We report on the novel room temperature method of synthesizing advanced nuclear fuels; a method that virtually eliminates any volatility of components. This process uses radiolysis to form stable nanoparticle (NP) nuclear transuranic (TRU) fuel surrogates and in-situ heated stage TEM to sinter the NPs. The radiolysis is performed at Sandia's Gamma Irradiation Facility (GIF) 60Co source (3 x 10{sup 6} rad/hr). Using this method, sufficient quantities of fuels for research purposes can be produced for accelerated advanced nuclear fuel development. We are focused on both metallic and oxide alloy nanoparticles of varying compositions, in particular d-U, d-U/La alloys and d-UO2 NPs. We present detailed descriptions of the synthesis procedures, the characterization of the NPs, the sintering of the NPs, and their stability with temperature. We have employed UV-vis, HRTEM, HAADF-STEM imaging, single particle EDX and EFTEM mapping characterization techniques to confirm the composition and alloying of these NPs.
Room temperature radiolysis, density functional theory, and various nanoscale characterization methods were used to synthesize and fully describe Ni-based alloy nanoparticles (NPs) that were synthesized at room temperature. These complementary methods provide a strong basis in understanding and describing metastable phase regimes of alloy NPs whose reaction formation is determined by kinetic rather than thermodynamic reaction processes. Four series of NPs, (Ag-Ni, Pd-Ni, Co-Ni, and W-Ni) were analyzed and characterized by a variety of methods, including UV-vis, TEM/HRTEM, HAADF-STEM and EFTEM mapping. In the first focus of research, AgNi and PdNi were studied. Different ratios of Ag{sub x}- Ni{sub 1-x} alloy NPs and Pd{sub 0.5}- Ni{sub 0.5} alloy NP were prepared using a high dose rate from gamma irradiation. Images from high-angle annular dark-field (HAADF) show that the Ag-Ni NPs are not core-shell structure but are homogeneous alloys in composition. Energy filtered transmission electron microscopy (EFTEM) maps show the homogeneity of the metals in each alloy NP. Of particular interest are the normally immiscible Ag-Ni NPs. All evidence confirmed that homogeneous Ag-Ni and Pd-Ni alloy NPs presented here were successfully synthesized by high dose rate radiolytic methodology. A mechanism is provided to explain the homogeneous formation of the alloy NPs. Furthermore, studies of Pd-Ni NPs by in situ TEM (with heated stage) shows the ability to sinter these NPs at temperatures below 800 C. In the second set of work, CoNi and WNi superalloy NPs were attempted at 50/50 concentration ratios using high dose rates from gamma irradiation. Preliminary results on synthesis and characterization have been completed and are presented. As with the earlier alloy NPs, no evidence of core-shell NP formation occurs. Microscopy results seem to indicate alloying occurred with the CoNi alloys. However, there appears to be incomplete reduction of the Na{sub 2}WO{sub 4} to form the W{sup 2+} ion in solution; the predominance of WO{sup +} appears to have resulted in a W-O-Ni complex that has not yet been fully characterized.
Shielded special nuclear material (SNM) is very difficult to detect and new technologies are needed to clear alarms and verify the presence of SNM. High-energy photons and neutrons can be used to actively interrogate for heavily shielded SNM, such as highly enriched uranium (HEU), since neutrons can penetrate gamma-ray shielding and gamma-rays can penetrate neutron shielding. Both source particles then induce unique detectable signals from fission. In this LDRD, we explored a new type of interrogation source that uses low-energy proton- or deuteron-induced nuclear reactions to generate high fluxes of mono-energetic gammas or neutrons. Accelerator-based experiments, computational studies, and prototype source tests were performed to obtain a better understanding of (1) the flux requirements, (2) fission-induced signals, background, and interferences, and (3) operational performance of the source. The results of this research led to the development and testing of an axial-type gamma tube source and the design/construction of a high power coaxial-type gamma generator based on the {sup 11}B(p,{gamma}){sup 12}C nuclear reaction.
