Effective diversion of surge currents is vital to prevent unwanted damage to sensitive electronics. Among the most successful and efficient strategies relies on a dielectric stimulated arc breakdown mechanism with high permittivity ceramic granules in a spark-gap geometry. Although generally regarded as a self-healing process, substantial energy deposition may occur that, over time, diminishes the ability to withstand repeated electrical assaults. We investigate the susceptibility of lead–magnesium–niobate–lead titanate (PMN–PT) granule microstructure and composition changes following many exposures to high voltage impulses resulting in arc breakdown. Scanning electron microscopy and energy-dispersive spectroscopy mapping reveal a broad range of thermal and mechanical defects entailing thermal reduction of constituent PMN–PT metal ions and recasting due to rapid eruption of volatile species. Additionally, evidence of local melting and microcracking are apparent that can have deleterious impact on the proper function of the granules, namely, the ability to concentrate electric fields across air gaps to establish and sustain discharge pathways. We propose that the localized nature of damage and stochasticity associated with the dielectric stimulated breakdown mechanism may allow granules to maintain functionality provided no permanent conduction paths are established.
Pb-Zr-Ti-O (PZT) perovskites span a large solid-solution range and have found widespread use due to their piezoelectric and ferroelectric properties that also span a large range. Crystal structure analysis via Rietveld refinement facilitates materials analysis via the extraction of the structural parameters. These parameters, often obtained as a function of an additional dimension (e.g., pressure), can help to diagnose materials response within a use environment. Often referred to as in-situ studies, these experiments provide an abundance of data. Viewing structural changes due to applied pressure conditions can give much-needed insight into materials performance. However, challenges exist for viewing/presenting results when the details are inherently three-dimensional (3D) in nature. For PZT perovskites, the use of polyhedra (e.g., Zr/Ti-O6 octahedra) to view bonding/connectivity is beneficial; however, the visualization of the octahedra behavior with pressure dependence is less easily demonstrated due to the complexity of the added pressure dimension. We present a more intuitive visualization by projecting structural data into virtual reality (VR). We employ previously published structural data for Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 as an exemplar for VR visualization of the PZT R3c crystal structure between ambient and 0.62 GPa pressure. This is accomplished via our in-house CAD2VR™ software platform and the new CrystalVR plugin. The use of the VR environment enables a more intuitive viewing experience, while enabling on-the-fly evaluation of crystal data, to form a detailed and comprehensive understanding of in-situ datasets. Discussion of methodology and tools for viewing are given, along with how recording results in video form can enable the viewing experience.
Thermal properties are an integral part of many diverse engineering applications, and additive manufacturing (AM), particularly laser powder bed fusion (LPBF) is shown to affect thermal properties due to the laser processing parameters. For 316L stainless steel, there is little prior research to determine the effects of the process on thermal properties. In this work, the temperature gradient is shown to create uniform, chess board-like distributions of grains in the build direction. These zones create dislocations which were visualized with EBSD techniques. Processing parameters cause hierarchal grain size distribution, with localized concentrations of small grains and large grains. Thermomechanical stresses in the rapid solidification increases dislocation density during grain formation. Previous research shows a higher density of dislocations decreases local thermal conductivity. Local and bulk thermal conductivity are shown in this work to have statistically lowered values to an average of 10-12 W/m-K compared to 14 W/m-K for conventional 316L.
Refractory complex concentrated alloys are an emerging class of materials that attracts attention due to their stability and performance at high temperatures. In this study, we investigate the variations in the mechanical and thermal properties across a broad compositional space for the refractory MoNbTaTi quaternary using high-throughput ab-initio calculations and experimental characterization. For all the properties surveyed, we note a good agreement between our modeling predictions and the experimentally measured values. We reveal the particular role of molybdenum (Mo) to achieve high strength when in high concentration. We trace the origin of this phenomenon to a shift from metallic to covalent bonding when the Mo content is increased. Additionally, a mechanistic, dislocation-based description of the yield strength further explains such high strength due to a combination of high bulk and shear moduli, accompanied by the relatively small size of the Mo atom compared to the other atoms in the alloy. Our analysis of the thermodynamics properties shows that regardless of the composition, this class of quaternary alloys shows good stability and low sensitivity to temperature. Taken together, these results pave the way for the design of new high-performance refractory alloys beyond the equimolar composition found in high-entropy alloys.
