 21218 Michael F. Toney IBM Almaden Research Center, San Jose, California 95120 John M. Zachara Environmental Molecular Sciences, Laboratory Pacific Northwest National Laboratory, Richland, Washington 99352 Received February 27, 1998 (Revised Manuscript Received November 9, 1998) 10.1021/cr980011z CCC: $35.00 © 1999 American Chemical Society Published on Web 12/24/1998 78 Chemical Reviews, 1999, Vol. 99, No. 1 Brown et al. Contents 5. Dissolution and Growth of Metal (Hydr)oxides 141 5.1. Reactivities of Metal (Hydr)oxide Oligomers: 141 1. Introduction 78 Models for Surface Complexes 2. Characterization of Clean Metal Oxide Surfaces 83 5.2. Structural Similarities between Aqueous Oxo 141 2.1. The Nature of Defects on Metal Oxide 83 and Hydroxo Oligomers and Simple Surfaces Surfaces 5.3. Dissolution Rates of Metal (Hydr)oxides and 142 2.2. Overview of UHV Surface Science Methods 84 Depolymerization of Surface (Hydr)oxide Used To Study Clean Metal Oxide Surfaces Polymers 2.3. Geometric and Electronic Structure of Clean, 86 6. Biotic Processes in Metal Oxide Surface 144 Well-Ordered Surfaces Chemistry 2.3.1. Atomic Geometry 86 6.1. Surface Attachment and Biofilm Formation 144 2.3.2. Electronic Structure 89 6.2. Metal Oxide Dissolution (Reductive and 145 Nonreductive) 2.4. Imperfections on Oxide Surfaces 91 6.2.1. Nonreductive Dissolution of Metal Oxides 145 2.4.1. Bulk Point Defects 91 6.2.2. Reductive Dissolution of Metal Oxides 146 2.4.2. Steps, Kinks, and Point Defects 92 6.3. Metal Oxide Formation 149 3. Water Vapor−Metal Oxide Interactions 92 6.3.1. Manganese Oxide Formation 149 3.1. Experimental Studies on Single-Crystal Metal 93 Oxides 6.3.2. Anaerobic Iron Oxide Formation 149 3.1.1. MgO and CaO 93 6.3.3. Magnetite Formation 150 7. Theory 150 3.1.2. R-Al2O3 95 7.1. Background 150 3.1.3. TiO2 (Rutile) 95 7.1.1. Thermodynamic Approaches 150 3.1.4. TiO2 (Anatase) 97 7.1.2. Molecular-Based Approaches 152 3.1.5. R-Fe2O3 97 3.2. NMR Studies of Amorphous and 98 7.2. Example Applications 154 Polycrystalline Samples under Ambient 7.2.1. Hydroxylation of MgO (100) and CaO 154 Conditions (100) 3.2.1. NMR Methods 98 7.2.2. Transferring Molecular Modeling Results 156 3.2.2. Cross-Polarization NMR as a 100 to Thermodynamic Models Surface-Selective Technique 7.2.3. Thermodynamic Modeling 157 3.2.3. NMR Applied to Metal Oxide Surfaces 100 8. Challenges and Future Directions 160 4. Aqueous Solution−Metal Oxide Interfaces 103 8.1. Surface Complexation Modeling Challenges 160 4.1. Metal Ions in Aqueous Solutions 103 8.2. Experimental Challenges 161 4.1.1. Complexation 104 8.2.1. Atomic-Scale Geometric and Electronic 161 4.1.2. Speciation 106 Structure 4.2. Solubility and Thermodynamics of Metal 108 8.2.2. Future Prospects for Experimental 162 Oxide Surfaces in Contact with Aqueous Studies of Interfacial Layers Solutions 8.2.3. Reaction Kinetics 163 4.2.1. Metal Oxide Dissolution/Solubility 108 8.2.4. Particles, Colloids, and Nanostructured 163 4.2.2. Thermodynamics of Surfaces in Contact 110 Materials with Aqueous Solution 8.2.5. Geomicrobiology 164 4.3. Experimental Studies of the Electrical Double 111 8.3. Theoretical Challenges 165 Layer 9. Acknowledgments 166 4.3.1. Experimental Issues Concerning the 111 10. References 166 Aqueous Solution−Metal Oxide Interface 4.3.2. Experimental Techniques 112 1. Introduction 4.3.3. The Electrical Double Layer 115 4.3.4. Geometric Structure of Metal Oxide 119 During the past decade, interest in chemical reac- Surfaces in Contact with Bulk Water tions occurring at metal oxide-aqueous solution 4.4. Chemical Reactions at Aqueous 120 interfaces has increased significantly because of their Solution−Metal Oxide Interfaces importance in a variety of fields, including atmo- 4.4.1. Conceptual Models of Sorption of 120 spheric chemistry, heterogeneous catalysis and pho- Aqueous Inorganic and Organic Species tocatalysis, chemical sensing, corrosion science, en- at Metal Oxide Surfaces vironmental chemistry and geochemistry, metallurgy 4.4.2. Experimental Studies of Metal