High-energy photons and neutrons can be used to actively interrogate for heavily shielded special nuclear material (SNM), such as HEU (highly enriched uranium), by detecting prompt and/or delayed induced fission signatures. In this work, we explore the underlying physics for a new type of photon source that generates high fluxes of mono-energetic gamma-rays from low-energy (<500 keV) proton-induced nuclear reactions. The characteristic energies (4- to 18-MeV) of the gamma-rays coincide with the peak of the photonuclear cross section. The source could be designed to produce gamma-rays of certain selected energies, thereby improving the probability of detecting shielded HEU or providing a capability to determine enrichment inside sealed containers. The fundamental physics of such an interrogation source were studied in this LDRD through scaled ion accelerator experiments and radiation transport modeling. The data were used to assess gamma and neutron yields, background, and photofission-induced signal levels from several (p,{gamma}) target materials under consideration.
GaN-based microwave power amplifiers have been identified as critical components in Sandia's next generation micro-Synthetic-Aperture-Radar (SAR) operating at X-band and Ku-band (10-18 GHz). To miniaturize SAR, GaN-based amplifiers are necessary to replace bulky traveling wave tubes. Specifically, for micro-SAR development, highly reliable GaN high electron mobility transistors (HEMTs), which have delivered a factor of 10 times improvement in power performance compared to GaAs, need to be developed. Despite the great promise of GaN HEMTs, problems associated with nitride materials growth currently limit gain, linearity, power-added-efficiency, reproducibility, and reliability. These material quality issues are primarily due to heteroepitaxial growth of GaN on lattice mismatched substrates. Because SiC provides the best lattice match and thermal conductivity, SiC is currently the substrate of choice for GaN-based microwave amplifiers. Obviously for GaN-based HEMTs to fully realize their tremendous promise, several challenges related to GaN heteroepitaxy on SiC must be solved. For this LDRD, we conducted a concerted effort to resolve materials issues through in-depth research on GaN/AlGaN growth on SiC. Repeatable growth processes were developed which enabled basic studies of these device layers as well as full fabrication of microwave amplifiers. Detailed studies of the GaN and AlGaN growth of SiC were conducted and techniques to measure the structural and electrical properties of the layers were developed. Problems that limit device performance were investigated, including electron traps, dislocations, the quality of semi-insulating GaN, the GaN/AlGaN interface roughness, and surface pinning of the AlGaN gate. Surface charge was reduced by developing silicon nitride passivation. Constant feedback between material properties, physical understanding, and device performance enabled rapid progress which eventually led to the successful fabrication of state of the art HEMT transistors and amplifiers.
Transmission electron microscopy and x-ray diffraction were used to assess the microstructure and strain of Al{sub x}Ga{sub 1?x}N(x = 0.61-0.64) layers grown on AlN. The compressively-strained AlGaN is partially relaxed by inclined threading dislocations, similar to observations on Si-doped AlGaN by P. Cantu, F. Wu, P. Waltereit, S. Keller, A. E. Romanov, U. K. Mishra, S. P. DenBaars, and J. S. Speck [Appl. Phys. Lett. 83, 674 (2003) ]; however, in our material, the dislocations bend before the introduction of any Si. The bending may be initiated by the greater lattice mismatch or the lower dislocation density of our material, but the presence of Si is not necessarily required. The relaxation by inclined dislocations is quantitatively accounted for with the model of A. E. Romanov and J. S. Speck [Appl. Phys. Lett. 83, 2569 (2003)], and we demonstrate the predicted linear dependence of relaxation on layer thickness. Notably, such relaxation was not found in tensile strained AlGaN grown on GaN [J. A. Floro, D. M. Follstaedt, P. Provencio, S. J. Hearne, and S. R. Lee, J. Appl. Phys. 96, 7087 (2004)], even though the same mechanism appears applicable.
We develop a reciprocal-space model that describes the (hkl) dependence of the broadened Bragg peakwidths produced by x-ray diffraction from a dislocated epilayer. We compare the model to experiments and find that it accurately describes the peakwidths of 16 different Bragg reflections in the [010] zone of both GaN and AlN heterolayers. Using lattice-distortion parameters determined by fitting the model to selected reflections, we estimate threading-dislocation densities for seven different GaN and AlGaN samples and find improved agreement with transmission electron microscopy measurements.
