The goals of this project are to understand the fundamental principles that govern the formation and function of novel nanoscale and nanocomposite materials. Specific scientific issues being addressed include: design and synthesis of complex molecular precursors with controlled architectures, controlled synthesis of nanoclusters and nanoparticles, development of robust two or three-dimensionally ordered nanocomposite materials with integrated functionalities that can respond to internal or external stimuli through specific molecular interactions or phase transitions, fundamental understanding of molecular self-assembly mechanisms on multiple length scales, and fundamental understanding of transport, electronic, optical, magnetic, catalytic and photocatalytic properties derived from the nanoscale phenomena and unique surface and interfacial chemistry for DOE's energy mission.
Fine powders of calcium zirconate (CaZrO{sub 3}, CZ) and calcium titanate (CaTiO{sub 3}, CT) were synthesized using a nonaqueous oxalate co-precipitation route from Ca(NO{sub 3}){sub 2}{center_dot}4 H{sub 2}O and group(IV) n-butoxides (Ti(OBu{sup n}){sub 4} or Zr(OBu{sup n}){sub 4}). Several reaction conditions and batch sizes (2-35 g) were explored to determine their influence on final particle size, morphology, and phase. Characterization of the as-prepared oxalate precursors, oven dried oxalate precursors (60-90 C), and calcined powders (635-900 C) were analyzed with TGA/DTA, XRD, TEM, and SEM. Densification and sintering studies on pressed CZ pellets at 1375 and 1400 C were also performed. Through the developed oxalate co-precipitation route, densification temperatures for CZ were lowered by 125 C from the 1500 C firing temperature required for conventional mixed oxide powders. Low field electrical tests of the CZ pellets indicated excellent dielectric properties with dielectric constants of {approx}30 and a dissipation factor of 0.0004 were measured at 1 kHz.
The synthesis of cysteine-capped CdS quantum dot nanocrystals (CdS-cys) between two interdiffusing reagent streams in a continuous flow microfluidic reactor was investigated. Spatially resolved fluorescence imaging and spectroscopy of the microreactor at various reactant concentrations and flow rates was used to study nucleation and growth of these particles. The laminar flow of the impinging streams allowed for controlled diffusional mixing of the reacting cadmium and sulfide ions at the boundary between the two solutions, while the capping agent was present in one or both of the solutions in excess. The results show that the photoluminescence of these particles grown under these microfluidic conditions differs from those grown in batch reactors.
Solution-based synthesis is a powerful approach for creating nano-structured materials. Although there have been significant recent successes in its application to fabricating nanomaterials, the general principles that control solution synthesis are not well understood. The purpose of this LDRD project was to develop the scientific principles required to design and build unique nanostructures in crystalline oxides and II/VI semiconductors using solution-based molecular self-assembly techniques. The ability to synthesize these materials in a range of different nano-architectures (from controlled morphology nanocrystals to surface templated 3-D structures) has provided the foundation for new opportunities in such areas as interactive interfaces for optics, electronics, and sensors. The homogeneous precipitation of ZnO in aqueous solution was used primarily as the model system for the project. We developed a low temperature, aqueous solution synthesis route for preparation of large arrays of oriented ZnO nanostructures. Through control of heterogeneous nucleation and growth, methods to predicatively alter the ZnO microstructures by tailoring the surface chemistry of the crystals were established. Molecular mechanics simulations, involving single point energy calculations and full geometry optimizations, were developed to assist in selecting appropriate chemical systems and understanding physical adsorption and ultimately growth mechanisms in the design of oxide nanoarrays. The versatility of peptide chemistry in controlling the formation of cadmium sulfide nanoparticles and zinc oxide/cadmium sulfide heterostructures was also demonstrated.
The impacts of small niobium additions to processing, microstructure, and electrical properties in the Zr-rich lead zirconate titanate ceramics (PZT 95/5) were investigated. The influence of niobium content on dielectric responses and the characteristics of ferroelectric behaviors, as well as the relative phase stability and the hydrostatic pressure induced ferroelectric-to- antiferroelectric phase transformation are reported. Results indicate that increasing the niobium concentration in the solid solutions enhances densification, refines the microstructure, decreases dielectric constant and spontaneous polarization, and stabilizes the ferroelectric phase. The stabilization of ferroelectric phase with respect to the antiferroelectric phase near PZT 95/5 composition dramatically increases the pressure required for the ferroelectric-to-antiferroelectric phase transformation. These observations were correlated to the creation of A-site vacancies and a slight modification of the crystal structure. The importance of these composition-property relationships on device application will be presented.