Cation and 122 and ore beneficiation, metal oxide crystal growth, soil Oxoanion Sorption at Metal science, semiconductor manufacturing and cleaning, Oxide−Aqueous Solution Interfaces and tribology. The metal oxide-aqueous solution 4.4.3. Heterogeneous Redox Reactions at Metal 131 interface is reactive due to acid-base, ligand- Oxide−Aqueous Solution Interfaces exchange, and/or redox chemistry involving protons 4.4.4. Precipitation Reactions in the Interfacial 138 (hydronium ions), hydroxyl groups, aqueous metal Region ions, and aqueous organic species and also complexes 4.4.5. Catalysis and Photocatalysis 139 among these species. Interfacial localization of those 4.4.6. Photocatalytic Effects of Oxides in the 141 species (adsorption) may result from electrostatic, Atmosphere chemical complexation, and hydrophobic interactions Metal Oxide Surfaces and Their Interactions Chemical Reviews, 1999, Vol. 99, No. 1 79 Gordon E. Brown, Jr., received his B.S. in chemistry and geology in 1965 Carrick Eggleston graduated from Dartmouth College in 1983. He worked in from Millsaps College, Jackson, MS, and his M.S. and Ph.D. in mineralogy the oil field and at a ski area before graduate school, received a National and crystallography from Virginia Polytechnic Institute & State University in Science Foundation graduate fellowship, and received a Ph.D. from Stanford 1968 and 1970, respectively. He is currently the D. W. Kirby Professor of University in 1991. He is presently an Assistant Professor at the University of Earth Sciences at Stanford University and Professor and Chair of the Stanford Wyoming. Synchrotron Radiation Laboratory Faculty at SLAC. Andrew R. Felmy is a Staff Scientist in the Environmental Dynamics and Victor E. Henrich received his Ph.D. in physics from the University of Michigan Simulation Directorate in the Environmental Molecular Sciences Laboratory in 1967. He is currently the Eugene Higgins Professor of Applied Science at at PNNL. He obtained his Ph.D. in 1968 under Professor John H. Weare Yale, and a Professor in the Departments of Applied Physics and of Physics. from the Department
Recommended publications
  • Understanding Pigments: the Third Step to Higher Quality And
    Understanding Pigments: The Third Mark Harber October, 2000 Step to Higher Quality and Consistency Putting great color in your product is part of the pigments. However, they are less opaque and systems approach for resolving issues of sub- would have to be used at higher loading levels to standard properties and appearance. achieve similar whiteness and opacity. This article on pigments is the third in a four-part Titanium Dioxide is used in the majority of the series about the interrelationship of the material products made by the cast polymer industry. Tita- components used in marble and solid surface nium Dioxide-based colors include most whites, manufacturing. These AOC-authored articles re- pastels, earth tones and off-whites such as bone, spond to the challenge that the cast polymer in- ivory, beige or biscuit. As noted in Table 1, non- dustries aspire to higher standards of quality and white synthetic oxides are combined with Titani- consistency. Because resolving cast polymer is- um Dioxide to create pastels and earth tones for sues requires a systems approach, other articles cultured marble and solid surface applications. in this series address resins, gel coats and pro- cessing. All articles begin with background infor- Phthalocyanine pigments, or "Phthalos," impart mation on the main subject matter, followed by deep colors such as the automotive "Hunter ten related issues and guidelines. Green" of a sport utility vehicle or the high strength Blue used in ballpoint pens. Because A BACKGROUND ON COLORANTS they are so deep when used by themselves, In their natural state, cast polymer resins meet a Phthalo Blue and Phthalo Green are normally variety of performance requirements but are lack- blended with other pigments, many times Titani- ing in the color that draws the customer to the um Dioxide.
