Outline — • I. General introduction Toward Controlled Creation of New − Our interests and facilities in − Nanoengineering Inorganic and Nanomaterial • II. Chemical of Architectures and material nanostructures − Liquid phase synthesis − Processing by external fields • III. “Molecular engineering” of Michael Z. Hu nanostructures − Arrays of inorganic nanochannels/nanotubes: Oak Ridge National Laboratory orientation/ordering control [email protected] − Space-confined self-assembly: nanostructure 800 o C 700 o C 500 o C

σ ZrO :1 0 % Y O 2 s 2 2 3 0.52eV e p ita x ia l film o n M g O - su b stra te σ in te rfa ce 1

control within inorganic nanowires surface/interface diffusion 0 0.93eV con tro lled (p red icted)

σ σ bulk σ -1 b nanocrystallinenanocrystalline film d = 20nm 865-574-8782 g 1.04eV -2 bulk diffusion Log conductivity (S/cm) conductivity Log controlled

-3 data for single Y SZ crystal & film s d > 60nm • IV. Potential applications 910111213 104 /T (K -1 ) − Fuel cells, solar cells, sensors, … • V. Concluding remarks OAK RIDGE NATIONAL LABORATORY OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY U. S. DEPARTMENT OF ENERGY

ORNL Is A World Leader in Nanosciences and Nation’s Premier Facilities in Advanced Materials Materials Research Nanoengineering Lab • Center for Nanophase Materials Sciences SNS (CNMS) Neutron & synchrotron sources • Spallation Neutron CNMS Source (SNS) & High DOE’s first nanoscience center Flux Isotope Reactor (HFIR) scattering facilities • High-Temperature Ultrascale computing Materials Laboratory HTML facilities Facilities (HTML) • (NEW!) Center for Radiation Detection Materials and Systems (CRDMS) OAK RIDGE NATIONAL LABORATORY Advanced Electronic Microscopy U. S. DEPARTMENT OF ENERGY Engineering vs. Science Our Interests: Develop “NanoEngineering” for Controlled Nanosize & Nanostructure • Definition (per Webster’s): − Science: “… a branch of knowledge or study dealing with a body of facts or truths • Chemical Processes systematically arranged and showing the (including biomimetic processes) operation of general laws … systematic knowledge of the physical or material world − “Bottom-up” in nature, using At Nanoscale …” and particles as building-block precursors Scalable processing (beyond today’s − Engineering: “… the art or science of making − Suitable for large-scale with nanoscale nanosciences and practical application of the knowledge of pure production economically process control ) sciences, as , , biology, etc. …” • Engineered Chemical Controlled or Large-Scale Processing of Nanomaterials Formation/Assembly of − Nanoengineering: ??? – a new paradigm Designed Nanostructure ¾ Must be enabling, not just the traditional shall go − Nanoscale chemical reaction scale-up problem beyond NanoScience ! () ¾ Beyond existing engineering: chemical - Process scale − Molecular engineering engineering, materials engineering, etc. - Level of precision of process (chemistry + molecular design ¾ Need a transition from nanoscale science control + self-assembly + process to nanoengineering - Production through-put rate engineering) Controlled - Dimension of products − Interface engineering Properties/Functions OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY

Nucleation and Growth and Self-Assembly Molecular Design and Process Engineering Are Enabling Approaches to “Build Up” Control the Growth of Nanostructure Advanced Nanomaterials examples of fundamental building blocks “Controlled” build-up (growth) • Allow bottom-up manufacturing of nanophase/particles/nanopores • A world of inorganic materials can be made by controlled Homogeneous Heterogeneous “living growth” “living growth” Tailored nanostructures Particle Film/Interface in advanced materials Porous inorganics Size & distribution Uniformity Engineered manufacturing of Nanopore size Shape Positioned surface growth advanced ceramics/composites Shape Crystallinity Nanophase grain size could impact various applications Orientation Surface chemistry Surface roughness 1 nm Domain scale ¾ and conversion Pore structure Crystal structure Nanoparticles, Films, Coatings, Nano-, Meso- Nanorod,wires (fuel cells, solar cells) Core-shell Patterned film Nanocrystals Membranes Porous Materials Nanocomposites ¾Separations (inorganic membranes) Colloidal crystal Film porosity Linked network Multilayer ¾Catalysis ¾Micro-/nano-electronics ¾Sensors, detectors, devices Chemical process understanding and control must be obtained to 1-dimensional Nanocrystalline Nanoscale Chemical process understanding and control must be obtained to ¾Targeted therapy, drug delivery, Nanowires, Fibers Dense Ceramics Patterned Film achieve nanoscale engineered build-up of materials etc. We Focus on Real-Time Process Monitoring and Control to Example: SAXS Monitoring of Sol-Gel Processing of understand & develop engineering processes for Nanomaterials in Solutions manufacturing nanomaterials We have developed capability for studying early stages (as short as 80 ms). • Small-Angle Scattering (SAXS and SANS) • Dynamic Light Scattering (DLS) SAXS from Early-Stage Zr-Nanoclusters (0.2 – 200 nm length scale for SAXS) (5 – 1000 nm nanosize range) Thermostatically Controlled Laser Power Enclosure Alcohol+ Alcohol+ Porod plot Supply Acid+H2O Alkoxide

Incident Beam Sample Cell He-Ne Laser Tube Mixing Scattered Light Tubing with adjustable length Photomultiplier Tube D = 1.8 → 2.4 Sample f Computer-Interfaced (weakly to strongly branched w/ a Power X-Ray Chamber consistent length of 8.3 + 0.5 & ) Digital Auto Correlator Supply (1-mm capillary Detector MCA 2 2 2 (BI 9000-AT) Source cell with 10-µm I(Q) = Ie(Q)Np(Δρν) exp (-Q Rg /3) Or FTIR thick wall)

• In-situ, high-temperature XRD (HTXRD) Mass fractal scattering model Scattering is Computer I(q) = NP(q) S(q) complementary to N = number density Waste electron Form factor (for spherical particles): 2 2 2 3 2 microscopy P(q) = V (Δρ) {3[sin(qr0) - qr0cos(qr0) ]/(qr0) } D HTML facility HRTEM A “Steady-State” Technique Based on Structure factor: S(q) = [1+1/(qr0) f DfΓ(Df-1)sin[(Df - 1)arctan(qξ)/[1+ 1/(q2 ξ2)](D -1)/2 offer existing Rapid Mixing Flow-Cell f capability J. Mater. Sci., 35, 1957 (2000). J. Non-Crystal. Solid, 246, 197 (1999).

Example: Engineered Processes Need to be Developed for Outline Novel DTS Processing of Monodispersed Oxides Highlight of Dielectric-Tuning Synthesis (DTS) Oxides: e.g. ZrO2, TiO2, BaTiO3, and ZrTiO4 • I. General introduction Uniqueness: • II. Chemical engineering of nanoparticles and • use inorganic precursors SEM material nanostructures • low temperature synthesis • III. Molecular “engineering” of nanostructures • different from − Array of nanochannels/nanotubes: sol-gel method orientation/ordering control • Capable of sol- gel processing − Space-confined self-assembly: nanostructure Features: control within nanowires XRD of • Size: near- • IV. Potential Applications monodispersed BaTiO3 • Phase: − Fuel cells, solar cells, sensors, … nanocrystalline or • V. Concluding Remarks amorphous • High purity • Nanoscale homogeneity • Controllable OAK RIDGE NATIONAL LABORATORY J. Colloid Inter. Sci.,222, 20 (2000). J. Mater. Sci. 35, 1 (2000). U. S. DEPARTMENT OF ENERGY J. Amer. Ceram. Soc., 82, 2313 (1999). morphology Powder Technol., 110, 2 (2000). Scale-up of DTS chemical process Besides large-scale production, control of assemblies is also a key engineering for nanoparticle synthesis issue (A) Nanocrystalline TiO2 Microspheres • Investigate engineering science issues: scale up, transition to continuous production (B)Nanocrystalline Microsphere Assemblies of BaTiO3

Glass vials (10-50mL)

Engineering reactors (C) Dispersed Nanocrystals of BaTiO3 by Designed Dis-aggregation from Microsphere (5000mL, better control in T, Assemblies P, mixing parameters)

OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY

New Arenas:Arenas Engineering Control of the Laser Processing: Induced Nanocrystal Size and Nanostructures Homogenization Is Possible

2 orders-of-magnitude reduction in polydispersity! Current “Naked” Metallic Nanocrystals by A 2 orders-of-magnitude reduction in polydispersity! (from 0.5 to 0.005) while size does not change nanoscience effort Chemistry, and Thermal Electrochemical Process in materials is engineering, etc. Scattering Characteristics of Sample Ag41 restrained inside (preliminary results) this box 1 0.9 0.8 without laser 0.7 Outside-the-Box Approach: “engineered” monitoring and control of processes 0.6 0.5 ™ Laser-assisted processing 0.4 Diversified physical/chemical 0.3 with laser ™ Field-directed processing Polydispersity means of engineering controls 0.2 (Electrical, Magnetic, Microwave…) 0.1 enable 0 ™ Electrochemical processing 0 10203040506070 • novel and refined ways of This process, developed at ORNL, Time (min) ™ Thermal processing manufacturing generates possibly a new class ™ Molecular assembly-assisted • creation of new nanostructures of Ag nanocrystals. Polydispersity: a parameter in dynamic light scattering processing • better or more precise control of measurement to quantify particle size distribution. • Size < 10 nm • < 0.02, for monodisperse or nearly monodisperse samples process parameters • Free from any organic capping • 0.02-0.08, for narrow size distributions molecules • > 0.08, for broader distribution • Colloidally stable Field-Coupled Chemical Processing Microwave Processing Offers More Flexibility than (Engineered Tailoring of Nanocluster Growth/Assembly Needs More R&D) Conventional Hydrothermal Processing Programmable Microwave Growth of Microfibrils Electrohydrodynamic

Hydrothermal Reactions in Electric Field Mixing Reactor (EMR) Synthesis Temp = 150oC Synthesis Temp = 180oC

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a 330 RV=0.88 A Sol-gel EMR P 320 Faster heating Slower heating 0 0.2 0.4 0.6 0.8 1 Micro/nano wires Volume Ratio (Rv)

Rv= 0.63 Rv= 0.63 • Improved nanoscale 693.4 nm 3006.4 nm • Microwave volumetric mixing overcomes mass heating overcomes heat transfer limitations; transfer limitations allows • field induce polarization • Particle size can be and new morphology by −greater control of controlled by manipulating oriented growth nucleation the nucleation rate • Inorganic long “hair”: −synthesis beyond sol- • Achieving computer gel processing limit programmed synthesis − morphology/diameter Various changes in zeolite particle size and can be tailored morphology can be realized.

Outline Natural Beauty and Diversity of Self-Assembled Nanomaterials • I. General introduction Silicic skeletons of unicellular organisms: Molecular self-assembly is the spontaneous and a, b – Radiolaria; c, d - diatoms reversible organization of building-blocks (molecules) • II. Chemical engineering of nanoparticles and under thermodynamic equilibrium conditions into material nanostructures structurally well-defined and rather stable arrangements through a number of noncovalent • III. “Molecular engineering” of inorganic interactions. (Shuguang Zhang 2002, Tirrell & Katz 2005) nanostructures – a new paradigm Inverted Spherical (Ns>1) − Array of nanochannels/nanotubes: (Ns=0.33) orientation/ordering control − Space-confined self-assembly: nanostructure control Cylindrical within nanowires (N =0.5) s Bicontinuous Structures • IV. Potential Applications (Ns≥1)

− Fuel cells, solar cells, sensors, … Planar Bilayers or Lamellar Vesicles (N =1) • V. Concluding Remarks s (Ns≅ 1)

Sanchez et al., Nature Mater. 2005 Hiemenz, Principles of Colloid and Interfacial Sciences OAK RIDGE NATIONAL LABORATORY • Biomimetism/bioinspiration Æ Design/creation of innovative materials/systems U. S. DEPARTMENT OF ENERGY • “Molecular engineering” = self-assembly + molecular design + processing engineering Case 1: Molecular-Based Surface Deposition Chemical Processing Allow Control and Interface Film Growth of Oxides Thickness and Nanostructure of TiO2 Film • Modify substrate with organic self-assembled Cl OH Cl Si (CH2)16SC(O)CH3 Strategy: SEM surface view monolayers (SAM) Cl o Si Cl Design of Molecular Complex Si 80 C, 6.5h OH Cl Si (CH2)16SC(O)CH3 • Chemical solution deposition of inorganic layer on SAM Cl Ti Species or Nanoclusters Anchoring 1-thioacetate-16-(trichlorosilyl)hexadecane in Bulk Solutions (trace H2O)