Chemically prepared zinc oxide powders are fabricated for the production of high aspect ratio varistor components. Colloidal processing in water was performed to reduce agglomerates to primary particles, form a high solids loading slurry, and prevent dopant migration. The milled and dispersed powder exhibited a viscoelastic to elastic behavioral transition at a volume loading of 43-46%. The origin of this transition was studied using acoustic spectroscopy, zeta potential measurements and oscillatory rheology. The phenomenon occurs due to a volume fraction solids dependent reduction in the zeta potential of the solid phase. It is postulated to result from divalent ion binding within the polyelectrolyte dispersant chain, and was mitigated using a polyethylene glycol plasticizing additive. Chemically prepared zinc oxide powders were processed for the production of high aspect ratio varistor components. Near net shape casting methods including slip casting and agarose gelcasting were evaluated for effectiveness in achieving a uniform green microstructure achieving density values near the theoretical maximum during sintering. The structure of the green parts was examined by mercury porisimetry. Agarose gelcasting produced green parts with low solids loading values and did not achieve high fired density. Isopressing the agarose cast parts after drying raised the fired density to greater than 95%, but the parts exhibited catastrophic shorting during electrical testing. Slip casting produced high green density parts, which exhibited high fired density values. The electrical characteristics of slip cast parts are comparable with dry pressed powder compacts. Alternative methods for near net shape forming of ceramic dispersions were investigated for use with the chemically prepared ZnO material. Recommendations for further investigation to achieve a viable production process are presented.
An environmentally friendly method and materials study for desalinating inland brackish waters (i.e., coal bed methane produced waters) using a set of ion-exchange materials is presented. This desalination process effectively removes anions and cations in separate steps with minimal caustic waste generation. The anion-exchange material, hydrotalcite (HTC), exhibits an ion-exchange capacity (IEC) of {approx} 3 mequiv g{sup -1}. The cation-exchange material, an amorphous aluminosilicate permutite-like material, (Na{sub x+2y}Al{sub x}Si{sub 1-x}O{sub 2+y}), has an IEC of {approx}2.5 mequiv g{sup -1}. These ion-exchange materials were studied and optimized because of their specific ion-exchange capacity for the ions of interest and their ability to function in the temperature and pH regions necessary for cost and energy effectiveness. Room temperature, minimum pressure column studies (once-pass through) on simulant brackish water (total dissolved solids (TDS) = 2222 ppm) resulted in water containing TDS = 25 ppm. A second once-pass through column study on actual produced water (TDS = {approx}11,000) with a high carbonate concentration used an additional lime softening step and resulted in a decreased TDS of 600 ppm.
A variety of solution deposition routes have been reported for processing complex perovskite-based materials such as ferroelectric oxides and conductive electrode oxides, due to ease of incorporating multiple elements, control of chemical stoichiometry, and feasibility for large area deposition. Here, we report an extension of these methods toward long length, epitaxial film solution deposition routes to enable biaxially oriented YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (YBCO)-coated conductors for superconducting transmission wires. Recent results are presented detailing an all-solution deposition approach to YBCO-coated conductors with critical current densities J{sub c} (77 K) > 1 MA/cm{sup 2} on rolling-assisted, biaxially textured, (200)-oriented Ni-W alloy tapes. Solution-deposition methods such as this approach and those of other research groups appear to have promise to compete with vapor phase methods for superconductor electrical properties, with potential advantages for large area deposition and low cost/kA {center_dot} m of wire.
The ability to precisely place nanomaterials at predetermined locations is necessary for realizing applications using these new materials. Using an organic template, we demonstrate directed growth of zinc oxide (ZnO) nanorods on silver films from aqueous solution. Spatial organization of ZnO nanorods in prescribed arbitrary patterns was achieved, with unprecedented control in selectivity, crystal orientation, and nucleation density. Surprisingly, we found that caboxylate endgroups of {omega}-alkanethiol molecules strongly inhibit ZnO nucleation. The mechanism for this observed selectivity is discussed.
