Metal hydride-based thermal energy storage systems

DOEpatents

Vajo, John J.; Fang, Zhigang

2017-10-03

The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

Development of a component design tool for metal hydride heat pumps

NASA Astrophysics Data System (ADS)

Waters, Essene L.

Given current demands for more efficient and environmentally friendly energy sources, hydrogen based energy systems are an increasingly popular field of interest. Within the field, metal hydrides have become a prominent focus of research due to their large hydrogen storage capacity and relative system simplicity and safety. Metal hydride heat pumps constitute one such application, in which heat and hydrogen are transferred to and from metal hydrides. While a significant amount of work has been done to study such systems, the scope of materials selection has been quite limited. Typical studies compare only a few metal hydride materials and provide limited justification for the choice of those few. In this work, a metal hydride component design tool has been developed to enable the targeted down-selection of an extensive database of metal hydrides to identify the most promising materials for use in metal hydride thermal systems. The material database contains over 300 metal hydrides with various physical and thermodynamic properties included for each material. Sub-models for equilibrium pressure, thermophysical data, and default properties are used to predict the behavior of each material within the given system. For a given thermal system, this tool can be used to identify optimal materials out of over 100,000 possible hydride combinations. The selection tool described herein has been applied to a stationary combined heat and power system containing a high-temperature proton exchange membrane (PEM) fuel cell, a hot water tank, and two metal hydride beds used as a heat pump. A variety of factors can be used to select materials including efficiency, maximum and minimum system pressures, pressure difference, coefficient of performance (COP), and COP sensitivity. The targeted down-selection of metal hydrides for this system focuses on the system's COP for each potential pair. The values of COP and COP sensitivity have been used to identify pairs of highest interest for

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the

AIR PASSIVATION OF METAL HYDRIDE BEDS FOR WASTE DISPOSAL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J; R. H. Hsu, R

2007-07-02

Metal hydride beds offer compact, safe storage of tritium. After metal hydride beds have reached the end of their useful life, the beds will replaced with new beds and the old beds prepared for disposal. One acceptance criteria for hydride bed waste disposal is that the material inside the bed not be pyrophoric. To determine the pyrophoric nature of spent metal hydride beds, controlled air ingress tests were performed. A simple gas handling manifold fitted with pressure transducers and a calibrated volume were used to introduce controlled quantities of air into a metal hydride bed and the bed temperature risemore » monitored for reactivity with the air. A desorbed, 4.4 kg titanium prototype hydride storage vessel (HSV) produced a 4.4 C internal temperature rise upon the first air exposure cycle and a 0.1 C temperature rise upon a second air exposure. A total of 346 scc air was consumed by the bed (0.08 scc per gram Ti). A desorbed, 9.66 kg LaNi{sub 4.25}Al{sub 0.75} prototype storage bed experienced larger temperature rises over successive cycles of air ingress and evacuation. The cycles were performed over a period of days with the bed effectively passivated after the 12th cycle. Nine to ten STP-L of air reacted with the bed producing both oxidized metal and water.« less

A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof

Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zidan, Ragaiy; Hardy, B. J.; Corgnale, C.

2016-01-31

The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce verymore » high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.« less

Hydrogen and dihydrogen bonding of transition metal hydrides

NASA Astrophysics Data System (ADS)

Jacobsen, Heiko

2008-04-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

Influence of uranium hydride oxidation on uranium metal behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, N.; Hambley, D.; Clarke, S.A.

2013-07-01

This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, ifmore » sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)« less

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.

Method of making alkali metal hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek

A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

Technical and economic aspects of hydrogen storage in metal hydrides

NASA Technical Reports Server (NTRS)

Schmitt, R.

1981-01-01

The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

Hydridable material for the negative electrode in a nickel-metal hydride storage battery

DOEpatents

Knosp, Bernard; Bouet, Jacques; Jordy, Christian; Mimoun, Michel; Gicquel, Daniel

1997-01-01

A monophase hydridable material for the negative electrode of a nickel-metal hydride storage battery with a "Lave's phase" structure of hexagonal C14 type (MgZn.sub.2) has the general formula: Zr.sub.1-x Ti.sub.x Ni.sub.a Mn.sub.b Al.sub.c Co.sub.d V.sub.e where ##EQU1##

Structural Characterization of Metal Hydrides for Energy Applications

NASA Astrophysics Data System (ADS)

George, Lyci

Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or

A nickel metal hydride battery for electric vehicles

NASA Astrophysics Data System (ADS)

Ovshinsky, S. R.; Fetcenko, M. A.; Ross, J.

1993-04-01

An efficient battery is the key technological element to the development of practical electric vehicles. The science and technology of a nickel metal hydride battery, which stores hydrogen in the solid hydride phase and has high energy density, high power, long life, tolerance to abuse, a wide range of operating temperature, quick-charge capability, and totally sealed maintenance-free operation, is described. A broad range of multi-element metal hydride materials that use structural and compositional disorder on several scales of length has been engineered for use as the negative electrode in this battery. The battery operates at ambient temperature, is made of nontoxic materials, and is recyclable. Demonstration of the manufacturing technology has been achieved.

Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.

2012-02-01

In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heatmore » released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and

DEVELOPMENT OF A FABRICATION PROCESS FOR SOL-GEL/METAL HYDRIDE COMPOSITE GRANULES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, E; Eric Frickey, E; Leung Heung, L

An external gelation process was developed to produce spherical granules that contain metal hydride particles in a sol-gel matrix. Dimensionally stable granules containing metal hydrides are needed for applications such as hydrogen separation and hydrogen purification that require columns containing metal hydrides. Gases must readily flow through the metal hydride beds in the columns. Metal hydrides reversibly absorb and desorb hydrogen and hydrogen isotopes. This is accompanied by significant volume changes that cause the metal hydride to break apart or decrepitate. Repeated cycling results in very fine metal hydride particles that are difficult to handle and contain. Fine particles tendmore » to settle and pack making it more difficult to flow gases through a metal hydride bed. Furthermore, the metal hydrides can exert a significant force on the containment vessel as they expand. These problems associated with metal hydrides can be eliminated with the granulation process described in this report. Small agglomerates of metal hydride particles and abietic acid (a pore former) were produced and dispersed in a colloidal silica/water suspension to form the feed slurry. Fumed silica was added to increase the viscosity of the feed slurry which helped to keep the agglomerates in suspension. Drops of the feed slurry were injected into a 27-foot tall column of hot ({approx}70 C), medium viscosity ({approx}3000 centistokes) silicone oil. Water was slowly evaporated from the drops as they settled. The drops gelled and eventually solidified to form spherical granules. This process is referred to as external gelation. Testing was completed to optimize the design of the column, the feed system, the feed slurry composition, and the operating parameters of the column. The critical process parameters can be controlled resulting in a reproducible fabrication technique. The residual silicone oil on the surface of the granules was removed by washing in mineral spirits. The granules

Storing energy in metal hydrides - A review of the physical metallurgy

NASA Astrophysics Data System (ADS)

Ivey, D. G.; Northwood, D. O.

1983-02-01

The properties of metal hydrides, which are significant in terms of their potential as a hydrogen storage medium, are discussed. Attention is given to bonding and electronic factors of metal hydrides, which, when combined with hydrogen, form saline, ionic, metallic, and covalent bonds, with the resultant materials being either solid, liquid, or gaseous. Metallic bonds are the most promising for hydrogen storage, and involve most of the elements of groups IIIA-VIIIA in the periodic table. An analysis of the thermodynamics and kinetics of metal hydrides is presented, noting the effects of alloy composition, crystal structure, and contaminants on the effectiveness of the materials as hydrides. Hysteresis has been found to occur when the transition pressure in a pressure-composition-temperature curve is higher for absorption than for desorption, although the actual causes for hysteresis are not understood. The AB group of intermetallics has been determined to store hydrogen at the lowest cost. Examples from tests using the AB compounds are outlined, and attempts to rectify storage requirement deficiencies by adjusting the alloy compositions are described.