O Si (CH2)16SC(O)CH3 Thioacetate-functionalized O SAM Molecular Si Cluster in O Si (CH2)16SC(O)CH3 Solutions In-situ Anatase Oxidation 25 Å thick, 4.3 Å head spacing Interaction affinity (CH ) SO H O Si 2 16 3 Sulfonate-functionalized Si O SAM O (CH ) SO H Substrate 100oC, 2.0h Si 2 16 3 TEM cross-section Si (Colorful mirror-like films) • Important for film growth as well as interface - Inter. J. Appl. Ceram. Technol., April (2004) - Solid State Ionics, 151, 69 (2002). engineering in nanocomosites • The approach has induced homogeneous Anatase deposition and improved Rutile

¾uniformity, roughness TiO2 ¾coherence, adherence • Nanocrystalline TiO2 films ¾possible selective deposition Æ soft Surface view 3D view (containing ~3 nm lithography nanocrystals) • We have grown and studied various oxide – high refractive index (2.2) deposition (ZrO , HfO , etc. ) 2 2 – large band-gap (up to 3.7 eV) Application to Solar Cells? Control (Bare Si Wafer) – low surface roughness

Case 2: Molecular-Templated Growth and A Novel Vapor-Phase Thermal Conversion Crystallization of Zeolite Particles Synthesis of MFI Zeolite Membranes • A good model system for Nanoporous crystal particles Fully crystallized (~70nm) Surface of membrane understanding large-scale alpha alumina 15 hr MFI 6 hr process, but with possible Wet precursor sol-gel layer C achievement of nanoscale Vapor of water Macroporous homogeneity α-alumina disc - Sub-nm micropores are Teflon stand Vapor of EDA/TEA/water created by molecular B 1 μm templating inside each

Liquid phase intensity Relative crystal particle - Small template molecules Stainless steel e Tim control the size, shape, autoclave Vapor of 1M TPAOH A and uniformity of the pores 2 μm Partially grown, irregular crystal • Challenges exists in 5 10152025 2 θ Cross-section of membrane 4.5 hr further development for Results of zeolite membrane synthesis under different efficiency, selectivity, and conditions. 1 hr cost saving for practical Synthesis sol-gel on substrate Liquid phase Top layer Thickness Quality (μm) MFI top layer applications in catalysts 7.0% SiO2 + 2.1% TPAOH + 0.8% NaOH + 1 M TPAOH MFI 3 Good and adsorbents 90.1% H2O EDA/TEA/H O 7.0% SiO + 2.1% TPAOH + 0.8% NaOH + 2 MFI 12 Poor α-Alumina - Growth of oriented 2 (8.1/30.7/61.2) 90.1% H2O support nanopore channels in a 3 hr 7.0% SiO2 + 2.1% TPAOH + 0.8% NaOH + H 2O Amorphous ------2 μm single crystal membrane is 90.1% H2O Amorphous gel Metastable a key 7.0% SiO2 + 2.9% NaOH + 90.1% H2O 1 M TPAOH NaP-cubic ------particle (50nm) J. Mater. Sci., 38 (5): 979 (2003). gel+crystal (~15 nm) EDA/TEA/H2O 7.0% SiO2 + 2.9% NaOH + 90.1% H2O ANA-cubic ------Ceramic Transactions, 137, 3-21 (2003). (8.1/30.7/61.2) Molecular Self-Assembly Processing of Inorganic Case 3: Rich Morphologies via Self Nanomaterials -- Grand Challenges Assembly and Organization of Polymers (a) Current state of the art in (b) Future realization of large-scale ordering Park C. et al., Polymer (2003) Park C. et al., Polymer (2003) molecular templated synthesis and control of orientation and wall function