    [Show full text]
  • Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 11
    This PDF is available from The National Academies Press at http://www.nap.edu/catalog.php?record_id=13374 Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 11 ISBN Committee on Acute Exposure Guideline Levels; Committee on 978-0-309-25481-6 Toxicology; National Research Council 356 pages 6 x 9 PAPERBACK (2012) Visit the National Academies Press online and register for... Instant access to free PDF downloads of titles from the NATIONAL ACADEMY OF SCIENCES NATIONAL ACADEMY OF ENGINEERING INSTITUTE OF MEDICINE NATIONAL RESEARCH COUNCIL 10% off print titles Custom notification of new releases in your field of interest Special offers and discounts Distribution, posting, or copying of this PDF is strictly prohibited without written permission of the National Academies Press. Unless otherwise indicated, all materials in this PDF are copyrighted by the National Academy of Sciences. Request reprint permission for this book Copyright © National Academy of Sciences. All rights reserved. Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 11 Committee on Acute Exposure Guideline Levels Committee on Toxicology Board on Environmental Studies and Toxicology Division on Earth and Life Studies Copyright © National Academy of Sciences. All rights reserved. Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 11 THE NATIONAL ACADEMIES PRESS 500 FIFTH STREET, NW WASHINGTON, DC 20001 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Insti- tute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance.
    [Show full text]
  • Nitrogen Dioxide
    Common Name: NITROGEN DIOXIDE CAS Number: 10102-44-0 RTK Substance number: 1376 DOT Number: UN 1067 Date: May 1989 Revision: April 2000 ----------------------------------------------------------------------- ----------------------------------------------------------------------- HAZARD SUMMARY * Nitrogen Dioxide can affect you when breathed in. * If you think you are experiencing any work-related health * Nitrogen Dioxide may cause mutations. Handle with problems, see a doctor trained to recognize occupational extreme caution. diseases. Take this Fact Sheet with you. * Contact can irritate and burn the skin and eyes with * Exposure to hazardous substances should be routinely possible eye damage. evaluated. This may include collecting personal and area * Breathing Nitrogen Dioxide can irritate the nose and air samples. You can obtain copies of sampling results throat. from your employer. You have a legal right to this * Breathing Nitrogen Dioxide can irritate the lungs causing information under OSHA 1910.1020. coughing and/or shortness of breath. Higher exposures can cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency, with severe shortness of WORKPLACE EXPOSURE LIMITS breath. OSHA: The legal airborne permissible exposure limit * High levels can interfere with the ability of the blood to (PEL) is 5 ppm, not to be exceeded at any time. carry Oxygen causing headache, fatigue, dizziness, and a blue color to the skin and lips (methemoglobinemia). NIOSH: The recommended airborne exposure limit is Higher levels can cause trouble breathing, collapse and 1 ppm, which should not be exceeded at any even death. time. * Repeated exposure to high levels may lead to permanent lung damage. ACGIH: The recommended airborne exposure limit is 3 ppm averaged over an 8-hour workshift and IDENTIFICATION 5 ppm as a STEL (short term exposure limit).
    [Show full text]
  • Kinetic Energy and Mass Analysis of Covalent Group Iv Cluster Ions in Pulsed-Laser Stimulated Field Evaporation T
    KINETIC ENERGY AND MASS ANALYSIS OF COVALENT GROUP IV CLUSTER IONS IN PULSED-LASER STIMULATED FIELD EVAPORATION T. Tsong, J. Liu To cite this version: T. Tsong, J. Liu. KINETIC ENERGY AND MASS ANALYSIS OF COVALENT GROUP IV CLUS- TER IONS IN PULSED-LASER STIMULATED FIELD EVAPORATION. Journal de Physique Col- loques, 1988, 49 (C6), pp.C6-75-C6-80. 10.1051/jphyscol:1988613. jpa-00228110 HAL Id: jpa-00228110 https://hal.archives-ouvertes.fr/jpa-00228110 Submitted on 1 Jan 1988 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. JOURNAL DE PHYSIQUE Colloque C6, supplbment au nO1l, Tome 49, novembre 1988 KINETIC ENERGY AND MASS ANALYSIS OF COVALENT GROUP IV CLUSTER IONS IN PULSED-LASER STIMULATED FIELD EVAPORATION T.T. TSONG and J. LIU Physics Department, The Pensylvania State University, University Park, Pennsylvania, PA 16802, U.S.A. Abstract - Multiply charged cluster ions of silicon and carbon can be formed in pulsed- laser stimulated field evaporation. In general, the signal intensity decreases monotonically with the cluster size. However, a few cluster ion species stand out; these are species of greater stability. For Si, they are ~i," and ~i,", and for C they are c3+ and c5+.
