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At least 1,387 records · Page 77

An electrochemical cell for in operando studies of lithium/sodium batteries using a conventional x-ray powder diffractometer

An electrochemical cell has been designed for powder X-ray diffraction studies of lithium ion batteries (LIB) and sodium ion batteries (SIB) in operando with high time resolution using a conventional powder X-ray diffractometer. The cell allows for studies of both anode and cathode electrode materials in reflection mode. The cell design closely mimics that of standard battery testing coin cells and allows obtaining powder X-ray diffraction patterns under representative electrochemical conditions. In addition, the cell uses graphite as the X-ray window instead of beryllium, and it is easy to operate and maintain. Test examples on lithium insertion/extraction in two spinel-type LIB electrode materials (Li{sub 4}Ti{sub 5}O{sub 12} anode and LiMn{sub 2}O{sub 4} cathode) are presented as well as first results on sodium extraction from a layered SIB cathode material (Na{sub 0.84}Fe{sub 0.56}Mn{sub 0.44}O{sub 2})

36 MATERIALS SCIENCE↗

Down-selection of candidate alloys for further testing of advanced replacement materials for LWR core internals

Life extension of the existing nuclear reactors imposes irradiation of high fluences to structural materials, resulting in significant challenges to the traditional reactor materials such as type 304 and 316 stainless steels. Advanced alloys with superior radiation resistance will increase safety margins, design flexibility, and economics for not only the life extension of the existing fleet but also new builds with advanced reactor designs. The Electric Power Research Institute (EPRI) teamed up with Department of Energy (DOE) Light Water Reactor Sustainability Program to initiate the Advanced Radiation Resistant Materials (ARRM) program, aiming to identify and develop advanced alloys with superior degradation resistance in light water reactor (LWR)-relevant environments by 2024.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Energy harvesting from low frequency applications using piezoelectric materials

In an effort to eliminate the replacement of the batteries of electronic devices that are difficult or impractical to service once deployed, harvesting energy from mechanical vibrations or impacts using piezoelectric materials has been researched over the last several decades. However, a majority of these applications have very low input frequencies. This presents a challenge for the researchers to optimize the energy output of piezoelectric energy harvesters, due to the relatively high elastic moduli of piezoelectric materials used to date. This paper reviews the current state of research on piezoelectric energy harvesting devices for low frequency (0–100 Hz) applications and the methods that have been developed to improve the power outputs of the piezoelectric energy harvesters. Various key aspects that contribute to the overall performance of a piezoelectric energy harvester are discussed, including geometries of the piezoelectric element, types of piezoelectric material used, techniques employed to match the resonance frequency of the piezoelectric element to input frequency of the host structure, and electronic circuits specifically designed for energy harvesters.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thermal Desorption/GCMS Analysis of Astrobiologically Relevant Organic Materials

Several macromolecular organic materials, both biologically-derived (type II kerogen and humic acid) and abiotic in origin (Murchison insoluble organic material, cyanide polymer, and Titan tholin) were subjected to thermal desorption using a Chromatoprobe attachment on a Varian Saturn 2000 GCMS system. Each sample was heated sequentially at 100, 200, and 300 C to release volatile components. The evolved compounds were then separated on a Supelco EC-1 dimethylsilica GC column and detected by the Saturn 2000 ion trap mass spectrometer. The various types of macromolecular organic material subjected to thermal desorption produced distinctly different GCMS chromatograms at each temperature, containing fractions of both low and high chromatographic mobility. The relative amounts of detectable volatiles released at each temperature also differed, with type II kerogen and cyanide polymer containing the highest percentage of low-temperature components. In all the samples, the highest yield of released compounds occurred at 300 C. Only cyanide polymer evolved a homologous hydrocarbon series, suggesting that it is the only material among those examined that contains a truly polymeric structure. Pyrolysis/gas chromatography/mass spectrometry has been used extensively for analysis of terrestrial organic macromolecular materials, and was also part of the instrument package on the Viking landers. Thorough analysis by pyrolysis usually employs temperatures of 500 C or higher, which for in situ analyses can be problematic given spacecraft power and materials constraints. This study demonstrates that heating of organic materials of astrobiological relevance to temperatures as low as 200-300 C for short periods releases volatile components that can be analyzed by gas chromatography and mass spectrometry. Even in the absence of full pyrolysis, useful chemical information on samples can be obtained, and materials from different biological and abiological sources can be distinguished. The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

McDonald, Gene D.↗

Assembly of Colloidal Materials Using Bioadhesive Interactions

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Hammer, Daniel A.↗

In-situ resonant band engineering of solution-processed semiconductors generates high performance n-type thermoelectric nano-inks