Metal Hydride Compression

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Terry A.; Bowman, Robert; Smith, Barton

Conventional hydrogen compressors often contribute over half of the cost of hydrogen stations, have poor reliability, and have insufficient flow rates for a mature FCEV market. Fatigue associated with their moving parts including cracking of diaphragms and failure of seal leads to failure in conventional compressors, which is exacerbated by the repeated starts and stops expected at fueling stations. Furthermore, the conventional lubrication of these compressors with oil is generally unacceptable at fueling stations due to potential fuel contamination. Metal hydride (MH) technology offers a very good alternative to both conventional (mechanical) and newly developed (electrochemical, ionic liquid pistons) methodsmore » of hydrogen compression. Advantages of MH compression include simplicity in design and operation, absence of moving parts, compactness, safety and reliability, and the possibility to utilize waste industrial heat to power the compressor. Beyond conventional H2 supplies of pipelines or tanker trucks, another attractive scenario is the on-site generating, pressuring and delivering pure H 2 at pressure (≥ 875 bar) for refueling vehicles at electrolysis, wind, or solar generating production facilities in distributed locations that are too remote or widely distributed for cost effective bulk transport. MH hydrogen compression utilizes a reversible heat-driven interaction of a hydride-forming metal alloy with hydrogen gas to form the MH phase and is a promising process for hydrogen energy applications [1,2]. To deliver hydrogen continuously, each stage of the compressor must consist of multiple MH beds with synchronized hydrogenation & dehydrogenation cycles. Multistage pressurization allows achievement of greater compression ratios using reduced temperature swings compared to single stage compressors. The objectives of this project are to investigate and demonstrate on a laboratory scale a two-stage MH hydrogen (H 2) gas compressor with a feed pressure

Metal hydride hydrogen compression: Recent advances and future prospects

DOE PAGES

Bowman, Jr., Robert C.; Yartys, Volodymyr A.; Lototskyy, Mykhaylo V.; ...

2016-03-17

Metal hydride (MH) thermal sorption compression is one of the more important applications of the metal hydrides. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units are analyzed. The paper includes also a theoretical modeling of a two-stage compressor aimed at both describing the performance of the experimentally studied systems, but, also, on their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS andmore » the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the metal hydride compression in the overall development of the hydrogen driven energy systems. Lastly, the work is based on the analysis of the development of the technology in Europe, USA and South Africa.« less

Fatigue stress concentration and notch sensitivity in nanocrystalline metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furnish, Timothy A.; Boyce, Brad L.; Sharon, John A.

Recent studies have shown the potential for nanocrystalline metals to possess excellent fatigue resistance compared to their coarse-grained counterparts. Although the mechanical properties of nanocrystalline metals are believed to be particularly susceptible to material defects, a systematic study of the effects of geometric discontinuities on their fatigue performance has not yet been performed. In the present work, nanocrystalline Ni–40 wt%Fe containing both intrinsic and extrinsic defects were tested in tension–tension fatigue. The defects were found to dramatically reduce the fatigue resistance, which was attributed to the relatively high notch sensitivity in the nanocrystalline material. Microstructural analysis within the crack-initiation zonesmore » underneath the defects revealed cyclically-induced abnormal grain growth (AGG) as a predominant deformation and crack initiation mechanism during high-cycle fatigue. Furthermore, the onset of AGG and the ensuing fracture is likely accelerated by the stress concentrations, resulting in the reduced fatigue resistance compared to the relatively defect-free counterparts.« less

Fatigue stress concentration and notch sensitivity in nanocrystalline metals

DOE PAGES

Furnish, Timothy A.; Boyce, Brad L.; Sharon, John A.; ...

2016-03-11

Recent studies have shown the potential for nanocrystalline metals to possess excellent fatigue resistance compared to their coarse-grained counterparts. Although the mechanical properties of nanocrystalline metals are believed to be particularly susceptible to material defects, a systematic study of the effects of geometric discontinuities on their fatigue performance has not yet been performed. In the present work, nanocrystalline Ni–40 wt%Fe containing both intrinsic and extrinsic defects were tested in tension–tension fatigue. The defects were found to dramatically reduce the fatigue resistance, which was attributed to the relatively high notch sensitivity in the nanocrystalline material. Microstructural analysis within the crack-initiation zonesmore » underneath the defects revealed cyclically-induced abnormal grain growth (AGG) as a predominant deformation and crack initiation mechanism during high-cycle fatigue. Furthermore, the onset of AGG and the ensuing fracture is likely accelerated by the stress concentrations, resulting in the reduced fatigue resistance compared to the relatively defect-free counterparts.« less

Production of nanocrystalline metal powders via combustion reaction synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frye, John G.; Weil, Kenneth Scott; Lavender, Curt A.

Nanocrystalline metal powders comprising tungsten, molybdenum, rhenium and/or niobium can be synthesized using a combustion reaction. Methods for synthesizing the nanocrystalline metal powders are characterized by forming a combustion synthesis solution by dissolving in water an oxidizer, a fuel, and a base-soluble, ammonium precursor of tungsten, molybdenum, rhenium, or niobium in amounts that yield a stoichiometric burn when combusted. The combustion synthesis solution is then heated to a temperature sufficient to substantially remove water and to initiate a self-sustaining combustion reaction. The resulting powder can be subsequently reduced to metal form by heating in a reducing gas environment.

Hydriding process

DOEpatents

Raymond, J.W.; Taketani, H.

1973-12-01

BS>A method is described for hydriding a body of a Group IV-B metal, preferably zirconium, to produce a crack-free metal-hydride bedy of high hydrogen content by cooling the body at the beta to beta + delta boundary, without further addition of hydrogen, to precipitate a fine-grained delta-phase metal hydride in the beta + delta phase region and then resuming the hydriding, preferably preceded by a reheating step. (Official Gazette)

Investigation of Lithium Metal Hydride Materials for Mitigation of Deep Space Radiation

NASA Technical Reports Server (NTRS)

Rojdev, Kristina; Atwell, William

2016-01-01

Radiation exposure to crew, electronics, and non-metallic materials is one of many concerns with long-term, deep space travel. Mitigating this exposure is approached via a multi-faceted methodology focusing on multi-functional materials, vehicle configuration, and operational or mission constraints. In this set of research, we are focusing on new multi-functional materials that may have advantages over traditional shielding materials, such as polyethylene. Metal hydride materials are of particular interest for deep space radiation shielding due to their ability to store hydrogen, a low-Z material known to be an excellent radiation mitigator and a potential fuel source. We have previously investigated 41 different metal hydrides for their radiation mitigation potential. Of these metal hydrides, we found a set of lithium hydrides to be of particular interest due to their excellent shielding of galactic cosmic radiation. Given these results, we will continue our investigation of lithium hydrides by expanding our data set to include dose equivalent and to further understand why these materials outperformed polyethylene in a heavy ion environment. For this study, we used HZETRN 2010, a one-dimensional transport code developed by NASA Langley Research Center, to simulate radiation transport through the lithium hydrides. We focused on the 1977 solar minimum Galactic Cosmic Radiation environment and thicknesses of 1, 5, 10, 20, 30, 50, and 100 g/cm2 to stay consistent with our previous studies. The details of this work and the subsequent results will be discussed in this paper.

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, Jeffrey A.; Rittner, Mindy N.; Youngdahl, Carl J.; Weertman, Julia R.

1998-01-01

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound.

The development of nickel-metal hydride technology for use in aerospace applications

NASA Technical Reports Server (NTRS)

Rampel, Guy; Johnson, Herschel; Dell, Dan; Wu, Tony; Puglisi, Vince

1992-01-01

The nickel metal hydride technology for battery application is relatively immature even though this technology was made widely known by Philips' scientists as long ago as 1970. Recently, because of the international environmental regulatory pressures being placed on cadmium in the workplace and in disposal practices, battery companies have initiated extensive development programs to make this technology a viable commercial operation. These hydrides do not pose a toxilogical threat as does cadmium. Also, they provide a higher energy density and specific energy when compared to the other nickel based battery technologies. For these reasons, the nickel metal hydride electrochemisty is being evaluated as the next power source for varied applications such as laptop computers, cellular telephones, electric vehicles, and satellites. A parallel development effort is under way to look at aerospace applications for nickel metal hydride cells. This effort is focused on life testing of small wound cells of the commercial type to validate design options and development of prismatic design cells for aerospace applications.