The need for fresh water has increased exponentially during the last several decades due to the continuous growth of human population and industrial and agricultural activities. Yet existing resources are limited often because of their high salinity. This unfavorable situation requires the development of new, long-term strategies and alternative technologies for desalination of saline waters presently not being used to supply the population growth occurring in arid regions. We have developed a novel environmentally friendly method for desalinating inland brackish waters. This process can be applied to either brackish ground water or produced waters (i.e., coal-bed methane or oil and gas produced waters). Using a set of ion exchange and sorption materials, our process effectively removes anions and cations in separate steps. The ion exchange materials were chosen because of their specific selectivity for ions of interest, and for their ability to work in the temperature and pH regions necessary for cost and energy effectiveness. For anion exchange, we have focused on hydrotalcite (HTC), a layered hydroxide similar to clay in structure. For cation exchange, we have developed an amorphous silica material that has enhanced cation (in particular Na{sup +}) selectivity. In the case of produced waters with high concentrations of Ca{sup 2+}, a lime softening step is included.
The electrical properties of lead zirconate titanate ceramics near the 95/5 composition are extremely sensitive to the chemical composition and processing conditions. To precisely control the lead stoichiometry in a solid solution has been a challenge because of lead volatility during high temperature sintering. In this study, we investigated the effect of the amount of lead in the solid solution on crystal structure, dielectric behavior, and phase transformation characteristics for chemically prepared niobium modified PZT 95/5 ceramics. Implications are important for process control and assurance of material performance.
The hydrostatically induced ferroelectric(FE)-to-antiferroelectric(AFE) phase transformation for chemically prepared niobium modified PZT 95/5 ceramics was studied as a function of density and pore former type (Lucite or Avicel). Special attention was placed on the effect of different pore formers on the charge release behavior associated with the FE-to-AFE phase transformation. Within the same density range (7.26 g/cm3 to 7.44 g/cm3), results showed that ceramics prepared with Lucite pore former exhibit a higher bulk modulus and a sharper polarization release behavior than those prepared with Avicel. In addition, the average transformation pressure was 10.7% greater and the amount of polarization released was 2.1% higher for ceramics with Lucite pore former. The increased transformation pressure was attributed to the increase of bulk modulus associated with Lucite pore former. Data indicated that a minimum volumetric transformational strain of -0.42% was required to trigger the hydrostatically induced FE-to-AFE phase transformation. This work has important implications for increasing the high temperature charge output for neutron generator power supply units.
We report for the first time a one-step, templateless method to directly prepare large arrays of oriented TiO{sub 2}-based nanotubes and continuous films. These titania nanostructures can also be easily prepared as conformal coatings on a substrate. The nanostructured films were formed on a Ti substrate seeded with TiO{sub 2} nanoparticles. SEM and TEM results suggested that a folding mechanism of sheetlike structures was involved in the formation of the nanotubes. The oriented arrays of TiO{sub 2} nanotubes, continuous films, and coatings are expected to have potentials for applications in catalysis, filtration, sensing, photovoltaic cells, and high surface area electrodes.
Niobium doped PZT 95/5 (lead zirconate-lead titanate) is the material used in voltage bars for all ferroelectric neutron generator power supplies. In June of 1999, the transfer and scale-up of the Sandia Process from Department 1846 to Department 14192 was initiated. The laboratory-scale process of 1.6 kg has been successfully scaled to a production batch quantity of 10 kg. This report documents efforts to characterize and optimize the production-scale process utilizing Design of Experiments methodology. Of the 34 factors identified in the powder preparation sub-process, 11 were initially selected for the screening design. Additional experiments and safety analysis subsequently reduced the screening design to six factors. Three of the six factors (Milling Time, Media Size, and Pyrolysis Air Flow) were identified as statistically significant for one or more responses and were further investigated through a full factorial interaction design. Analysis of the interaction design resulted in developing models for Powder Bulk Density, Powder Tap Density, and +20 Mesh Fraction. Subsequent batches validated the models. The initial baseline powder preparation conditions were modified, resulting in improved powder yield by significantly reducing the +20 mesh waste fraction. Response variation analysis indicated additional investigation of the powder preparation sub-process steps was necessary to identify and reduce the sources of variation to further optimize the process.