    [Show full text]
  • Emerging Technology
    INDUSTRY NEWS EMERGING TECHNOLOGY Iron-based superconductors reinforce link to magnetism BRIEFS A new class of iron-oxyarsenide-based superconductors discovered earlier this year shares IDES Inc., a plastic similar unusual magnetic properties with previously known high-temperature superconductors materials information based on copper-oxide materials, report researchers at the National Institute of Standards and management company, Technology, Gaithersburg, Md. The work emphasizes a critical but as yet unexplained link be- and Firehole Technologies Inc., a tween magnetism and high-temperature superconductors. developer of innovative The importance of magnetism to high-temperature superconductors is remarkable because simulation technologies magnetism strongly interferes with conventional, low-temperature superconductors, but now for composite materials may prove to be an integral element of such materials. and structures, have The team used neutron beams to demonstrate that, like copper-oxide superconductors, the entered into a strategic new iron-oxyarsenide HTc materials discovered by Japanese researchers share an unusual partnership to develop a magnetic structure with magnetically active layers interspersed with layers of nonmagnetic searchable composite material. materials database. For more information: Qingzhen Huang, National Institute of Standards & Technology, 100 www.ides.com Bureau, Gaithersburg, MD 20899; tel: 301/ 975-6164; [email protected]; www.nist.gov. Intel Corp., Samsung Electronics, Copper nanowire arrays grown on different surfaces and Taiwan A simple process to grow upright copper nanowires on a variety of materials is under develop- Semiconductor ment by researchers at the University of Illinois in Urbana Champaign. The nanowire arrays Manufacturing could be suitable for field-emission displays, a new type of display technology that promises to pro- Company (TSMC) vide brighter, more vivid pictures than ex- have reached agreement on the need for industry- isting flat-panel displays.
    [Show full text]
  • 2.6 Deltahedral Zintl Ions of Tin: Synthesis, Structure, and Reactivity Slavi C
    OTE/SPH OTE/SPH JWBK199-02.1 JWBK199-Gielen May 30, 2008 13:36 Printer: Yet to come 138 Tin Chemistry: Fundamentals, Frontiers and Applications 2.6 Deltahedral Zintl Ions of Tin: Synthesis, Structure, and Reactivity Slavi C. Sevov Department of Chemistry and Biochemistry, University of Notre Dame,USA 2.6.1 Introduction One little-known area of chemistry is the chemistry of heavy main-group p elements, mostly metals and semimetals, in negative oxidation states. While the chemistry of Sn2+ and Sn4+, for example, is very well studied and we all learn about it very early in our education, not many people are aware of the fact that tin atoms can accept electrons and exhibit completely different reactivity when negatively charged. For example, catenation and clustering are uncommon for cationic tin, but is the norm for 6− anions, both in inter-metallics and molecular compounds. Thus, cyclopentadienyl-like Sn5 is found in the inter-metallic compounds Na8AeSn6 (Ae = Ba, Eu), Li9−x AeSn6+x (Ae = Ca, Eu), Li5Ca7Sn11, 1 4− and Li6Eu5Sn9, isolated tetrahedra of Sn4 and alkali-metal cations constitute the structures of A4Sn4 2 (A = alkali metal), while Na4CaSn6 and Li2Ln5Sn7 (Ln = Ce, Pr, Sm, Eu) contain infinite anionic 16− 3,4 chains and heptane-like Sn7 oligomers, respectively. Notice that, as might be expected, the negative oxidation states are achieved when the more electronegative p element, tin in this case, is combined with much more electropositive s or f element such as the alkali, alkaline-earth, or rare-earth metals. Notice also that, for the purpose of structure rationalization and systematic description, the formal oxidation state assignments assume complete electron transfer from the more electropositive atoms to the p element.