Nanocrystalline ceramic materials

DOEpatents

Siegel, Richard W.; Nieman, G. William; Weertman, Julia R.

1994-01-01

A method for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material.

Nanocrystalline ceramic materials

DOEpatents

Siegel, R.W.; Nieman, G.W.; Weertman, J.R.

1994-06-14

A method is disclosed for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material. 19 figs.

CO2 hydrogenation on a metal hydride surface.

PubMed

Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, J.A.; Rittner, M.N.; Youngdahl, C.J.; Weertman, J.R.

1998-03-17

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound. 6 figs.

Hydrogen Storage in Metal Hydrides

DTIC Science & Technology

1990-08-01

TitlePage 1. Properties of Reticulated Carbon Foam 26 2. Hydrogen Storage Capacity of Various Metal Hydrides 27 iv INTRODUCTION This is the final technical...pores, and results in coating of only the surface. The substrate for the fabrication of the magnesium foam was a reticulated carbon foam. This...material is an open-pore foam composed solely of vitreous carbon . It has an exceptionally high void volume (97%) and a high surface area, combined with self

(abstract) Studies on AB(sub 5) Metal Hydride Alloys with Sn Additives

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Surampudi, S.; Stefano, S. Di; Halpert, G.; Witham, C.; Fultz, B.

1994-01-01

The use of metal hydrides as negative electrodes in alkaline rechargeable cells is becoming increasingly popular, due to several advantages offered by the metal hydrides over conventional anode materials (such as Zn, Cd) in terms of specific energy environmental cycle life and compatibility. Besides, the similarities in the cell voltage pressure characteristics, and charge control methods of the Ni-MH cells to the commonly used Ni-Cd point to a projected take over of 25% of the Ni-Cd market for consumer electronics by the Ni-MH cells in the next couple of years. Two classes of metal hydrides alloys based on rare earth metals (AB(sub 5)) and titanium (AB(sub 2)) are being currently developed at various laboratories. AB(sub 2) alloys exhibit higher specific energy than the AB(sub 5) alloys but the state of the art commercial Ni-MH cells are predominately manufactured using AB(sub 5) alloys.

Thin-film metal hydrides.

PubMed

Remhof, Arndt; Borgschulte, Andreas

2008-12-01

The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

PubMed

Humphries, T D; Sheppard, D A; Buckley, C E

2015-06-30

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

Application of ASTAR(TM)/Precession Electron Diffraction Technique to Quantitatively Study Defects in Nanocrystalline Metallic Materials

NASA Astrophysics Data System (ADS)

Ghamarian, Iman

Nanocrystalline metallic materials have the potential to exhibit outstanding performance which leads to their usage in challenging applications such as coatings and biomedical implant devices. To optimize the performance of nanocrystalline metallic materials according to the desired applications, it is important to have a decent understanding of the structure, processing and properties of these materials. Various efforts have been made to correlate microstructure and properties of nanocrystalline metallic materials. Based on these research activities, it is noticed that microstructure and defects (e.g., dislocations and grain boundaries) play a key role in the behavior of these materials. Therefore, it is of great importance to establish methods to quantitatively study microstructures, defects and their interactions in nanocrystalline metallic materials. Since the mechanisms controlling the properties of nanocrystalline metallic materials occur at a very small length scale, it is fairly difficult to study them. Unfortunately, most of the characterization techniques used to explore these materials do not have the high enough spatial resolution required for the characterization of these materials. For instance, by applying complex profile-fitting algorithms to X-ray diffraction patterns, it is possible to get an estimation of the average grain size and the average dislocation density within a relatively large area. However, these average values are not enough for developing meticulous phenomenological models which are able to correlate microstructure and properties of nanocrystalline metallic materials. As another example, electron backscatter diffraction technique also cannot be used widely in the characterization of these materials due to problems such as relative poor spatial resolution (which is 90 nm) and the degradation of Kikuchi diffraction patterns in severely deformed nano-size grain metallic materials. In this study, ASTAR(TM)/precession electron

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

PubMed Central

Ley, Morten B.; Meggouh, Mariem; Moury, Romain; Peinecke, Kateryna; Felderhoff, Michael

2015-01-01

This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM) fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability. PMID:28793541

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

2017-06-20

A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

PubMed Central

Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

2017-01-01

Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries

PubMed Central

Oumellal, Yassine; Bonnet, Jean-Pierre

2015-01-01

Summary The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0) and the lowest electrode polarization (<0.2 V) for conversion materials. Conversion process reaction mechanisms with lithium are subsequently detailed for MgH2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to

High temperature metal hydrides as heat storage materials for solar and related applications.

PubMed

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 degrees C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

PubMed Central

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described. PMID:19333448

Stacking fault energies and slip in nanocrystalline metals.

PubMed

Van Swygenhoven, H; Derlet, P M; Frøseth, A G

2004-06-01

The search for deformation mechanisms in nanocrystalline metals has profited from the use of molecular dynamics calculations. These simulations have revealed two possible mechanisms; grain boundary accommodation, and intragranular slip involving dislocation emission and absorption at grain boundaries. But the precise nature of the slip mechanism is the subject of considerable debate, and the limitations of the simulation technique need to be taken into consideration. Here we show, using molecular dynamics simulations, that the nature of slip in nanocrystalline metals cannot be described in terms of the absolute value of the stacking fault energy-a correct interpretation requires the generalized stacking fault energy curve, involving both stable and unstable stacking fault energies. The molecular dynamics technique does not at present allow for the determination of rate-limiting processes, so the use of our calculations in the interpretation of experiments has to be undertaken with care.

Theoretical study of hydrogen storage in metal hydrides.

PubMed

Oliveira, Alyson C M; Pavão, A C

2018-05-04

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

2014-03-25

A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

Effect of delivery condition on desorption rate of ZrCo metal hydride bed for fusion fuel cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, H.G.; Yun, S.H.; Chung, D.

2015-03-15

For the safety of fusion fuel cycle, hydrogen isotope gases including tritium are stored as metal hydride form. To satisfy fueling requirement of fusion machine, rapid delivery from metal hydride bed is one of major factors for the development of tritium storage and delivery system. Desorption from metal hydride depends on the operation scenario by pressure and temperature control of the bed. The effect of operation scenario and pump performance on desorption rate of metal hydride bed was experimentally investigated using ZrCo bed. The results showed that the condition of pre-heating scenario before actual delivery of gas affected the deliverymore » performance. Different pumps were connected to desorption line from bed and the effect of pump capacity on desorption rate were also found to be significant. (authors)« less

Hydrogen storage properties of nano-structural carbon and metal hydrides composites

NASA Astrophysics Data System (ADS)

Miyaoka, Hiroki; Ichikawa, Takayuki; Isobe, Shigehito; Fujii, Hironobu

2006-08-01

Thermodynamic and structural properties of some ball-milled mixtures composed of the hydrogenated nanostructural carbon (C nanoH x) and metal hydride (MH; M=Li, Na, Mg and Ca) were examined from thermal desoroption mass spectroscopy and powder X-ray diffraction, respectively. The results showed that the hydrogen desorption temperatures are significantly lowered from those of each hydride (C nanoH x, MH) in the composites. This indicates that a new type of interaction exists between C nanoH x and MH, which destabilizes C-H and/or M-H bonding as well. Therefore, the above Metal-C-H system would be recognized as a new family of hydrogen storage materials.

Metal hydrides as negative electrode materials for Ni- MH batteries

NASA Astrophysics Data System (ADS)

Yartys, V.; Noreus, D.; Latroche, M.

2016-01-01

Structural, thermodynamical and electrochemical properties of metallic hydrides belonging to the pseudo-binary family A-Mg-Ni ( A: rare earths) are reviewed and compared. Technology aspects of bipolar cells are also discussed.