The electric discharge across a varistor granule filled air gap under a fast-rising voltage pulse was investigated for surge protection applications. The effects of temperature and pressure on the arc and the electrical conduction were analyzed by the characteristic changes in voltage waveforms triggered by a fast-rising high voltage pulse. In addition to the gap size, experimental results show that competing mechanisms among arc conduction, conduction through the varistor granule network, thermionic emission from Joule heating at granule-to-granule contact points, and the magnitude of the switching voltage dictate the maximum surge protection voltage for the filled air gap. Experimental evidence indicated that accumulated degradation was created at small contact points between varistor granules by repetitive assaults from longer duration, high voltage pulses. The uniqueness of using varistor over other dielectric granules in an air gap for surge protection is identified and discussed.
Electric discharge across an air gap can be self-healing, providing a unique capability for repetitive, fast, high-voltage/current switching applications through arc conduction. Furthermore, incorporating dielectric granules in the air gap stimulates gas ionization, which lowers the breakdown voltage and narrows breakdown voltage distribution, thereby enabling engineered surge protection from multiple lightning strikes on aerospace vehicles and sensitive solid-state electronics in critical systems. This study investigates the effect of the permittivity of dielectric granules, gap filling, surface roughness, and metal work function on fast-rising, high-voltage breakdowns. In addition to the air gap width, these factors play important roles in gas ionization, field concentration, and initiation of electrical discharge and arcing. Therefore, they could potentially be used to control and narrow operational breakdown voltages for practical applications. Additionally, a modified Langevin-Debye model is developed to correlate the breakdown voltage and the permittivity of the dielectric filler. These investigations identify and highlight key underpinning mechanisms governing the gas discharge behavior across a dielectric filled air gap during voltage surge events.
This report documents an effort to improve the energy resolution for a thallium doped cesium iodide (CsI:T1) scintillator paired with a spectrum matching photomultiplier tube (PMT). A comparison of the differences in the pulse height spectra from thallium doped (CsI:T1) and sodium doped (CsI:Na) single crystals with PMTs of different spectrum responses was performed. Results show that energy resolution of the detector only improves 0.5% at room temperature when these scintillators are coupled with a spectrum matching PMT. Based on a spectrum matching PMT, the best results for energy resolution are 7.39% and 7.88% for CsI:T1 and CsI:Na scintillators, respectively. The improvement is primarily attributed to the increase of photon statistics from the increase of photons (N) being detected in the spectrum matching PMT. Other factors, such as optical quantum yield and non-proportionality of the CsI:T1 and CsI:Na crystals, that can affect the energy resolution were also studied and reported. The results indicate that although the use of a spectrum matching PMT enhances the photon statistics, it also exacerbates the nonproportionality response. Consequently, a promised improvement on energy resolution due solely to photon statistics was not fully realized.
TlBr can surpass CZT as the leading semiconductor for γ- A nd X-radiation detection. Unfortunately, the optimum properties of TlBr quickly decay when an operating electrical field is applied. Quantum mechanical studies indicated that if this property degradation comes from the conventional mechanism of ionic migration of vacancies, then an unrealistically high vacancy concentration is required to account for the rapid aging of TlBr seen in experiments. In this work, we have applied large scale molecular dynamics simulations to study the effects of dislocations on ionic migration of TlBr crystals under electrical fields. We found that electrical fields can drive the motion of edge dislocations in both slip and climb directions. These combined motions eject enormous vacancies in the dislocation trail. Both dislocation motion and a high vacancy concentration can account for the rapid aging of the TlBr detectors. These findings suggest that strengthening methods to pin dislocations should be explored to increase the lifetimes of TlBr crystals.