Chemical microsensors rely on partitioning of airborne chemicals into films to collect and measure trace quantities of hazardous vapors. Polymer sensor coatings used today are typically slow to respond and difficult to apply reproducibly. The objective of this project was to produce a durable sensor coating material based on graphitic nanoporous-carbon (NPC), a new material first studied at Sandia, for collection and detection of volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical warfare agents (CWA) and nuclear processing precursors (NPP). Preliminary studies using NPC films on exploratory surface-acoustic-wave (SAW) devices and as a {micro}ChemLab membrane preconcentrator suggested that NPC may outperform existing, irreproducible coatings for SAW sensor and {micro}ChemLab preconcentrator applications. Success of this project will provide a strategic advantage to the development of a robust, manufacturable, highly-sensitive chemical microsensor for public health, industrial, and national security needs. We use pulsed-laser deposition to grow NPC films at room-temperature with negligible residual stress, and hence, can be deposited onto nearly any substrate material to any thickness. Controlled deposition yields reproducible NPC density, morphology, and porosity, without any discernable variation in surface chemistry. NPC coatings > 20 {micro}m thick with density < 5% that of graphite have been demonstrated. NPC can be 'doped' with nearly any metal during growth to provide further enhancements in analyte detection and selectivity. Optimized NPC-coated SAW devices were compared directly to commonly-used polymer coated SAWs for sensitivity to a variety of VOC, TIC, CWA and NPP. In every analyte, NPC outperforms each polymer coating by multiple orders-of-magnitude in detection sensitivity, with improvements ranging from 103 to 108 times greater detection sensitivity! NPC-coated SAW sensors appear capable of detecting most analytes tested to concentrations below parts-per-billion. In addition, the graphitic nature of NPC enables thermal stability > 600 C, several hundred degrees higher than the polymers. This superior thermal stability will enable higher-Temperature preconcentrator operation, as well as greatly prolonged device reliability, since polymers tend to degrade with time and repeated thermal cycling.
Solid-state light sources emitting at wavelengths less than 300 nm would enable technological advances in many areas such as fluorescence-based biological agent detection, non-line-of-sight communications, water purification, and industrial processing including ink drying and epoxy curing. In this paper, we present our recent progress in the development of LEDs with emission between 237 and 297 nm. We will discuss growth and design issues of deep-UV LEDs, including transport in Si-doped AlGaN layers. The LEDs are designed for bottom emission so that improved heat sinking and light extraction can be achieved by flip chipping. To date, we have demonstrated 2.25 mW of output power at 295 nm from 1 mm x 1 mm LEDs operated at 500 mA. Shorter wavelength LEDs emitting at 276 nm have achieved an output power of 1.3 mW at 400 mA. The heterostructure designs that we have employed have suppressed deep level emission to intensities that are up to 330 x lower than the primary quantum well emission.
This SAND report is the final report on Sandia's Grand Challenge LDRD Project 27328, 'A Revolution in Lighting -- Building the Science and Technology Base for Ultra-Efficient Solid-state Lighting.' This project, which for brevity we refer to as the SSL GCLDRD, is considered one of Sandia's most successful GCLDRDs. As a result, this report reviews not only technical highlights, but also the genesis of the idea for Solid-state Lighting (SSL), the initiation of the SSL GCLDRD, and the goals, scope, success metrics, and evolution of the SSL GCLDRD over the course of its life. One way in which the SSL GCLDRD was different from other GCLDRDs was that it coincided with a larger effort by the SSL community - primarily industrial companies investing in SSL, but also universities, trade organizations, and other Department of Energy (DOE) national laboratories - to support a national initiative in SSL R&D. Sandia was a major player in publicizing the tremendous energy savings potential of SSL, and in helping to develop, unify and support community consensus for such an initiative. Hence, our activities in this area, discussed in Chapter 6, were substantial: white papers; SSL technology workshops and roadmaps; support for the Optoelectronics Industry Development Association (OIDA), DOE and Senator Bingaman's office; extensive public relations and media activities; and a worldwide SSL community website. Many science and technology advances and breakthroughs were also enabled under this GCLDRD, resulting in: 55 publications; 124 presentations; 10 book chapters and reports; 5 