Thermoelectric devices possess enormous potential to reshape the global energy landscape by converting waste heat into electricity, yet their commercial implementation has been limited by their high cost to output power ratio. No single “champion” thermoelectric material exists due to a broad range of material-dependent thermal and electrical property optimization challenges. While the advent of nanostructuring provided a general design paradigm for reducing material thermal conductivities, there exists no analogous strategy for homogeneous, precise doping of materials. Here, we demonstrate a nanoscale interface-engineering approach that harnesses the large chemically accessible surface areas of nanomaterials to yield massive, finely-controlled, and stable changes in the Seebeck coefficient, switching a poor nonconventional p- type thermoelectric material, tellurium, into a robust n -type material exhibiting stable properties over months of testing. These remodeled, n -type nanowires display extremely high power factors (~500 µW m -1 K -2 ) that are orders of magnitude higher than their bulk p -type counterparts.

42 ENGINEERING↗

Long-Term Thermal Aging Effect Evaluation for Grade 92 and 316L at The LWR Relevant Temperature

Life extension of the existing nuclear reactors imposes accumulated damages, such as higher fluences and longer periods of corrosion, to structural materials, which would result in significant challenges to the traditional reactor materials such as type 304 and 316 stainless steels. Advanced alloys with superior radiation resistance will increase safety margins, design flexibility, and economics for not only the life extension of the existing fleet but also new builds with advanced reactor designs. The Electric Power Research Institute (EPRI) initiated a collaboration with the Department of Energy (DOE) Light Water Reactor Sustainability (LWRS) Program on the Advanced Radiation Resistant Materials (ARRM) program, focused on developing and test degradation resistant alloys for light water reactor (LWR)- relevant environments. Based on a comprehensive microstructure and property screening, the ARRM program selected a total of five alloys (i.e., Grade 92, 310, 690, 718A, and 725), together with 316L and X-750 as references, for further investigations.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Applications of high thermal conductivity composites to electronics and spacecraft thermal design

Recently, high thermal conductivity graphite fiber-reinforced metal matrix composites (MMCs) have become available that can save weight over present methods of heat conduction. Another significant advantage is that these materials can be used without the plumbing and testing complexities that accompany the use of liquid heat pipes. A spinoff of this research was the development of other MMCs as electronic device heat sinks. These use particulates rather than fibers and are formulated to match the coefficient of thermal expansion of electronic substrates in order to alleviate thermally induced stresses. The development of both types of these materials as viable weight-saving substitutes for the traditional methods of thermal control for electronics packaging and also for spacecraft thermal control applications are the subjects of this report.

Sharp, G. Richard↗

Applications of high thermal conductivity composites to electronics and spacecraft thermal design

Recently, high thermal conductivity continuous graphite fiber reinforced metal matrix composites (MMC's) have become available that can save much weight over present methods of heat conduction. These materials have two or three times higher thermal conductivity in the fiber direction than the pure metals when compared on a thermal conductivity to weight basis. Use of these materials for heat conduction purposes can result in weight savings of from 50 to 70 percent over structural aluminum. Another significant advantage is that these materials can be used without the plumbing and testing complexities that accompany the use of liquid heat pipes. A spinoff of this research was the development of other MMC's as electronic device heat sinks. These use particulates rather than fibers and are formulated to match the coefficient of thermal expansion of electronic substrates in order to alleviate thermally induced stresses. The development of both types of these materials as viable weight saving substitutes for traditional methods of thermal control for electronics packaging and also for spacecraft thermal control applications are the subject of this report.

Sharp, G. Richard↗

A molten battery consisting of Li metal anode, AlCl3-LiCl cathode and solid electrolyte

High performance rechargeable batteries are crucially needed to address the demands of grid-scale stationary energy storage. High temperature battery systems, such as Na-S battery, Na-NiCl2 battery (ZEBRA battery) and liquid metal electrode (LME) battery, exhibit advantages like high power density and high cyclic stability, but also suffer from the high operating temperature. We recently invented new concept of molten lithium metal batteries, consisting of liquid lithium anodes, alloy (Sn, Bi, Pb) liquid cathodes and lithium ion conductor as solid electrolytes. Here we demonstrate a molten metal chloride battery that operates at a relatively low temperature of 210 °C. The battery has been designed to include molten (AlCl3-LiCl) cathode, solid electrolyte (garnet-type Li6.4La3Ta0.6Zr1.4O12 (LLZTO) ceramic tube) and molten lithium anode. The assembled AlCl3-LiCl||LLZTO||Li full cell has an average discharge voltage of 1.55 V and energy efficiency of 83% and has been successfully cycled for 100 cycles (800 h) without capacity fade. The theoretical specific energy of cell is 350 Wh/kg and the estimated cost is $11.6/kWh based on the weight of electrode materials. Considering the high performance, high safety, low operating temperature and low cost of raw materials, this novel type of molten-electrode battery system opens up new opportunities for stationary energy storage.