It has been widely believed that crystalline TlBr can surpass CdZnTe to become the leading semiconductor for γ- and X- radiation detection. The major hurdle to this transition is the rapid aging of TlBr under the operating electrical field. Here, while ionic migration of vacancies has been traditionally the root cause for property degradation, quantum mechanical calculations indicated that the vacancy concentration needed to cause the observed aging must be orders of magnitude higher than the usual theoretical estimate. Recent molecular dynamics simulations and X-ray diffract ion experiments have shown that electrical fields can drive the motion of edge dislocations in both slip and climb directions. Furthermore, these combined motions eject a large number of vacancies. Both dislocation mot ion and vacancy ejection can account for the rapid aging of the TlBr detectors. Based on these new discoveries, the present work applies molecular dynamics simulations to “develop” aging-resistant TlBr crystals by inhibiting dislocation motions.
A preliminary finite-element model has been developed using the ALEGRA-FE code for explosive driven depoling of a PZT 95/5 ferroelectric generator. The ferroelectric material is characterized using hysteresis-loop and hydrostatic depoling tests. These characteristics are incorporated into ALEGRA-FE simulations that model the explosive drive mechanism and shock environment in the material leading to depoling, as well as the ferroelectric response and the behavior of a coupled circuit. The ferroelectric-to-antiferroelectric phase transition is captured, producing an output voltage pulse that matches experimental data to within 10% in rise time, and to within about 15% for the final voltage. Both experimental and modeled pulse magnitudes are less than the theoretical maximum output of the material. Observations from materials characterization suggest that unmodeled effects such as trapped charge in the stored FEG material may have influenced the experimentally observed output.
Various versions of deep borehole nuclear waste disposal have been proposed in the past in which effective sealing of a borehole after waste emplacement is generally required. In a high temperature disposal mode, the sealing function will be fulfilled by melting the ambient granitic rock with waste decay heat or an external heating source, creating a melt that will encapsulate waste containers or plug a portion of the borehole above a stack of the containers. However, there are certain drawbacks associated with natural materials, such as high melting temperatures, inefficient consolidation, slow crystallization kinetics, the resulting sealing materials generally being porous with low mechanical strength, insufficient adhesion to waste container surface, and lack of flexibility for engineering controls. In this study, we showed that natural granitic materials can be purposefully engineered through chemical modifications to enhance the sealing capability of the materials for deep borehole disposal. The present work systematically explores the effect of chemical modification and crystallinity (amorphous vs. crystalline) on the melting and crystallization processes of a granitic rock system. The approach can be applied to modify granites excavated from different geological sites. Several engineered granitic materials have been explored which possess significantly lower processing and densification temperatures than natural granites. Those new materials consolidate more efficiently by viscous flow and accelerated recrystallization without compromising their mechanical integrity and properties.
The powder-bed laser additive manufacturing (AM) process is widely used in the fabrication of three-dimensional metallic parts with intricate structures, where kinetically controlled diffusion and microstructure ripening can be hindered by fast melting and rapid solidification. Therefore, the microstructure and physical properties of parts made by this process will be significantly different from their counterparts produced by conventional methods. This work investigates the microstructure evolution for an AM fabricated AlSi10Mg part from its nonequilibrium state toward equilibrium state. Special attention is placed on silicon dissolution, precipitate formation, collapsing of a divorced eutectic cellular structure, and microstructure ripening in the thermal annealing process. These events alter the size, morphology, length scale, and distribution of the beta silicon phase in the primary aluminum, and changes associated with elastic properties and microhardness are reported. The relationship between residual stress and silicon dissolution due to changes in lattice spacing is also investigated and discussed.