    [Show full text]
  • The Oxidation of Carbon Monoxide Using a Tin Oxide
    THE OXIDATION OF CARBON MONOXIDE USING A TIN OXIDE CATALYST Christopher F. Sampson and Nicholas J. Gudde United Kingdom Atomic Energy Authority A.E.R.E. Harwell, Didcot, Oxon. United Kingdom SUMMARY This paper outlines some of the steps involved in the development by the United Kingdom Atomic Energy Authority (UKAEA) of a catalytic device for the recombination of carbon monoxide and oxygen in a C02 laser system. It contrasts the differences between CO oxidation for air purification and for laser environmental control, but indicates that there are similarities between the physical specifications. The principal features of catalytic devices are outlined and some experimental work described. This includes measurements concerning the structure and mechanical properties of the artifact, the preparation of the catalyst coating and its interaction with the gaseous environment. The paper concludes with some speculation about the method by which the reaction actually occurs. INTRODUCTION During the late 1970's, the United Kingdom Atomic Energy Authority at Harwell became involved in sol-gel technology as a result of oxide fuel development. The sol-gel method was found to be suitable for the preparation of catalytic materials which eventually led to their use in car exhaust catalytic converters and for air purification catalysts. Such catalysts were usually in the form of coatings applied to supporting artifacts such as monoliths, formed from either cordierite or from a corrosion resistant metal such as Fecralloy steel (R). The UKAEA has experience in the use of sol-gel catalysts for CO removal from air and so has a technological link to a system intended to recombine O2 and CO formed in sealed C02 lasers.
    [Show full text]
  • Zinc Oxide Sulfide Scavenger Contains a High-Quality Zinc Oxide
    ZINC OXIDE ZINC OXIDE sulfide scavenger contains a high-quality ZINC OXIDE. The very fine particle-size of ZINC OXIDE scavenger results in a maximum amount of surface area for fast, efficient sulfide scavenging. It reacts with sulfides (see APPLICATIONS below) to form ZnS. This precipitate is an insoluble, inert, fine solid that remains harmlessly in the mud system or is removed by the solids-control equipment. Typical Physical Properties Physical appearance ������������������������������������������������������������������������������������������������������������������������������������������������������������������������������ White to off-white powder Specific gravity .......................................................................................................................................................................................................................... 5.4 – 5.6 Bulk density ........................................................................................................................................................................................................ 164 lb/ft3 (2627 kg/m3) Applications Under operating conditions, ZINC OXIDE scavenger reacts with sulfides to form ZnS, as shown in these equations: Zn2+ + HS- + OH- → ZnS ↓ + 2+ 2- H2O Zn + S → ZnS ↓ INC XIDE Z O scavenger is effective at the pH levels found in drilling fluids. It is recommended that a pH above 11 be maintained whenever H2S is - 2- expected. This high alkalinity converts the dangerous H2S gas to less toxic bisulfide
    [Show full text]
  • New Capabilities for Molecular Surface and In-Depth Analysis with Cluster Secondary Ion Mass Spectrometry
    New Capabilities for Molecular Surface and in-Depth Analysis with Cluster Secondary Ion Mass Spectrometry A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Science and Engineering 2018 Huriyyah Ahmed Alturaifi The University of Manchester Faculty of Science and Engineering School of Chemistry 1 Contents List of Figures 6 List of Tables 15 List of Equations 17 Abbreviations 18 Abstract 20 Declaration 21 Copyright Statements 21 Acknowledgements 22 1. Introduction 23 1.1. Secondary Ion Mass Spectrometry (SIMS) 23 1.2. Generation of Secondary Ions 25 1.2.1. The Sputtering Process 26 1.2.2. Ionisation 29 1.2.2.1. Nascent Ion Molecule Model 29 1.2.2.2. Deposition Ionisation Model 30 1.3. Models of Operations of SIMS 31 1.3.1. Dynamic SIMS 31 1.3.2. Static SIMS 32 1.3.3. Imaging SIMS 32 1.4. Cluster SIMS 33 1.5. Damage Cross-Section 36 1.6. Cross-linking 38 1.7. Molecular Depth Profiling 41 1.8. Molecular Dynamic Simulation 58 1.9. Aims of the Study 61 1.10. References 62 2. Instrumentation 70 2.1. ToF-SIMS Instrumentation 70 2.1.1. ToF Mass Analyser 70 2.1.2. ToF-SIMS Instrumentation Development 73 2 2.1.2.1. Sample Holder 76 2.1.2.1.1. Sample Holder insertion into the Instrumentation 77 2.1.2.1.2. Sample Handling Systems 78 2.1.2.2. Instrumentation Control 79 2.1.2.3. Electron Flood Gun 80 2.1.2.4.