U.S. patent applications including 1 already issued; and 14 patent disclosures not yet applied for. Twenty-six invited talks were given, at prestigious venues such as the American Physical Society Meeting, the Materials Research Society Meeting, the AVS International Symposium, and the Electrochemical Society Meeting. This report contains a summary of these science and technology advances and breakthroughs, with Chapters 1-5 devoted to the five technical task areas: 1 Fundamental Materials Physics; 2 111-Nitride Growth Chemistry and Substrate Physics; 3 111-Nitride MOCVD Reactor Design and In-Situ Monitoring; 4 Advanced Light-Emitting Devices; and 5 Phosphors and Encapsulants. Chapter 7 (Appendix A) contains a listing of publications, presentations, and patents. Finally, the SSL GCLDRD resulted in numerous actual and pending follow-on programs for Sandia, including multiple grants from DOE and the Defense Advanced Research Projects Agency (DARPA), and Cooperative Research and Development Agreements (CRADAs) with SSL companies. Many of these follow-on programs arose out of contacts developed through our External Advisory Committee (EAC). In h s and other ways, the EAC played a very important role. Chapter 8 (Appendix B) contains the full (unedited) text of the EAC reviews that were held periodically during the course of the project.
Experiments using high-resolution size exclusion chromatography (HRSEC), dynamic light scattering, and transmission electron microscopy are conducted to investigate the effects of aging of Au nanoclusters in the presence of surfactant ligands. It is observed that contrary to the expectation that aging in solution will always broaden the size dispersion and increase the average size (Ostwald ripening), a narrowing of the size dispersion and change in average size can occur with time under ambient conditions.
We describe the synthesis of highly magnetic iron nanoparticles using a novel surfactant, a {beta}-diketone. We have produced 6 nm iron nanoparticles with an unusually high saturation magnetization of more than 80% the value of bulk iron. Additionally, we measured a particle susceptibility of 14 (MKS units), which is far above the value possible for micron-scale spherical particles. These properties will allow for formation of composites that can be highly structured by magnetic fields.
We report studies of the magnetic response of dilute frozen solutions of nanocrystalline Co particles grown in inverse micelles. Crystalline nanoclusters which initially exhibit only a small fraction of the bulk saturation moment restructure in solution without any change in cluster size or blocking temperature over a period of {approx}30-60 days, finally yielding a moment/atom which exceeds that of bulk Co. The saturation magnetism maintains its enhanced value for temperatures up to the melting point of the solvent matrix, but is strongly dependent on surface active additives and molecular oxygen.
We have conducted surface treatment and alloying experiments with Al, Fe, and Ti-based metals on the RHEPP-1 accelerator (0.8 MV, 20 W, 80 ns FHWM, up to 1 Hz repetition rate) at Sandia National Laboratories. Ions are generated by the MAP gas-breakdown active anode, which can yield a number of different beam species including H, N, and C, depending upon the injected gas. Beams of intense pulsed high-power ion beams have been used to produce surface modification by changes in microstructure caused by rapid heating and cooling of the surface. Increase of beam power leads to ablation of a target surface, and redeposition of ablated material onto a separate substrate. Experiments are described in which ion beams are used in an attempt to increase high-voltage breakdown of a treated surface. Surface alloying of coated Pt and Hf layers is also described. This mixing of a previously deposited thin-film layer into a Ti-alloy substrate leads to significantly enhanced surface wear durability, compared to either untreated Ti-alloy alone, or the Ti alloy alone treated with the ion beam. Thin-film layers have been produced from a number of target materials. Films of fine-grain Pt and Er are described, and are compared to conventionally formed films. First attempts to form high-dielectric constant BaTiO{sub 3} are described.
We report high-pressure liquid chromatography (HPLC) and transmission electron microscopy (TEM) studies of the size distributions of nanosize gold clusters dispersed in organic solvents. These metal clusters are synthesized in inverse micelles at room temperature, and those investigated range in diameter from 1 to 10 nm. HPLC is sensitive enough to discern changes in hydrodynamic volume corresponding to only 2 carbon atoms of the passivating agent or metal core size changes of less than 4 angstrom. We have determined for the first time how the total cluster volume (metal core + passivating organic shell) changes with the size of the passivating agent.