TlBr has the properties to become the leading radiation detection semiconductor. It has not yet been deployed due to a short lifetime of only hours to weeks. While the rapid structural deteriorations must come from ionic conduction under operating electrical fields, detailed aging mechanisms have not been understood. As a result, progress to extend lifetime has been limited despite extensive studies in the past. We have developed new atomistic simulation capabilities to enable study of ionic conduction under electrical fields. Our combined simulations and experiments indicate that dislocations in TlBr climb under electrical fields. This climb is the root cause for structural deterioration. Hence, we discovered new strengthening methods to reduce aging. Our new atomistic simulation approach can have broader impact on other Sandia programs including battery research. Our project results in 4 publications, a new invention, new LAMMPS capabilities, solution to mission relevant materials, and numerous presentations.
TlBr crystals have superior radiation detection properties; however, their properties degrade in the range of hours to weeks when an operating electrical field is applied. To account for this rapid degradation using the widely-accepted vacancy migration mechanism, the vacancy concentration must be orders of magnitude higher than any conventional estimates. The present work has incorporated a new analytical variable charge model in molecular dynamics (MD) simulations to examine the structural changes of materials under electrical fields. Our simulations indicate that dislocations in TlBr move under electrical fields. This discovery can lead to new understanding of TlBr aging mechanisms under external fields.
TlBr is promising for g- and x- radiation detection, but suffers from rapid performance degradation under the operating external electric fields. To enable molecular dynamics (MD) studies of this degradation, we have developed a Stillinger-Weber type of TlBr interatomic potential. During this process, we have also addressed two problems of wider interests. First, the conventional Stillinger-Weber potential format is only applicable for tetrahedral structures (e.g., diamond-cubic, zinc-blende, or wurtzite). Here we have modified the analytical functions of the Stillinger-Weber potential so that it can now be used for other crystal structures. Second, past modifications of interatomic potentials cannot always be applied by a broad community because any new analytical functions of the potential would require corresponding changes in the molecular dynamics codes. Here we have developed a polymorphic potential model that simultaneously incorporates Stillinger-Weber, Tersoff, embedded-atom method, and any variations (i.e., modified functions) of these potentials. As a result, we have implemented this polymorphic model in MD code LAMMPS, and demonstrated that our TlBr potential enables stable MD simulations under external electric fields.
Elpasolite scintillators are a large family of halides which includes compounds reported to meet the NA22 program goals of <3% energy resolution at 662 keV1. This work investigated the potential to produce quality elpasolite compounds and alloys of useful sizes at reasonable cost, through systematic experimental and computational investigation of crystal structure and properties across the composition space. Discovery was accelerated by computational methods and models developed previously to efficiently identify cubic members of the elpasolite halides, and to evaluate stability of anion and cation exchange alloys.
An ideal 3He detector replacement for the near- to medium-term future will use materials that are easy to produce and well understood, while maintaining thermal neutron detection efficiency and gamma rejection close to the 3He standard. Toward this end, we investigated the use of standard alkali halide scintillators interfaced with 6Li and read out with photomultiplier tubes (PMTs). Thermal neutrons are captured on 6Li with high efficiency, emitting high-energy and triton (3H) reaction products. These particles deposit energy in the scintillator, providing a thermal neutron signal; discrimination against gamma interactions is possible via pulse shape discrimination (PSD), since heavy particles produce faster pulses in alkali halide crystals. We constructed and tested two classes of detectors based on this concept. In one case 6Li is used as a dopant in polycrystalline NaI; in the other case a thin Li foil is used as a conversion layer. In the configurations studied here, these systems are sensitive to both gamma and neutron radiation, with discrimination between the two and good energy resolution for gamma spectroscopy. We present results from our investigations, including measurements of the neutron efficiency and gamma rejection for the two detector types. We also show a comparison with Cs2LiYCl6:Ce (CLYC), which is emerging as the standard scintillator for simultaneous gamma and thermal neutron detection, and also allows PSD. We conclude that 6Li foil with CsI scintillating crystals has near-term promise as a thermal neutron detector in applications previously dominated by 3He detectors. The other approach, 6Li-doped alkali halides, has some potential, but require more work to understand material properties and improve fabrication processes.