The Development of a Compact Refrigeration System using Metal Hydrides

NASA Astrophysics Data System (ADS)

Bae, Sang-Chul; Ogawa, Masahito; Katsuta, Masafumi

The MH refrigeration systems are regarded as important and compact ones for solving energy and environmental issues. Our purposes are to develop the compact refrigeration system for the vending machine and the show case using MH, and to attain a refrigeration temperature of 243K by using a heat source of 403∼423K. The kinetics of MH hydriding and dehydriding reactions is of importance relative to their practical use as a refrigerator system. The kinetics of the reaction between hydrogen and MHHigh (Ti0.18Zr0.84Cr1.0FeO.7Mn0.3CuO.057)has been followed in this paper. A relatively rapid absorption of hydrogen takes place for values of relative composition to about 0.3∼0.4. It is evident that a hydrogen diffusion plays a minor role during this stage, as that part of the metal not covered by hydride is always in contact with hydrogen. The direct chemical reaction between the hydrogen and the exposed metal surface is therefore postulated as the rate-controlling process. The rate of the reaction then decreases, and for values of relative composition above about 0.8, the reaction becomes slow. After the metal particles have been completely covered by a hydride layer, the transport of materials through the layer by diffusion becomes rate controlling process

An all-solid-state metal hydride - Sulfur lithium-ion battery

NASA Astrophysics Data System (ADS)

López-Aranguren, Pedro; Berti, Nicola; Dao, Anh Ha; Zhang, Junxian; Cuevas, Fermín; Latroche, Michel; Jordy, Christian

2017-07-01

A metal hydride is used for the first time as anode in a complete all-solid-state battery with sulfur as cathode and LiBH4 as solid electrolyte. The hydride is a nanocomposite made of MgH2 and TiH2 counterparts. The battery exhibits a high reversible capacity of 910 mAh g-1 with discharge plateaus at 1.8 V and 1.4 V. Moreover, the capacity remains to 85% of the initial value over the 25 first charge/discharge cycles.

Ni/metal hydride secondary element

DOEpatents

Bauerlein, Peter

2005-04-19

A Ni/metal hydride secondary element having a positive nickel hydroxide electrode, a negative electrode having a hydrogen storage alloy, and an alkaline electrolyte, the positive electrode, provided with a three-dimensional metallic conductive structure, also contains an aluminum compound which is soluble in the electrolyte, in addition to nickel hydroxide and cobalt oxide. The aluminum compound is aluminum hydroxide and/or aluminum oxide, and the mass of the aluminum compound which is present in the positive bulk material mixture is 0.1 to 2% by weight relative to the mass of the nickel hydroxide which is present. In combination with aluminum hydroxide or aluminum oxide, the positive electrode further contains lanthanoid oxidic compounds Y.sub.2 O.sub.3, La.sub.2 O.sub.3 and Ca(OH).sub.2, as well as mixtures of these compounds.

Effects of electron doping on the stability of the metal hydride NaH

NASA Astrophysics Data System (ADS)

Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

2017-04-01

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

Nickel metal hydride LEO cycle testing

NASA Technical Reports Server (NTRS)

Lowery, Eric

1995-01-01

The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

Development of nickel-metal hydride cell

NASA Technical Reports Server (NTRS)

Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

1993-01-01

National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

METHOD OF PREPARING SINTERED ZIRCONIUM METAL FROM ITS HYDRIDES

DOEpatents

Angier, R.P.

1958-02-11

The invention relates to the preparation of metal shapes from zirconium hydride by powder metallurgical techniques. The zirconium hydride powder which is to be used for this purpose can be prepared by rendering massive pieces of crystal bar zirconium friable by heat treatment in purified hydrogen. This any then be ground into powder and powder can be handled in the air without danger of it igniting. It may then be compacted in the normal manner by being piaced in a die. The compact is sintered under vacuum conditions preferably at a temperature ranging from 1200 to 1300 deg C and for periods of one to three hours.

Process for production of a metal hydride

DOEpatents

Allen, Nathan Tait; Butterick, III, Robert; Chin, Arthur Achhing; Millar, Dean Michael; Molzahn, David Craig

2014-08-12

A process for production of a metal hydride compound MH.sub.x, wherein x is one or two and M is an alkali metal, Be or Mg. The process comprises combining a compound of formula (R.sup.1O).sub.xM with aluminum, hydrogen and at least one metal selected from among titanium, zirconium, hafnium, niobium, vanadium, tantalum and iron to produce a compound of formula MH.sub.x. R.sup.1 is phenyl or phenyl substituted by at least one alkyl or alkoxy group. A mole ratio of aluminum to (R.sup.1O).sub.xM is from 0.1:1 to 1:1. The catalyst is present at a level of at least 200 ppm based on weight of aluminum.

A study of H+ production using metal hydride and other compounds by means of laser ion source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sekine M.; Kondo K.; Okamura, M.

2012-02-22

A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH2 and ZrH2) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be usedmore » as a target for proton laser ion source.« less

Optical properties of metal-hydride switchable films

NASA Astrophysics Data System (ADS)

Griessen, Ronald

2001-03-01

In 1996 we discovered that yttrium-, lanthanum-, and rare-earth-hydride (REHx) films [1] protected by a thin palladium layer, exhibit spectacular changes in their optical properties when the hydrogen concentration x is increased from 2 to 3. For example, a 500 nm thick YH2 film is metallic and shiny while YH3 is yellowish and transparent. The transition is reversible, fast [2, 3], and can simply be induced by adding or removing hydrogen from the gas phase, an electrolyte or from an H containing liquid. The optical switching that occurs near the metal-insulator transition of these hydrides is remarkably robust as it is not affected by structural or compositional disorder. It occurs in polycrystalline and epitaxial films, in alloys with cubic or hexagonal crystal structures,and deuterides [4] switch as well as hydrides. At small length scales epitaxial YHx films exhibit surprising structural properties which open the way to pixel-by-pixel optical switching [5]. Colour-neutral switchable mirrors based on RE-Mg alloys [6] can be used in all-solid-state switchable devices. Newest results for Rare-Earth free switchable mirrors will be presented. [1] J. N. Huiberts, R. Griessen, J. H. Rector, R. J. Wijngaarden, J. P. Dekker, D. G. de Groot and N. J. Koeman, Nature 380 (1996) 231; [2] S. J. van der Molen, J. W. J. Kerssemakers, J. H. Rector, N. J. Koeman, B. Dam, R. Griessen, J. Appl. Phys. 86 (1999) 6107; [3] F. J. A. den Broeder, S. J. van der Molen, et al., Nature 394 (1998)656; [4] A. T. M. van Gogh, E. S. Kooij, R. Griessen, Phys. Rev. Lett. 83 (1999) 4614; [5] J. W. J. Kerssemakers, S. J. van der Molen and R. Griessen, Nature 406 (2000) 489; [6] P. van der Sluis, M. Ouwerkerk and P. A. Duine, Appl. Phys. Lett. 70 (1997) 3356.

Impedance and self-discharge mechanism studies of nickel metal hydride batteries for energy storage applications

NASA Astrophysics Data System (ADS)

Zhu, Wenhua; Zhu, Ying; Tatarchuk, Bruce

2013-04-01

Nickel metal hydride battery packs have been found wide applications in the HEVs (hybrid electric vehicles) through the on-board rapid energy conservation and efficient storage to decrease the fossil fuel consumption rate and reduce CO2 emissions as well as other harmful exhaust gases. In comparison to the conventional Ni-Cd battery, the Ni-MH battery exhibits a relatively higher self-discharge rate. In general, there are quite a few factors that speed up the self-discharge of the electrodes in the sealed nickel metal hydride batteries. This disadvantage eventually reduces the overall efficiency of the energy conversion and storage system. In this work, ac impedance data were collected from the nickel metal hydride batteries. The self-discharge mechanism and battery capacity degradation were analyzed and discussed for further performance improvement.

Process of forming a sol-gel/metal hydride composite

DOEpatents

Congdon, James W [Aiken, SC

2009-03-17

An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

Metal hydride reasearch and development program at Brookhaven National Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, J.R.; Reilly, J.J.

1978-01-01

A progress report is presented covering work performed in the hydrogen materials development program at Brookhaven National Laboratory (BNL) for FY78 which encompasses the time period from October 1, 1977 through September 30, 1978. The subjects to be discussed here concern properties of importance in the utilization of metal hydrides as energy storage media. Most of the areas of research were initiated prior to FY78, however all of the results contained in this manuscript were obtained during the aforementioned period of time. The following subjects will be discussed: the properties of ferro-titanium and chrome-titanium alloy hydrides.