Chemically prepared zinc oxide powders are fabricated for the production of high aspect ratio varistor components. Colloidal processing was performed to reduce agglomerates to primary particles, form a high solids loadingslurry, and prevent dopant migration. The milled and dispersed powder exhibited a viscoelastic to elastic behavioral transition at a volume loading of 43-46%. The origin of this transition was studied using acoustic spectroscopy, zeta potential measurements, and oscillatory rheology. The phenomenon occurs due to a volume fraction solids dependent reduction in the zeta potential of the solid phase. It is postulated to result from divalent ion binding within the polyelectrolyte dispersant chain and was mitigated using a polyethylene glycol plasticizing additive. This allowed for increased solids loading in the slurry and a green body fabrication study to be presented in our companion paper.
Chemically prepared zinc oxide powders were processed for the production of high aspect ratio varistor components (length/diameter >5). Near-net-shape casting methods including slip casting and agarose gelcasting were evaluated for effectiveness in achieving a uniform green microstructure that densifies to near theoretical values during sintering. The structure of the green parts was examined by mercury porisimetry. Agarose gelcasting produced green parts having low solids loading values and did not achieve high fired density. Isopressing the agarose cast parts after drying raised the fired density to greater than 95%, but the parts exhibited catastrophic shorting during electrical testing. Slip casting produced high green density parts, which exhibit high fired density values. The electrical characteristics of slip-cast parts are comparable with dry-pressed powder compacts.
The Materials Chemistry Department 1846 has developed a lab-scale chem-prep process for the synthesis of PNZT 95/5, referred to as the ''SP'' process (Sandia Process). This process (TSP) has been successfully transferred to and scaled-up by Department 14192 (Ceramics and Glass Department), producing the larger quantities of PZT powder required to meet the future supply needs of Sandia for neutron generator production. The particle size distributions of TSP powders routinely have been found to contain a large particle size fraction that was absent in development (SP) powders. This SAND report documents experimental studies focused on characterizing these particles and assessing their potential impact on material performance. To characterize these larger particles, fractionation of several TSP powders was performed. The ''large particle size fractions'' obtained were characterized by particle size analysis, SEM, and ICP analysis and incorporated into compacts and sintered. Large particles were found to be very similar in structure and composition as the bulk of the powder. Studies showed that the large-size fractions of the powders behave similarly to the non-fractionated powder with respect to the types of microstructural features once sintered. Powders were also compared that were prepared using different post-synthesis processing (i.e. differences in precipitate drying). Results showed that these powders contained different amounts and sizes of porous inclusions when sintered. How this affects the functional performance of the PZT 95/5 material is the subject of future investigations.
The particular lead zirconate/titanate composition PZT 95/5-2Nb was identified many years ago as a promising ferroelectric ceramic for use in shock-driven pulsed power supplies. The bulk density and the corresponding porous microstructure of this material can be varied by adding different types and quantities of organic pore formers prior to bisque firing and sintering. Early studies showed that the porous microstructure could have a significant effect on power supply performance, with only a relatively narrow range of densities providing acceptable shock wave response. However, relatively few studies were performed over the years to characterize the shock response of this material, yielding few insights on how microstructural features actually influence the constitutive mechanical, electrical, and phase-transition properties. The goal of the current work was to address these issues through comparative shock wave experiments on PZT 95/5-2Nb materials having different porous microstructures. A gas-gun facility was used to generate uniaxial-strain shock waves in test materials under carefully controlled impact conditions. Reverse-impact experiments were conducted to obtain basic Hugoniot data, and transmitted-wave experiments were conducted to examine both constitutive mechanical properties and shock-driven electrical currents. The present work benefited from a recent study in which a baseline material with a particular microstructure had been examined in detail. This study identified a complex mechanical behavior governed by anomalous compressibility and incomplete phase transformation at low shock amplitudes, and by a relatively slow yielding process at high shock amplitudes. Depoling currents are reduced at low shock stresses due to the incomplete transformation, and are reduced further in the presence of a strong electrical field. At high shock stresses, depoling currents are driven by a wave structure governed by the threshold for dynamic yielding. This wave structure is insensitive to the final wave amplitude, resulting in depoling currents that do not increase with shock amplitude for stresses above the yield threshold. In the present study, experiments were conducted under matched experimental conditions to directly compare with the behavior of the baseline material. Only subtle differences were observed in the mechanical and electrical shock responses of common-density materials having different porous microstructures, but large effects were observed when initial density was varied.