This work was funded by the U.S. Department of Energy Office of Nonproliferation Research to develop elpasolite materials, with an emphasis on high-atomic-number rare-earth elpasolites for gamma-ray spectrometer applications. Low-cost, high-performance gamma-ray spectrometers are needed for detection of nuclear proliferation. Cubic materials, such as some members of the elpasolite family (A2BLnX6; Ln-lanthanide and X-halogen), hold promise due to their high light output, proportionality, and potential for scale-up. Using both computational and experimental studies, a systematic investigation of the compositionstructureproperty relationships of these high-atomic-number elpasolite halides was performed. The results reduce the barrier to commercialization of large single crystals or transparent ceramics, and will facilitate economical scale-up of elpasolites for high-sensitivity gamma-ray spectroscopy.
Ceramic based nanocomposites have recently demonstrated the ability to provide enhanced permittivity, increased dielectric breakdown strength, and reduced electromechanical strain making them potential materials systems for high energy density applications. A systematic characterization and optimization of barium titanate and PLZT based nanoparticle composites employing a glass or polymer matrix to yield a high energy density component will be presented. This work will present the systematic characterization and optimization of barium titanate and lead lanthanum zirconate titanate nanoparticle based ceramics. The nanoparticles have been synthesized using solution and pH-based synthesis processing routes and employed to fabricate polycrystalline ceramic and nanocomposite based components. The dielectric/ferroelectric properties of these various components have been gauged by impedance analysis and electromechanical response and will be discussed.
A2BLnX6 elpasolites (A, B: alkali; Ln: lanthanide; X: halogen), LaBr3 lanthanum bromide, and AX alkali halides are three classes of the ionic compound crystals being explored for {gamma}-ray detection applications. Elpasolites are attractive because they can be optimized from combinations of four different elements. One design goal is to create cubic crystals that have isotropic optical properties and can be grown into large crystals at lower costs. Unfortunately, many elpasolites do not have cubic crystals and the experimental trial-and-error approach to find the cubic elpasolites has been prolonged and inefficient. LaBr3 is attractive due to its established good scintillation properties. The problem is that this brittle material is not only prone to fracture during services, but also difficult to grow into large crystals resulting in high production cost. Unfortunately, it is not always clear how to strengthen LaBr3 due to the lack of understanding of its fracture mechanisms. The problem with alkali halides is that their properties decay rapidly over time especially under harsh environment. Here we describe our recent progress on the development of atomistic models that may begin to enable the prediction of crystal structures and the study of fracture mechanisms of multi-element compounds.
Attractive for numerous technological applications, ferroelectronic oxides constitute an important class of multifunctional compounds. Intense experimental efforts have been made recently in synthesizing, processing and understanding ferroelectric nanostructures. This work will present the systematic characterization and optimization of barium titanate and lead lanthanum zirconate titanate nanoparticle based ceramics. The nanoparticles have been synthesized using several solution and pH-based synthesis processing routes and employed to fabricate polycrystalline ceramic and nanocomposite based components. The dielectric and ferroelectric properties of these various components have been gauged by impedance analysis and electromechanical response and will be discussed.
Structural phase transformations between ferroelectric (FE), antiferroelectric (AFE), and paraelectric (FE) phases are frequently observed in the zirconia-rich phase region on the lead zirconate-titanate (PZT) phase diagram. Since the free energy difference among these phases is small, phase transformation can be easily induced by temperature, pressure and electric field. These induced transformation characteristics have been used for many practical applications. This study focuses on a hydrostatic pressure induced FE-to-AFE phase transformation in a tin modified PZT ceramic (PSZT). The relative phase stability between FE and AFE phases is determined by the dielectric permittivity measurement as a function of temperature from -60 C to 125 C. A pressure-temperature phase diagram for the PSZT system will be presented.