Powders Containing Oriented Nanopores Guest-Host Nanocomposite Randomly Oriented (~1-100 nm dia.) in Superstructures Small Domains of Membrane Layer Ordered Mesopores

Beyond what nature Zoom in can create or or or

Parallel pore channels is Schematic phase diagram showing the various “classical” Film Layers containing in perpendicular to the BCP morphologies adopted by non-crystalline linear diblock layer or substrate surface copolymer. The blue component represents the minority randomly oriented, phase and the matrix, majority phase surounds it. disordered mesopores Polycrystalline to Schematic of morphologies for linear ABC triblock single crystal copolymer. A combination of block sequence (ABC, Substrate Nanostructure control inside nanowire •Polymorph selection in porous block copolymers ACB, BAC), composition and block molecular weights Ward, Hillmyer, J. Am. Chem. Soc., 126, 3382 (2004) provides an enormous parameter space for the •Tailored pore wall functionality creation of new morphologies. Microdomains are Hillmyer et al., Macromolecules, 38, 3 (2005) colored as shown by the copolymer strand at the top, ibid, Faraday Disc. 128, 149 (2005) with monomer types A, B, and C confined to regions colored blue, red, and green, respectively. Enhanced or New Functions

Molecular Design-Based Build-up Self-Assembly of P123 Developing Hybrid Molecular Self-Assembly of Oxide Mesostructures P123: (PEO)20(PPO)70(PEO)20 PEO (hydrophilic)

Formation of HORIZONTAL SiO2 MESOSTRUCTURE via block copolymer

Phase diagram in aqueous solutions

PPO (hydrophobic) Z-contrast STEM images: Bright region representing silica. Channels (7.5-nm gap) exhibit a highly connected horizontal structure. (V. F. de Almeida, D. A. Blom, L. F. Allard, M. Z. Hu, S. Dai, C. Tsouris, Z. Hydrophobic effect Zhang, Microscopy and Microanalysis 2003, San Antonio, Texas, August 3-7, 2003.) in dilute aqueous Key Issues: solution causes the • Orientation control: let meso-channels standing up normal to substrate? self-assembly • Expanding domain size of ordering • Structure stability Wanka G. et al., Macromolecules 27, 4145 (1994).

OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY Molecular Engineering-Based Build-up Process Engineering Enables Channel Orientation in Nano/Mesoporous Films

•Achieved Vertical SiO2 Mesostructure (black dots are channel pores, bright region-SiO2) Pore size diameter of 7.5 nm; channels are hexagonally arranged perpendicular to the film surface.

•Observed Transition SiO2 Mesostructure (from vertical to some degree of horizontal connectivity)

Engineering sciences (that control the mechanisms of channel orientation, - Very large area of hexagonal ordering: achieved mm range OcontrolAK RIDGE ofN aspectATIONAL ratioLABORATORY and pore connectivity, ordering scale-up, etc.) still need - Possible hard template for arrays of nanoscale vertical channel columns U.to S. beDEPARTMENT fully developed. OF ENERGY - Many potential applications (fuel cells, solar cells, sensors, catalysts, etc. )

Molecular Design-Based Build-up Challenges Still Exists in Controlled Self- Assembly Mesopore Orientation in Many Other Oxides with Unlimited Applications

High-resolution TEM images of titania layer mesostructures containing parallel pore channels with spacing Nano-in-Nano Control: Space-Confined Self- of ~10nm. Dark pore Assembly of Organic-Inorganic Wires in channel lines correspond to titania 100 nm 50 nm 10 nm Nanopore Channels (0.5 – 200nm) phase. TiO2 STEM images of mesostructured titania showing distorted hexagonal phases (TE- transmission mode; ZC – Z-contrast mode, brighter 60 nm 60 nm 60 nm areas correspond to titania phase). (Hu, unpublished results) OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY Self Assembly in Confined Pore Channels: Guest-Host Nanocomposite Superstructures Revealing “layered” structure with STEM

Potential Applications • Wires inside pore channels Electronic materials, Fuel-cell electrolyte, Optical consist of oriented, parallel materials, Detectors, Sensors, Magnetism, stacked layers of oxide (10-nm thick) Catalysts, Nanocomposites “Layered” Results from Statistical Mechanical Theory Imprinted nanostructure and EMD simulation wire “Hose” 1 nm (SEM)