25 ENERGY STORAGE↗

Increased p-type conductivity in GaN{sub x}Sb{sub 1−x}, experimental and theoretical aspects

The large increase in the p-type conductivity observed when nitrogen is added to GaSb has been studied using positron annihilation spectroscopy and ab initio calculations. Doppler broadening measurements have been conducted on samples of GaN{sub x}Sb{sub 1−x} layers grown by molecular beam epitaxy, and the results have been compared with calculated first-principle results corresponding to different defect structures. From the calculated data, binding energies for nitrogen-related defects have also been estimated. Based on the results, the increase in residual hole concentration is explained by an increase in the fraction of negative acceptor-type defects in the material. As the band gap decreases with increasing N concentration, the ionization levels of the defects move closer to the valence band. Ga vacancy-type defects are found to act as positron trapping defects in the material, and the ratio of Ga vacancy-type defects to Ga antisites is found to be higher than that of the p-type bulk GaSb substrate. Beside Ga vacancies, the calculated results imply that complexes of a Ga vacancy and nitrogen could be present in the material.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The application of orthogonal photolithography to micro-scale organic field effect transistors and complementary inverters on flexible substrate

Micro-scale pentacene organic field effect transistors (OFETs) were fabricated on a flexible poly(ethylene terephthalate) (PET) substrate. By applying a highly fluorinated developing solvents and its compatible photoresist materials, it has become possible to make the micro-scale patterning for organic devices using standard photolithography without damaging the underlying polymer layers. The flexible pentacene OFETs with 3 μm-sized channel length exhibited stable electrical characteristics under bent configurations and under a large number of repetitive bending cycles. Furthermore, we demonstrated micro-scale organic complementary inverters on a flexible PET substrate using p-type pentacene and n-type copper hexadecafluorophthalocyanine materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Technical Performance of Refractory Liners for Molten Chloride Salt Thermal Energy Storage Systems

A chloride-based molten-salt system that uses a ternary blend of MgCl2/KCl/NaCl is investigated to provide higher temperature thermal energy storage capability. Despite higher thermal stability, molten chlorides present several unique challenges, including the design of internal refractory-ceramic liners to prevent the corrosion and thermal stress of alloy tank shells. This work discusses issues and potential solutions related to containment of molten chloride salt, specifically the optimization of the refractory material at the molten salt interface (hot face). The down-selected hot face candidate limits permeation of salt through the material and forms a highly stable secondary surface phase in equilibrium with the molten salt. A mortar is created using the corrosion resistant hot face brick. Brick and mortar composite are subjected to mechanical stress/strain analysis, in order to calculate composite material properties and better inform thermomechanical models. The U.S. Department of Energy Generation 3 (DOE Gen3) program seeks to develop higher efficiency CSP plants that can provide cost-competitive, flexible power in the U.S. electric grid. The proposed Gen3 Liquid Pathway CSP plant closely resembles the configuration of current nitrate salt power towers with two-tank storage (Gen2). The differences between Gen2 and Gen3 include the types of compatible materials used in salt storage tank construction. Stainless steel loses strength at Gen3 temperatures, and although nickel superalloys would be capable of withstanding sustained high temperatures, these materials are prohibitively expensive at scale. Uninsulated tank shells also pose a significant risk as common steels are highly susceptible to chemical attack from molten chloride salt. To address these concerns, refractory-ceramic based containment materials are proposed to line the inside of the hot and cold storage tanks. In doing so, stainless or carbon steel shells may be used in construction depending on the level of insulation provided. The composition of the internal liner requires careful consideration to maximize the efficacy of multiple parameters including corrosion resistance, strength at operating temperature, durability, and cost. This is particularly true for the material at the interface with the salt, known as the "hot face", which is responsible for protecting the insulating layers between the tank shell and the hot face brick layer. The molten salt in this system is superheated over 300 °C above its freeze temperature. Therefore, unlike other industrial processes which use refractory-lined vessels, it is not expected that a freeze plane will develop in the hot face. Therefore, the hot face must be designed to withstand chemical corrosion and inhibit permeation of molten salt into the insulating layers. A down selection was performed to identify a hot face candidate best equipped to maintain thermal, mechanical, and chemical integrity when exposed to molten salt over extended periods of time. Long-duration chemical capability experiments were conducted with the down selected hot face refractory fully immersed in molten chloride salt for up to 3000 hours. The average salt penetration does not exceed 100 microns. When extrapolated to 20 and 30 years of continuous exposure, the expected salt penetration depth is approximately 2.0 mm and 2.9 mm, respectively. A magnesium-rich secondary phases develops at the salt/refractory interface. X-ray diffraction identifies the material as forsterite (Mg2SiO4), which is reported to form synthetically in molten chloride salt solutions. These results suggest the selected hot face will adequately inhibit salt permeation. While there is optimism that the hot face brick will inhibit salt permeation, mortar joints are typically the weakest point of a refractory brick liner. From a thermochemical perspective, differing thermal expansion coefficients may result in the mortar and brick to grow independent of each other, creating gaps through which molten salt can penetrate. To address this issue, NREL has developed an in-house mortar composed of the down selected hot face brick that has been shown to be compatible with the salt. Compressive stress/strain analyses have been performed on the brick/ mortar composites to generate stress/strain curves. Modulus of elasticity and Poisson's ratio of the composite may be calculated from the stress/strain curves, in order to provide more representative data to finite element mechanical models for accurate approximation of stress on the tank shell and the amount of thermal expansion expected within the tank liner.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Enhanced Uranium Ore Concentrate Analysis by Handheld Raman Sensor: FY15 Status Report