The development of more reliable scintillator materials can significantly advance the gamma-ray detection technology. Scintillator materials such as lanthanum halides (e.g., LaBr{sub 3}, CsBr{sub 3}), elpasolites (e.g., Cs{sub 2}LiLaBr{sub 6}, Cs{sub 2}NaLaBr{sub 6}, and Cs{sub 2}LiLaI{sub 6}), and alkali halides (e.g., CsI, NaI) are extremely brittle. The fracture of the materials is often a problem causing the failure of the devices. Lanthanum halides typically have a hexagonal crystal structure. These materials have highly anisotropic thermal and mechanical properties, and therefore they are likely to fracture under cyclic thermal and mechanical loading conditions. For example, fracture of lanthanum halides is known to occur in the field. Fracture during synthesis also complicates the growth of large lanthanum halide single crystals needed for sensitive radiation detection, and accounts for the high production cost of these materials. Elpasolites can have both cubic and non-cubic crystal structures depending on the constituent elements and composition of the compounds. This provides an opportunity to design cubic elpasolites with more isotropic properties and therefore improved mechanical performances. However, the design of an optimized cubic elpasolite crystal remains elusive because there is a tremendous number of possible elpasolites and the design criterion for cubic crystals is not clear. Alkali halides have cubic crystal structures. Consequently, large CsI and NaI crystals have been grown and used in devices. However, these materials suffer from an aging problem, i.e., the properties decay rapidly over time especially under harsh environment. Unfortunately, the fundamental mechanisms of this aging have not been understood and the path to improve the alkali halide-based scintillators is not developed. Clearly, improved scintillator materials can be achieved via strengthened/toughened lanthanum halides, optimized cubic elpasolites, or new alkali halide-based crystals that are more resistant to aging. Without a fundamental understanding of the atomic origins of the mechanical and the thermodynamic properties of materials, past experimental efforts to develop improved scintillator materials have been prolonged. Here we report our recent progress on the development of atomistic models that can be used to accelerate the discovery of new scintillator materials with improved properties. First, we have developed a novel embedded-ion method interatomic potential approach that analytically addresses the variable charge interactions between atoms in ionic compound material systems. Based on this potential, molecular dynamics simulations have been used to study the mechanical properties of LaBr3 including slip systems, dislocation core structures, and material strength. We have also developed an atomistic model that can already be used to predict crystal structures and to derive crystal stability rules for alkali halides. This model is under further development for prediction of crystal structures of elpasolites. These efforts will facilitate the design of better scintillator materials.
This late start RTBF project started the development of barium titanate (BTO)/glass nanocomposite capacitors for future and emerging energy storage applications. The long term goal of this work is to decrease the size, weight, and cost of ceramic capacitors while increasing their reliability. Ceramic-based nanocomposites have the potential to yield materials with enhanced permittivity, breakdown strength (BDS), and reduced strain, which can increase the energy density of capacitors and increase their shot life. Composites of BTO in glass will limit grain growth during device fabrication (preserving nanoparticle grain size and enhanced properties), resulting in devices with improved density, permittivity, BDS, and shot life. BTO will eliminate the issues associated with Pb toxicity and volatility as well as the variation in energy storage vs. temperature of PZT based devices. During the last six months of FY09 this work focused on developing syntheses for BTO nanoparticles and firing profiles for sintering BTO/glass composite capacitors.
Nanocrystalline and nanostructured materials offer unique microstructure-dependent properties that are superior to coarse-grained materials. These materials have been shown to have very high hardness, strength, and wear resistance. However, most current methods of producing nanostructured materials in weapons-relevant materials create powdered metal that must be consolidated into bulk form to be useful. Conventional consolidation methods are not appropriate due to the need to maintain the nanocrystalline structure. This research investigated new ways of creating nanocrystalline material, new methods of consolidating nanocrystalline material, and an analysis of these different methods of creation and consolidation to evaluate their applicability to mesoscale weapons applications where part features are often under 100 {micro}m wide and the material's microstructure must be very small to give homogeneous properties across the feature.