Recycling of nickel-metal hydride battery scrap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyman, J.W.; Palmer, G.R.

1994-12-31

Nickel-metal hydride (Ni-MH) battery technology is being developed as a NiCd replacement for applications in consumer cells and electric vehicle batteries. The U.S. Bureau of Mines is investigating hydrometallurgical recycling technology that separates and recovers individual components from Ni-MH battery scrap. Acid dissolution and metal recovery techniques such as precipitation and solvent extraction produced purified products of rare-earths, nickel, and other metals associated with AB{sub 2} and AB{sub 5} Ni-MH scrap. Tests were conducted on scrap cells of a single chemistry that had been de-canned to reduce iron content. Although recovery techniques have been identified in principal, their applicability tomore » mixed battery waste stream and economic attractiveness remain to be demonstrated. 14 refs.« less

New twinning route in face-centered cubic nanocrystalline metals.

PubMed

Wang, Lihua; Guan, Pengfei; Teng, Jiao; Liu, Pan; Chen, Dengke; Xie, Weiyu; Kong, Deli; Zhang, Shengbai; Zhu, Ting; Zhang, Ze; Ma, Evan; Chen, Mingwei; Han, Xiaodong

2017-12-15

Twin nucleation in a face-centered cubic crystal is believed to be accomplished through the formation of twinning partial dislocations on consecutive atomic planes. Twinning should thus be highly unfavorable in face-centered cubic metals with high twin-fault energy barriers, such as Al, Ni, and Pt, but instead is often observed. Here, we report an in situ atomic-scale observation of twin nucleation in nanocrystalline Pt. Unlike the classical twinning route, deformation twinning initiated through the formation of two stacking faults separated by a single atomic layer, and proceeded with the emission of a partial dislocation in between these two stacking faults. Through this route, a three-layer twin was nucleated without a mandatory layer-by-layer twinning process. This route is facilitated by grain boundaries, abundant in nanocrystalline metals, that promote the nucleation of separated but closely spaced partial dislocations, thus enabling an effective bypassing of the high twin-fault energy barrier.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

Oxidation kinetics of hydride-bearing uranium metal corrosion products

NASA Astrophysics Data System (ADS)

Totemeier, Terry C.; Pahl, Robert G.; Frank, Steven M.

The oxidation behavior of hydride-bearing uranium metal corrosion products from Zero Power Physics Reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2, Ar-9%O 2, and Ar-20%O 2. Ignition of corrosion product samples from two moderately corroded plates was observed between 125°C and 150°C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride.

Deformation-mechanism map for nanocrystalline metals by molecular-dynamics simulation.

PubMed

Yamakov, V; Wolf, D; Phillpot, S R; Mukherjee, A K; Gleiter, H

2004-01-01

Molecular-dynamics simulations have recently been used to elucidate the transition with decreasing grain size from a dislocation-based to a grain-boundary-based deformation mechanism in nanocrystalline f.c.c. metals. This transition in the deformation mechanism results in a maximum yield strength at a grain size (the 'strongest size') that depends strongly on the stacking-fault energy, the elastic properties of the metal, and the magnitude of the applied stress. Here, by exploring the role of the stacking-fault energy in this crossover, we elucidate how the size of the extended dislocations nucleated from the grain boundaries affects the mechanical behaviour. Building on the fundamental physics of deformation as exposed by these simulations, we propose a two-dimensional stress-grain size deformation-mechanism map for the mechanical behaviour of nanocrystalline f.c.c. metals at low temperature. The map captures this transition in both the deformation mechanism and the related mechanical behaviour with decreasing grain size, as well as its dependence on the stacking-fault energy, the elastic properties of the material, and the applied stress level.

Investigation of long term stability in metal hydrides

NASA Technical Reports Server (NTRS)

Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

1991-01-01

It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

Hydride Microstructure at the Metal-Oxide Interface of Zircaloy-4 from H.B. Robinson Nuclear Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut N; Edmondson, Philip D; Terrani, Kurt A

2017-01-01

This study investigates the hydride rim microstructure at the metal-oxide interface of Zircaloy-4 cladding segment removed from H.B. Robinson Nuclear Reactor by utilizing high resolution electron microscopy techniques with energy dispersive x-ray spectroscopy at Oak Ridge National Laboratory under the NSUF Rapid Turnout Experiment program. A complex stacking and orientation of hydride platelets has been observed below the sub-oxide layer. Furthermore, radial hydride platelets have been observed. EDS signals of both Fe and Cr has been reduced within hydrides whereas EDS signal of Sn is unaffected.

The storage of hydrogen in the form of metal hydrides: An application to thermal engines

NASA Technical Reports Server (NTRS)

Gales, C.; Perroud, P.

1981-01-01

The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

Grain growth behavior at absolute zero during nanocrystalline metal indentation

NASA Astrophysics Data System (ADS)

Sansoz, F.; Dupont, V.

2006-09-01

The authors show using atomistic simulations that stress-driven grain growth can be obtained in the athermal limit during nanocrystalline aluminum indentation. They find that the grain growth results from rotation of nanograins and propagation of shear bands. Together, these mechanisms are shown to lead to the unstable migration of grain boundaries via process of coupled motion. An analytical model is used to explain this behavior based on the atomic-level shear stress acting on the interfaces during the shear band propagation. This study sheds light on the atomic mechanism at play during the abnormal grain coarsening observed at low temperature in nanocrystalline metals.

Direct synthesis of catalyzed hydride compounds

DOEpatents

Gross, Karl J.; Majzoub, Eric

2004-09-21

A method is disclosed for directly preparing alkali metal aluminum hydrides such as NaAlH.sub.4 and Na.sub.3 AlH.sub.6 from either the alkali metal or its hydride, and aluminum. The hydride thus prepared is doped with a small portion of a transition metal catalyst compound, such as TiCl.sub.3, TiF.sub.3, or a mixture of these materials, in order to render them reversibly hydridable. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen while heating the mixture to about 125.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

Positive ions of the first- and second-row transition metal hydrides

NASA Technical Reports Server (NTRS)

Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

1987-01-01

Theoretical dissociation energies for the first- and second-row transition metal hydride positive ions are critically compared against recent experimental values obtained from ion beam reactive scattering methods. Theoretical spectroscopic parameters and dipole moments are presented for the ground and several low-lying excited states. The calculations employ large Gaussian basis sets and account for electron correlation using the single-reference single- and double-excitation configuration interaction and coupled-pair-functional methods. The Darwin and mass-velocity contributions to the relativistic energy are included in the all-electron calculations on the first-row systems using first-order perturbation theory, and in the second-row systems using the Hay and Wadt relativistic effective core potentials. The theoretical D(0) values for the second-row transition metal hydride positive ions should provide a critical measure of the experimental values, which are not as refined as many of those in the first transition row.

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE PAGES

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha; ...

2017-11-24

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Method and composition in which metal hydride particles are embedded in a silica network

DOEpatents

Heung, Leung K.

1999-01-01

A silica embedded metal hydride composition and a method for making such a composition. The composition is made via the following process: A quantity of fumed silica is blended with water to make a paste. After adding metal hydride particles, the paste is dried to form a solid. According to one embodiment of the invention, the solid is ground into granules for use of the product in hydrogen storage. Alternatively, the paste can be molded into plates or cylinders and then dried for use of the product as a hydrogen filter. Where mechanical strength is required, the paste can be impregnated in a porous substrate or wire network.

Predicted energy densitites for nickel-hydrogen and silver-hydrogen cells embodying metallic hydrides for hydrogen storage

NASA Technical Reports Server (NTRS)

Easter, R. W.

1974-01-01

Simplified design concepts were used to estimate gravimetric and volumetric energy densities for metal hydrogen battery cells for assessing the characteristics of cells containing metal hydrides as compared to gaseous storage cells, and for comparing nickel cathode and silver cathode systems. The silver cathode was found to yield superior energy densities in all cases considered. The inclusion of hydride forming materials yields cells with very high volumetric energy densities that also retain gravimetric energy densities nearly as high as those of gaseous storage cells.

Interaction of electrons with light metal hydrides in the transmission electron microscope.