25

20 1/2 ) ε 15 (m -2

σ 10 highly oriented and 5 viscosity, 0 ordered hexagonal Self-diffusion -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 z/ σ 1.6 mesophases 1.4 1.2 3

σ 1.0 0.8 (STEM)

0.6

density, n 0.4 0.2 0.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 z/σ

J.O AKNanosci.RIDGE Nanotechnol.NATIONAL L2ABORATORY, 209 (2002). OAK RIDGE NATIONAL LABORATORY Ceram.U. S. DEPARTMENT Trans. 137,OF 101E NERGY(2002). U. S. DEPARTMENT OF ENERGY

Molecular & Process Engineering Approach Could Outline Enable Refined “Nano-in-Nano” Control of Nanostructures • I. General introduction • II. Chemical engineering of nanoparticles (a) (b) Various oriented and ordered inorganic oxide nanostructures and material nanostructures inside space-confined wires/channels can be created. • III. “Molecular engineering” of inorganic (a) Random oriented mesopores nanostructures – a new paradigm and small domain size of − Array of nanochannels/nanotubes: hexagonal phases, (b) Parallel lamellar phase oriented orientation/ordering control (c) (d) in perpendicular to the pore − Space-confined self-assembly: nanostructure channel, control within nanowires (c) Lamellar phase oriented in parallel to the pore channel, • IV. Potential Applications (d) Highly ordered and oriented hexagonal mesopores (7.5nm − Fuel cells, solar cells, sensors, … dia.). • V. Concluding Remarks

OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY Success Could Directly Impact Energy Materials Concluding Remarks of the Future: Solar Cells and Fuel Cells • Chemical engineering and “molecular engineering” of nanosize and nanostructure are frontiers for new discovery and creation of innovative materials. − Chemical processing offers great opportunities in large-scale manufacturing and production while allowing precise control of material nanostructures and functions

• At ORNL, we endeavor to develop new engineering sciences and manufacturing capabilities in nanomaterials for energy, security, and other applications − Materials NanoEngineering Laboratory: focuses on chemical processing and engineering at molecular level − State-of-the-art instrument facilities: on real-time process monitoring and nanoscale characterization (HTML, CNMS, SNS, …) • Future nanofabrication demand “process understanding-based” control at higher levels: Size Æ Shape Æ Ordering Æ Orientation

OAK RIDGE NATIONAL LABORATORY OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY U. S. DEPARTMENT OF ENERGY

Overview: Process Engineering and Molecular Engineering Enable Acknowledgments Tailored Chemical Processing of Diversified Nanostructures “Engineered” Post-Docs: L. Pozhar, J. Dong, A. Singhal Chemical Molecular Design Students: P. Lai, X. Wang, L. Khatri, J. Zielke, S. Morton, A. DeBaille, Heterogeneous Processing Templating nucleation & V. Kurian, G. Miller, K. Booth, B. Grant, J. Clavier Self-Assembly growth on Homogeneous ORNL Colleagues: C. Easterly, D. DePaoli, R. Hunt, A. Payzant, J.-S. Surface surfaces nucleation & growth Engineering In bulk Lin, C. Rawn,. Allard, D. Blom, I. Anderson, G. Jellison, Y. Wei, P. w/ SAM Becher, T. Armstrong, C. Mattus, J. Wang, V. de Almeida In-situ deposition of nanoclusters Collaborators: D.-L. Shi, M. T. Harris, D. Green, B. Lee, Y.-S. Lin, M. 1 nm (<100nm) DeGuire, N. Xu Films, Coatings, Nanoparticles, Fibers, Wires • Research sponsored by Membranes − Division of Materials Sciences, Material Chemistry Program, Office of Consolidation Sciences, U.S. Department of Energy (DOE) Sintering ORNL HTML facility Nanograins • Nano/Mesoporous Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the U.S. Dept. of Solid Materials & Energy under contract DE-AC05-00OR22725 Nanocrystals Ceramics or advanced & Assembly Cermets nanocomposites OAK RIDGE NATIONAL LABORATORY (Nanophase) (1-50nm pores, ordering, U. S. DEPARTMENT OF ENERGY and orientation control)