From the results of the different bacterial cells seen, it is fairly certain that Gallionella is present because of the bean-shaped cells and twisted stalks found with the TEM. The authors cannot confirm, though, what other iron-oxidizing genera exist in the tubes, since the media was only preferential and not one that isolated a specific genus of bacteria. Based on the environment in which they live and the source of the water, they believe their cultures contain Gallionella, Leptothrix, and possibly Crenothrix and Sphaerotilus. They believe the genus Leptothrix rather than Sphaerotilus exist in the tubes because the water source was fresh, unlike the polluted water in which Sphaerotilus are usually found. The TEM preparations worked well. The cryogenic method rapidly froze the cells in place and allowed them to view their morphology. The FAA method, as stated previously, was the best of the three methods because it gave the best contrast. The gluteraldehyde samples did not come out as well. It is possible that the gluteraldehyde the authors prepared was still too concentrated and did not mix well. Although these bacteria were collected from springs and then cultured in an environment containing a presumably pure iron-bearing metal, it seems the tube already containing Manganese Gradient Medium could be used with a piece of metal containing these bacteria. A small piece of corroding metal could then be inserted into the test tube and cultured to study the bacteria.
The density of threading dislocations (TD) in GaN grown directly on flat sapphire substrates is typically greater than 10{sup 9}/cm{sup 2}. Such high dislocation densities degrade both the electronic and photonic properties of the material. The density of dislocations can be decreased by orders of magnitude using cantilever epitaxy (CE), which employs prepatterned sapphire substrates to provide reduced-dimension mesa regions for nucleation and etched trenches between them for suspended lateral growth of GaN or AlGaN. The substrate is prepatterned with narrow lines and etched to a depth that permits coalescence of laterally growing III-N nucleated on the mesa surfaces before vertical growth fills the etched trench. Low dislocation densities typical of epitaxial lateral overgrowth (ELO) are obtained in the cantilever regions and the TD density is also reduced up to 1 micrometer from the edge of the support regions.
Highly crystalline germanium (Ge) nanocrystals in the size range 2--10 nm were grown in inverse micelles and purified and size-separated by high pressure liquid chromatography with on-line optical and electrical diagnostics. The nanocrystals retain the diamond structure of bulk Ge down to at least 2.0 nm (containing about 150 Ge atoms). The background- and impurity-free extinction and photoluminescence (PL) spectra of these nanocrystals revealed rich structure which was interpreted in terms of the bandstructure of Ge shifted to higher energies by quantum confinement. The shifts ranged from {minus}0.1 eV to over 1 eV for the various transitions. PL in the range 350--700 nm was observed from nanocrystals 2--5 nm in size. The 2.0 nm nanocrystals yielded the most intense PL (at 420 nm) which is believed to be intrinsic and attributed to direct recombination at {Gamma}. Excitation at high energy (250 nm) populates most of the conduction bands resulting in competing recombination channels and the observed broad PL spectra.
The authors have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C{sub 6} to C{sub 18} were used as hydrophobic ligands, and with some of these they were able to form 2-D and/or 3-D superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function of the particle centers, from which they can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the gaps between particles within superlattice domains increases, but more slowly than one might expect, possibly indicating thiol chain interdigitation.
The authors have investigated the formation of 2-D and 3-D superlattices of Au nanoclusters synthesized in nonionic inverse micelles, and capped with alkyl thiol ligands, with alkane chains ranging from C{sub 6} to C1{sub 18}. The thiols are found to play a significant role in the ripening of these nanoclusters, and in the formation of superlattices. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function, from which one can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the nanoclusters become more polydisperse and larger, and the gaps between particles within superlattice domains increases. Annealing studies at elevated temperatures confirm nanocluster ripening. Finally, the effect of the particle gaps on physical properties is illustrated by computing the effective dielectric constant, and it is shown that the gap size now accessible in superlattices is rather large for dielectric applications.