PubMed

Wang, Yongming; Wakasugi, Takenobu; Isobe, Shigehito; Hashimoto, Naoyuki; Ohnuki, Somei

2014-12-01

Transmission electron microscope (TEM) observation of light metal hydrides is complicated by the instability of these materials under electron irradiation. In this study, the electron kinetic energy dependences of the interactions of incident electrons with lithium, sodium and magnesium hydrides, as well as the constituting element effect on the interactions, were theoretically discussed, and electron irradiation damage to these hydrides was examined using in situ TEM. The results indicate that high incident electron kinetic energy helps alleviate the irradiation damage resulting from inelastic or elastic scattering of the incident electrons in the TEM. Therefore, observations and characterizations of these materials would benefit from increased, instead decreased, TEM operating voltage. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Bipolar Nickel-Metal Hydride Battery Development Project

NASA Technical Reports Server (NTRS)

Cole, John H.

1999-01-01

This paper reviews the development of the Electro Energy, Inc.'s bipolar nickel metal hydride battery. The advantages of the design are that each cell is individually sealed, and that there are no external cell terminals, no electrode current collectors, it is compatible with plastic bonded electrodes, adaptable to heat transfer fins, scalable to large area, capacity and high voltage. The design will allow for automated flexible manufacturing, improved energy and power density and lower cost. The development and testing of the battery's component are described. Graphic presentation of the results of many of the tests are included.

Sodium-based hydrides for thermal energy applications

NASA Astrophysics Data System (ADS)

Sheppard, D. A.; Humphries, T. D.; Buckley, C. E.

2016-04-01

Concentrating solar-thermal power (CSP) with thermal energy storage (TES) represents an attractive alternative to conventional fossil fuels for base-load power generation. Sodium alanate (NaAlH4) is a well-known sodium-based complex metal hydride but, more recently, high-temperature sodium-based complex metal hydrides have been considered for TES. This review considers the current state of the art for NaH, NaMgH3- x F x , Na-based transition metal hydrides, NaBH4 and Na3AlH6 for TES and heat pumping applications. These metal hydrides have a number of advantages over other classes of heat storage materials such as high thermal energy storage capacity, low volume, relatively low cost and a wide range of operating temperatures (100 °C to more than 650 °C). Potential safety issues associated with the use of high-temperature sodium-based hydrides are also addressed.

Solid state consolidation nanocrystalline copper-tungsten using cold spray

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hall, Aaron Christopher; Sarobol, Pylin; Argibay, Nicolas

It is well known that nanostructured metals can exhibit significantly improved properties compared to metals with conventional grain size. Unfortunately, nanocrystalline metals typically are not thermodynamically stable and exhibit rapid grain growth at moderate temperatures. This severely limits their processing and use, making them impractical for most engineering applications. Recent work has shown that a number of thermodynamically stable nanocrystalline metal alloys exist. These alloys have been prepared as powders using severe plastic deformation (e.g. ball milling) processes. Consolidation of these powders without compromise of their nanocrystalline microstructure is a critical step to enabling their use as engineering materials. Wemore » demonstrate solid-state consolidation of ball milled copper-tantalum nanocrystalline metal powder using cold spray. Unfortunately, the nanocrystalline copper-tantalum powder that was consolidated did not contain the thermodynamically stable copper-tantalum nanostructure. Nevertheless, this does this demonstrates a pathway to preparation of bulk thermodynamically stable nanocrystalline copper-tantalum. Furthermore, it demonstrates a pathway to additive manufacturing (3D printing) of nanocrystalline copper-tantalum. Additive manufacturing of thermodynamically stable nanocrystalline metals is attractive because it enables maximum flexibility and efficiency in the use of these unique materials.« less

New Possibilities for Understanding Complex Metal Hydrides via Synchrotron X-ray Studies

NASA Astrophysics Data System (ADS)

Dobbins, Tabbetha

2008-03-01

Ultrasmall-angle x-ray scattering (USAXS) and X-ray absorption spectroscopy (XAS) are used for the study of chemical and morphological changes in metal hydride powder (e.g. NaAlH4) both before and after transition metal salt catalytic dopant additions by high energy ball milling. The variation in surface fractal dimension and particle size with milling time and dopant content were tracked. These studies show that dopant content level (e.g. 2 mol % and 4 mol %) and dopant type (i.e. TiCl2, TiCl3, VCl3, and ZrCl4) markedly affects NaAlH4 powder particle surface area (determined using USAXS surface fractal dimension). As well, the chemical reaction between the catalyst and hydride powder was further elucidated using XAS. Ti-metal reacts with the Al desorption product (from NaAlH4) to form TiAlx product phases. These studies were able to link powder particle surface area to catalytic doping and were able to link dopant chemical state with dehydrogenation reactant and product phases.

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

Fukuzumi, Shunichi; Suenobu, Tomoyoshi

2013-01-07

The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

Studies on hydride-forming alloys as the active material of a metal hydride electrode for a nickel metal hydride cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Zelter, G.R.; Allison, D.U.

1997-12-01

Multi-component AB{sub 5} hydrides are attractive replacements for the cadmium electrode in nickel-cadmium batteries. The archetype compound of the AB{sub 5} alloy class is LaNi{sub 5}, but in a typical battery electrode mischmetal is substituted for La and Ni is substituted in part by variety of metals. This paper deals with the effect on cycle life upon the partial substitution of various lanthanides for La and Sn, In, Al, Co, and Mn for Ni. The presence of Ce was shown to enhance cycle life as did Sn in some cases. An electrode of La{sub 0.67}Ce{sub 0.33}B{sub 5} alloy gave overmore » 3,500 cycles (to specific capacity of 200 mAh/g), indicating that it is a very attractive alloy for a practical Ni/MH{sub x} cell.« less

Low density metal hydride foams

DOEpatents

Maienschein, Jon L.; Barry, Patrick E.

1991-01-01

Disclosed is a low density foam having a porosity of from 0 to 98% and a density less than about 0.67 gm/cc, prepared by heating a mixture of powered lithium hydride and beryllium hydride in an inert atmosphere at a temperature ranging from about 455 to about 490 K for a period of time sufficient to cause foaming of said mixture, and cooling the foam thus produced. Also disclosed is the process of making the foam.

The Planck Sorption Cooler: Using Metal Hydrides to Produce 20 K

NASA Technical Reports Server (NTRS)

Pearson, David P.; Bowman, R.; Prina, M.; Wilson, P.

2006-01-01

The Jet Propulsion Laboratory has built and delivered two continuous closed cycle hydrogen Joule-Thomson (JT) cryocoolers for the ESA Planck mission, which will measure the anisotropy in the cosmic microwave background. The metal hydride compressor consists of six sorbent beds containing LaNi4.78Sn0.22 alloy and a low pressure storage bed of the same material. Each sorbent bed contains a separate gas-gap heat switch that couples or isolates the bed with radiators during the compressor operating cycle. ZrNiHx hydride is used in this heat switch. The Planck compressor produces hydrogen gas at a pressure of 48 Bar by heating the hydride to approx.450 K. This gas passes through a cryogenic cold end consisting of a tube-in-tube heat exchanger, three pre-cooling stages to bring the gas to nominally 52 K, a JT value to expand the gas into the two-phase regime at approx.20 K, and two liquid - vapor heat exchangers that must remove 190 and 646 mW of heat respectively.

Advanced nickel-metal hydride cell development at Hughes: A joint work with US government

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Pickett, D.F.; Stockel, J.F.

1995-07-01

Hughes is currently engaged in the development of an advanced nickel-metal hydride (Ni/MHx) cell for spacecraft application with performance goals of 15 years of operation in a geosynchronous earth orbit at 805 depth of discharge and over 30,000 cycles of life at 30% depth of discharge in a typical low earth orbit. The authors have developed the basic fabrication technique for a lightweight and potentially long life nickel electrode which is usable in space Ni/MHx cells. The authors have developed several attractive hydride alloys which are usable in hydride electrodes and basic fabrication techniques for lightweight, inexpensive, and potentially longmore » life hydride electrodes for a Ni/MHx cell. Utilizing Hughes extensive experiences in development of advanced Ni/Cd and Ni/H{sub 2} cells, the authors plan to develop a first generation space Ni/MHx cell design by 1995 and have the cell flight ready by 1997.« less

Materials considerations in the design of a metal-hydride heat pump for an advanced extravehicular mobility unit

NASA Technical Reports Server (NTRS)

Liebert, B. E.