    [Show full text]
  • Characterization of Local Chemistry and Disorder in Synthetic and Natural A-AL03 Materials by X-Ray Absorption Near Edge Structure Spectroscopy
    iTRS’oo'tiQ LABORATOR NAZIONALI Dl FRASCATI SIS - Pubblicazioni LNF-97/041 (P) 27 Novembre 1997 Characterization of Local Chemistry and Disorder in Synthetic and Natural a-AL03 Materials by X-ray Absorption Near Edge Structure Spectroscopy A. Mottana1’3), T. Murata2), A. Marcelli3), G. Della Ventura4’ 3\ G. Cibin 3), Z. Wu3), R. Tessadri^) b Universita' di Roma Tre, Dip. di Scienze Geologiche, Largo San Leonardo Murialdo 1, 1-00146 Roma RM, Italy 2) Kyoto Universityof Education, Department of Physics, 1 Fujinomori-cho, Fukakusa, Fushimi-ku, Kyoto 612, Japan 3) Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, Via Fermi 40,1-00044 Frascati RM, Italy 4) Univ. di Roma Tre, Dipartimento di Scienze Geologiche, Largo San Leonardo Murialdo 1, 1-00146 Roma RM, Italy 5 ) Commissariat a l’Energie Atomique, DSM/DRECAM/SRSIM, Bat 462, CE Saclay, 91191 Gif-sur-Yvette Cedex, France 6 ) Universitat Innsbruck, Institut fiir Mineralogie und Petrographic, Innrain 62, A-6020 Innsbruck, Austria Abstract X-ray absorption fine spectra at the A1 K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic a-Al203 (a-alumina), a natural “ruby/sapphire” (corundum) and a series of artificial “corundums ” produced for technical purposes and used as geochemical standards. The A1 K- edge spectra differ despite of the identical coordination (short-range arrangement) assumed byO around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects).
    [Show full text]
  • Preparation and Spectra of Some Hexanuclear Niobium Halide Cluster Compounds Peter Barry Fleming Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1968 Preparation and spectra of some hexanuclear niobium halide cluster compounds Peter Barry Fleming Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Fleming, Peter Barry, "Preparation and spectra of some hexanuclear niobium halide cluster compounds " (1968). Retrospective Theses and Dissertations. 3662. https://lib.dr.iastate.edu/rtd/3662 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received 08-.14 787 FLEMING, Peter Barry, 1941- PREPARATION AND SPECTRA OF SOME HEXANUCLEAR NIOBIUM HALIDE CLUSTER COMPOUNDS. Iowa State University, PhuD., 1968 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan PREPARATION AND SPECTRA OF SOME HEXANUCLEAR NIOBIUM HALIDE CLUSTER COMPOUNDS by Peter Barry Fleming A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Inorganic Chemistry Approved: Signature was redacted for privacy. Signature was redacted for privacy. Head of
    [Show full text]
  • Heteroatomic Deltahedral Clusters of Main-Group Elements: Synthesis and Structure of 3- 2- 2- the Zintl Ions [In4bi5] , [Inbi3] , and [Gabi3]
    Inorg. Chem. 2000, 39, 5383-5389 5383 Heteroatomic Deltahedral Clusters of Main-Group Elements: Synthesis and Structure of 3- 2- 2- the Zintl Ions [In4Bi5] , [InBi3] , and [GaBi3] Li Xu and Slavi C. Sevov* Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 ReceiVed August 11, 2000 Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, 3- indium or gallium and bismuth. Nine-atom clusters [In4Bi5] are characterized in two different compounds, (Na-crypt)3[In4Bi5](4, P21/n, a ) 23.572(6) Å, b ) 15.042(4) Å, c ) 24.071(4) Å, â ) 106.00(3)°, Z ) 4) and (K-crypt)6[In4Bi5][In4Bi5]‚1.5en‚0.5tol (5, P21/c, a ) 28.532(2) Å, b ) 23.707(2) Å, c ) 28.021(2) Å, â ) 2- 2- 93.274(4)°, Z ) 4). Tetrahedra of [InBi3] or [GaBi3] are found in (K-crypt)2[InBi3]‚en (1, P21, a ) 12.347(4) Å, b ) 20.884(4) Å, c ) 12.619(7) Å, â ) 119.02(4)°, Z ) 2) and in the isostructural (Rb-crypt)2[InBi3]‚en (2, a ) 12.403(8) Å, b ) 20.99(1) Å, c ) 12.617(9) Å, â ) 118.83(4)°) and (K-crypt)2[GaBi3]‚en (3, a ) 12.324(5) Å, b ) 20.890(8) Å, c ) 12.629(5) Å, â ) 118.91(3)°). All compounds are crystallized from ethylenediamine/ crypt solutions of precursors with nominal composition “A5E2Bi4” where A ) Na, K, or Rb and E ) Ga or In.
    [Show full text]