High-purity uranium ore concentrates (UOC) represent a potential proliferation concern. A cost-effective, “point and shoot” in-field analysis capability to identify ore types, phases of materials present, and impurities, as well as estimate the overall purity would be prudent. Handheld, Raman-based sensor systems are capable of identifying chemical properties of liquid and solid materials. While handheld Raman systems have been extensively applied to many other applications, they have not been broadly studied for application to UOC, nor have they been optimized for this class of chemical compounds. PNNL was tasked in Fiscal Year 2015 by the Office of International Safeguards (NA-241) to explore the use of Raman for UOC analysis and characterization. This report summarizes the activities in FY15 related to this project. The following tasks were included: creation of an expanded library of Raman spectra of a UOC sample set, creation of optimal chemometric analysis methods to classify UOC samples by their type and level of impurities, and exploration of the various Raman wavelengths to identify the ideal instrument settings for UOC sample interrogation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Nanoscale semiconductor hybrids: fundamental physics and advanced devices

Key summary: Low dimensional hybrids: more flexibility and better controllability of materials properties. Type-II Antimonide-based superlattice: system of interacting quantum wells, for infrared detection and imaging. Hetero-designs in core/multi-shell nanowires: promising candidate for high performance electronic and sensing applications. An interdisciplinary research plan could trigger interest and collaboration within RIT.

36 MATERIALS SCIENCE↗

Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This sample will be used to assess the linearity of the magnetic field gradient and to ensure authentic image reconstruction. A second major task was to secure the computer capability to enable image reconstruction from projection data generated by the magnetic field gradients. To this end, commercially available and public domain software packages which perform inverse Fourier Transform and convoluted (filtered) back projection functions are being integrated into the existing EPR data processing system.

Suleman, Naushadalli K.↗

ZrCoBi based half Heuslers with high thermoelectric conversion efficiency

A ZrCoBi-based p-type half-Heusler material can have a formula: ZrCoBi$_{1-x-y}$Sn$_{x}$Sb$_{y}$, where x can vary between 0.01 and 0.25, and y can vary between 0 and 0.2. An average dimensionless figure-of-merit (ZT) for the material can be greater than or equal to about 0.80 as calculated by an integration method for temperatures between 300 and 973 K. A ZrCoBi-based n-type half-Heusler material can have a formula: ZrCo$_{1-x}$Ni$_{x}$Bi$_{1-y}$Sb$_{y}$, where x can vary between 0.01 and 0.25, and y can vary between 0 and 0.3. The material has an average dimensionless figure-of-merit (ZT) is greater than or equal to about 0.65 as calculated by an integration method for temperatures between 300 and 973 K.

Ren, Zhifeng↗

The influence of buoyant forces and volume fraction of particles on the particle pushing/entrapment transition during directional solidification of Al/SiC and Al/graphite composites

Directional solidification experiments in a Bridgman-type furnace were used to study particle behavior at the liquid/solid interface in aluminum metal matrix composites. Graphite or silicon-carbide particles were first dispersed in aluminum-base alloys via a mechanically stirred vortex. Then, 100-mm-diameter and 120-mm-long samples were cast in steel dies and used for directional solidification. The processing variables controlled were the direction and velocity of solidification and the temperature gradient at the interface. The material variables monitored were the interface energy, the liquid/particle density difference, the particle/liquid thermal conductivity ratio, and the volume fraction of particles. These properties were changed by selecting combinations of particles (graphite or silicon carbide) and alloys (Al-Cu, Al-Mg, Al-Ni). A model which consideres process thermodynamics, process kinetics (including the role of buoyant forces), and thermophysical properties was developed. Based on solidification direction and velocity, and on materials properties, four types of behavior were predicted. Sessile drop experiments were also used to determine some of the interface energies required in calculation with the proposed model. Experimental results compared favorably with model predictions.

Stefanescu, Doru M.↗