1986-01-01

A metal-hydride heat pump (HHP) has been proposed to provide an advanced regenerable nonventing thermal sink for the liquid-cooled garment worn during an extravehicular activity (EVA). The conceptual design indicates that there is a potential for significant advantages over the one presently being used by shuttle crew personnel as well as those that have been proposed for future use with the space station. Compared to other heat pump designs, a HHP offers the potential for extended use with no electrical power requirements during the EVA. In addition, a reliable, compact design is possible due to the absence of moving parts other than high-reliability check valves. Because there are many subtleties in the properties of metal hydrides for heat pump applications, it is essential that a prototype hydride heat pump be constructed with the selected materials before a committment is made for the final design. Particular care must be given to the evaporator heat exchanger worn by the astronaut since the performance of hydride heat pumps is generally heat transfer limited.

Hydrometallurgical treatment of nickel-metal hydride battery electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyman, J.W.; Palmer, G.R.

1995-12-31

Nickel-metal hydride (Ni-MH) battery electrodes have been developed as a substitute for cadmium-containing negative electrodes. Use of NI-MH electrodes offers enhanced electrochemical properties in many instances as well as reduced environmental toxicity. Rechargeable batteries using NI-MH electrodes are also strong candidates for electric vehicles. During the production and secondary reclamation of these battery types, recycling procedures will be needed to prevent environmental impact caused by these wastes as well as to recover the value inherent in the scrap. The US Bureau of Mines (USBM) is investigating hydrometallurgical technology that separates and recovers purified metallic components from Ni-MH battery scrap ofmore » two types, AB{sub 2} and AB{sub 5}. An investigation of acid dissolution and metal recovery techniques has determined several processing alternatives that may be used to promote the successful recycling of much of the battery fabrication scrap and eventual secondary scrap. The metals recovered are Ni, Co, and rare earth metals. Although recovery techniques have been identified in principal, their applicability to mixed battery waste stream and economic attractiveness remain to be demonstrated.« less

Activated aluminum hydride hydrogen storage compositions and uses thereof

DOEpatents

Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

2010-11-23

In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

Thermodynamic and Kinetic Properties of Metal Hydrides from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Michel, Kyle Jay

In an effort to minimize the worldwide dependence on fossil fuels, much research has focused on the development of hydrogen fuel cell vehicles. Among the many challenges currently facing the transition to such an alternative energy economy is the storage of hydrogen in an economical and practical way. One class of materials that has presented itself as a possible candidate is solid metal hydrides. These materials chemically bind hydrogen and on heating, release the gas which can then be used to generate power as needed for the vehicle. In order to meet guidelines that have been set for such a storage system, hydrogen must be released rapidly in a narrow temperature range of -40 to 80°C with all reactions being reversible. This sets both thermodynamic and kinetic requirements for the design of candidate metal hydrides. First-principles calculations are well-suited for the task of exploring reactions involving metal hydrides. Here, density-functional theory is used to calculate properties of these materials at the quantum mechanical level of accuracy. In particular, three systems have been investigated: 1. Li-Mg-N-H. Reactions between all known compounds in this system are systematically investigated in order to predict thermodynamically allowed reactions that release hydrogen. The properties of these reactions are compared to the requirements set for hydrogen storage systems. Additionally, ground-state structures are predicted for Li2Mg(NH)2 and Li 4Mg(NH)3. 2. Na-Al-H. The kinetics of mass transport during the (de)hydrogenation of the well-known metal hydride NaAlH4 are investigated. A model is developed to study the flux of native defects through phases involved in these reactions. Since it is also known that titanium is an effective catalyst for both dehydrogenation and rehydrogenation, the effect of Ti substitution in bulk lattices on the kinetics of mass transport is investigated. Results are compared to experiments in order to determine if mass transport

Hydrogen /Hydride/-air secondary battery

NASA Technical Reports Server (NTRS)

Sarradin, J.; Bronoel, G.; Percheron-Guegan, A.; Achard, J. C.

1979-01-01

The use of metal hydrides as negative electrodes in a hydrogen-air secondary battery seems promising. However, in an unpressurized cell, more stable hydrides that LaNi5H6 must be selected. Partial substitutions of nickel by aluminium or manganese increase the stability of hydrides. Combined with an air reversible electrode, a specific energy close to 100 Wh/kg can be expected.

In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

NASA Astrophysics Data System (ADS)

Yang, Xiao Guang; Liaw, Bor Yann

Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

Hydrogen isotope exchange in a metal hydride tube

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, David B.

2014-09-01

This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Karl Johnson

The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. Newmore » materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.« less

Simulation of high temperature thermal energy storage system based on coupled metal hydrides for solar driven steam power plants

DOE PAGES

d'Entremont, Anna; Corgnale, Claudio; Hardy, Bruce; ...

2018-01-11

Concentrating solar power plants can achieve low cost and efficient renewable electricity production if equipped with adequate thermal energy storage systems. Metal hydride based thermal energy storage systems are appealing candidates due to their demonstrated potential for very high volumetric energy densities, high exergetic efficiencies, and low costs. The feasibility and performance of a thermal energy storage system based on NaMgH 2F hydride paired with TiCr 1.6Mn 0.2 is examined, discussing its integration with a solar-driven ultra-supercritical steam power plant. The simulated storage system is based on a laboratory-scale experimental apparatus. It is analyzed using a detailed transport model accountingmore » for the thermochemical hydrogen absorption and desorption reactions, including kinetics expressions adequate for the current metal hydride system. The results show that the proposed metal hydride pair can suitably be integrated with a high temperature steam power plant. The thermal energy storage system achieves output energy densities of 226 kWh/m 3, 9 times the DOE SunShot target, with moderate temperature and pressure swings. Also, simulations indicate that there is significant scope for performance improvement via heat-transfer enhancement strategies.« less

Simulation of high temperature thermal energy storage system based on coupled metal hydrides for solar driven steam power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

d'Entremont, Anna; Corgnale, Claudio; Hardy, Bruce

Concentrating solar power plants can achieve low cost and efficient renewable electricity production if equipped with adequate thermal energy storage systems. Metal hydride based thermal energy storage systems are appealing candidates due to their demonstrated potential for very high volumetric energy densities, high exergetic efficiencies, and low costs. The feasibility and performance of a thermal energy storage system based on NaMgH 2F hydride paired with TiCr 1.6Mn 0.2 is examined, discussing its integration with a solar-driven ultra-supercritical steam power plant. The simulated storage system is based on a laboratory-scale experimental apparatus. It is analyzed using a detailed transport model accountingmore » for the thermochemical hydrogen absorption and desorption reactions, including kinetics expressions adequate for the current metal hydride system. The results show that the proposed metal hydride pair can suitably be integrated with a high temperature steam power plant. The thermal energy storage system achieves output energy densities of 226 kWh/m 3, 9 times the DOE SunShot target, with moderate temperature and pressure swings. Also, simulations indicate that there is significant scope for performance improvement via heat-transfer enhancement strategies.« less

Iron hydrides formation in interstellar clouds

NASA Astrophysics Data System (ADS)

Bar-Nun, A.; Pasternak, M.; Barrett, P. H.

1980-07-01

A recent Moessbauer study with Fe-57 in a solid hydrogen or hydrogen-argon matrix demonstrated the formation of an iron hydride molecule (FeH2) at 2.5-5 K. Following this and other studies, the possible existence of iron hydride molecules in interstellar clouds is proposed. In clouds, the iron hydrides FeH and FeH2 would be formed only on grains, by encounters of H atoms or H2 molecules with Fe atoms which are adsorbed on the grains. The other transition metals, Sc, Ti, V, Cr, Mn, Co, N, Cd and also Cu and Ca form hydrides of the type M-H, which could be responsible, at least in part, for the depletion of these metals in clouds.