This paper reports the preparation of cubically ordered, self-assembled nanostructural crystals on micropatterned surfaces. Large ordered arrays of octahedral crystals were formed on substrates with triangular-shaped micropatterns that match the shape of the {111} surface morphology of the crystals. Many crystals became self-aligned in X, Y, and Z orientations through the interaction with the matching micropatterns. However, line micropatterns did not produce such well-defined crystals and crystal alignment. This work is among the first examples to show 3D crystal alignment independent of the long rodlike micellar structure that is characteristic of the hexagonal phases. Significantly, it also suggests that the geometry of the underline patterns has a large effect on the crystal morphology and orientation. We hope that these results will be helpful in developing microdevices based on self-assembled nanoscale materials.
We have undertaken the synthesis of a thin film ''All Ceramic Battery'' (ACB) using solution route processes. Based on the literature and experimental results, we selected SnO{sub 2}, LiCoO{sub 2}, and LiLaTiO{sub 3} (LLT) as the anode, cathode, and electrolyte, respectively. Strain induced by lattice mismatch between the cathode and bottom electrode, as estimated by computational calculations, indicate that thin film orientations for batteries when thicknesses are as low as 500 {angstrom} are strongly controlled by surface energies. Therefore, we chose platinized silicon as the basal platform based on our previous experience with this material. The anode thin films were generated by standard spin-cast methods and processing using a solution of [Sn(ONep)]{sub 8} and HOAc which was found to form Sn{sub 6}(O){sub 4}(ONep){sub 4}. Electrochemical evaluation showed that the SnO{sub 2} was converted to Sn{sup o} during the first cycle. The cathode was also prepared by spin coating using the novel [Li(ONep)]{sub 8} and Co(OAc){sub 2}. The films could be electrochemically cycled (i.e., charged/discharged), with all of the associated structural changes being observable by XRD. Computational models indicated that the LLT electrolyte would be the best available ceramic material for use as the electrolyte. The LLT was synthesized from [Li(ONep)]{sub 8}, [Ti(ONep){sub 4}]{sub 2}, and La(DIP){sub 3}(py){sub 3} with RTP processing at 900 C being necessary to form the perovskite phase. Alternatively, a novel route to thin films of the block co-polymer ORMOLYTE was developed. The integration of these components was undertaken with each part of the assembly being identifiably by XRD analysis (this will allow us to follow the progress of the charge/discharge cycles of the battery during use). SEM investigations revealed the films were continuous with minimal mixing. All initial testing of the thin-film cathode/electrolyte/anode ACB devices revealed electrical shorting. Alternative approaches for preparing non-shorted devices (e.g. inverted and side-by-side) are under study.
The Materials Chemistry Department 1846 has developed a lab-scale chem-prep process for the synthesis of PNZT 95/5, a ferroelectric material that is used in neutron generator power supplies. This process (Sandia Process, or SP) has been successfully transferred to and scaled by Department 14192 (Ceramics and Glass Department), (Transferred Sandia Process, or TSP), to meet the future supply needs of Sandia for its neutron generator production responsibilities. In going from the development-size SP batch (1.6 kg/batch) to the production-scale TSP powder batch size (10 kg/batch), it was important that it be determined if the scaling process caused any ''performance-critical'' changes in the PNZT 95/5 being produced. One area where a difference was found was in the particle size distributions of the calcined PNZT powders. Documented in this SAND report are the results of an experimental study to determine the origin of the differences in the particle size distribution of the SP and TSP powders.
Robocasting, a computer controlled slurry deposition technique, was used to fabricate ceramic monoliths and composites of chemically prepared Pb(Zr{sub 0.95}Ti{sub 0.05})O{sub 3} (PZT 95/5) ceramics. Densities and electrical properties of the robocast samples were equivalent to those obtained for cold isostatically pressed (CIP) parts formed at 200 MPa. Robocast composites consisting of alternate layers of the following sintered densities: (93.9%--96.1%--93.9%), were fabricated using different levels of organic pore former additions. Modification from a single to a multiple material deposition robocaster was essential to the fabrication of composites that could withstand repeated cycles of saturated polarization switching under 30 kV/cm fields. Further, these composites withstood 500 MPa hydrostatic pressure induced poled ferroelectric (FE) to antiferroelectric (AFE) phase transformation during which strain differences on the order of 0.8% occurred between composite elements.