Metal hydrides as electrode/catalyst materials for oxygen evolution/reduction in electrochemical devices

DOEpatents

Bugga, Ratnakumar V.; Halpert, Gerald; Fultz, Brent; Witham, Charles K.; Bowman, Robert C.; Hightower, Adrian

1997-01-01

An at least ternary metal alloy of the formula, AB.sub.(5-Y)X(.sub.y), is claimed. In this formula, A is selected from the rare earth elements, B is selected from the elements of groups 8, 9, and 10 of the periodic table of the elements, and X includes at least one of the following: antimony, arsenic, and bismuth. Ternary or higher-order substitutions, to the base AB.sub.5 alloys, that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

Hydrogen Storage Engineering Center of Excellence Metal Hydride Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motyka, T.

2014-05-31

The Hydrogen Storage Engineering Center of Excellence (HSECoE) was established in 2009 by the U.S. Department of Energy (DOE) to advance the development of materials-based hydrogen storage systems for hydrogen-fueled light-duty vehicles. The overall objective of the HSECoE is to develop complete, integrated system concepts that utilize reversible metal hydrides, adsorbents, and chemical hydrogen storage materials through the use of advanced engineering concepts and designs that can simultaneously meet or exceed all the DOE targets. This report describes the activities and accomplishments during Phase 1 of the reversible metal hydride portion of the HSECoE, which lasted 30 months from Februarymore » 2009 to August 2011. A complete list of all the HSECoE partners can be found later in this report but for the reversible metal hydride portion of the HSECoE work the major contributing organizations to this effort were the United Technology Research Center (UTRC), General Motors (GM), Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL) and the Savannah River National Laboratory (SRNL). Specific individuals from these and other institutions that supported this effort and the writing of this report are included in the list of contributors and in the acknowledgement sections of this report. The efforts of the HSECoE are organized into three phases each approximately 2 years in duration. In Phase I, comprehensive system engineering analyses and assessments were made of the three classes of storage media that included development of system level transport and thermal models of alternative conceptual storage configurations to permit detailed comparisons against the DOE performance targets for light-duty vehicles. Phase 1 tasks also included identification and technical justifications for candidate storage media and configurations that should be capable of reaching or exceeding the DOE targets. Phase 2 involved bench-level testing and

Optimization and comprehensive characterization of metal hydride based hydrogen storage systems using in-situ Neutron Radiography

NASA Astrophysics Data System (ADS)

Börries, S.; Metz, O.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Bücherl, T.; Dornheim, M.; Klassen, T.; Schreyer, A.

2016-10-01

For the storage of hydrogen, complex metal hydrides are considered as highly promising with respect to capacity, reversibility and safety. The optimization of corresponding storage tanks demands a precise and time-resolved investigation of the hydrogen distribution in scaled-up metal hydride beds. In this study it is shown that in situ fission Neutron Radiography provides unique insights into the spatial distribution of hydrogen even for scaled-up compacts and therewith enables a direct study of hydrogen storage tanks. A technique is introduced for the precise quantification of both time-resolved data and a priori material distribution, allowing inter alia for an optimization of compacts manufacturing process. For the first time, several macroscopic fields are combined which elucidates the great potential of Neutron Imaging for investigations of metal hydrides by going further than solely 'imaging' the system: A combination of in-situ Neutron Radiography, IR-Thermography and thermodynamic quantities can reveal the interdependency of different driving forces for a scaled-up sodium alanate pellet by means of a multi-correlation analysis. A decisive and time-resolved, complex influence of material packing density is derived. The results of this study enable a variety of new investigation possibilities that provide essential information on the optimization of future hydrogen storage tanks.

Hydride heat pump

DOEpatents

Cottingham, James G.

1977-01-01

Method and apparatus for the use of hydrides to exhaust heat from one temperature source and deliver the thermal energy extracted for use at a higher temperature, thereby acting as a heat pump. For this purpose there are employed a pair of hydridable metal compounds having different characteristics working together in a closed pressure system employing a high temperature source to upgrade the heat supplied from a low temperature source.

METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

DOEpatents

Weeks, I.F.; Goeddel, W.V.

1960-03-22

A method is described of evenly dispersing uranlum metal in a zirconium hydride moderator to produce a fuel element for nuclear reactors. According to the invention enriched uranium hydride and zirconium hydride powders of 200 mesh particle size are thoroughly admixed to form a mixture containing 0.1 to 3% by weight of U/sup 235/ hydride. The mixed powders are placed in a die and pressed at 100 tons per square inch at room temperature. The resultant compacts are heated in a vacuum to 300 deg C, whereby the uranium hydride deoomposes into uranium metal and hydrogen gas. The escaping hydrogen gas forms a porous matrix of zirconium hydride, with uramum metal evenly dispersed therethrough. The advantage of the invention is that the porosity and uranium distribution of the final fuel element can be more closely determined and controlled than was possible using prior methods of producing such fuel ele- ments.

Grain boundary character distribution in nanocrystalline metals produced by different processing routes

DOE PAGES

Bober, David B.; Kumar, Mukal; Rupert, Timothy J.; ...

2015-12-28

Nanocrystalline materials are defined by their fine grain size, but details of the grain boundary character distribution should also be important. Grain boundary character distributions are reported for ball-milled, sputter-deposited, and electrodeposited Ni and Ni-based alloys, all with average grain sizes of ~20 nm, to study the influence of processing route. The two deposited materials had nearly identical grain boundary character distributions, both marked by a Σ3 length percentage of 23 to 25 pct. In contrast, the ball-milled material had only 3 pct Σ3-type grain boundaries and a large fraction of low-angle boundaries (16 pct), with the remainder being predominantlymore » random high angle (73 pct). Furthermore, these grain boundary character measurements are connected to the physical events that control their respective processing routes. Consequences for material properties are also discussed with a focus on nanocrystalline corrosion. As a whole, the results presented here show that grain boundary character distribution, which has often been overlooked in nanocrystalline metals, can vary significantly and influence material properties in profound ways.« less

Transition-Metal Hydride Radical Cations.

PubMed

Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

2016-08-10

Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2] (+) (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark R.; Chang, Christopher H.; Curtis, Calvin J.

2008-07-07

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2]+ (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark; Chang, Christopher H.; Curtis, Calvin J.

2008-06-23

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Nickel-metal hydride battery development. Final technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1995-06-01

Rechargeable batteries are used as the power source for a broad range of portable equipment. Key battery selection criteria typically are weight, volume, first cost, life cycle cost, and environmental impact. Rechargeable batteries are favored from a life cycle cost and environmental impact standpoint over primary batteries. The nickel-metal hydride (Ni-MH) battery system has emerged as the battery of choice for many applications based on its superior characteristics when judged on the above criteria against other battery types. In most cases commercial Ni-MH batteries are constructed with coiled electrodes in cylindrical metal containers. Electro Energy, Inc. (EEI) has been developingmore » a novel flat bipolar configuration of the Ni-MH system that offers weight, volume, and cost advantages when compared to cylindrical cells. The unique bipolar approach consists of fabricating individual flat wafer cells in conductive, carbon-filled, plastic face plates. The individual cells contain a nonconductive plastic border which is heat sealed around the perimeter to make a totally sealed unit cell. Multi-cell batteries are fabricated by stacking the individual wafer cells in such a way that the positive face of one cell contacts the negative face of the adjacent cell. The stack is then contained in an outer housing with end contacts. The purpose of this program was to develop, evaluate, and demonstrate the capabilities of the EEI Ni-MH battery system for consumer applications. The work was directed at the development and evaluation of the compact bipolar construction for its potential advantages of high power and energy density. Experimental investigations were performed on various nickel electrode types, hydride electrode formulations, and alternate separator materials. Studies were also directed at evaluating various oxygen recombination techniques for low pressure operation during charge and overcharge.« less

Advanced nickel-metal hydride cell development at Hughes: A joint work with US government

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Pickett, D.F.; Stockel, J.F.

1995-01-25

Hughes is currently engaged in the development of an advanced nickel-metal hydride (Ni/MHx) cell for spacecraft application with performance goals of 15 years of opertion in a geosynchronous earth orbit at 80% depth of discharge and over 30,000 cycles of life at 30% depth of discharge in a typical low earth orbit. We have developed the basic fabrication technique for a lightweight and potentially long life nickel electrode which is useable in space Ni/MHx cells. We have developed several attractive hydride alloys which are useable in hydride electrodes and basic fabrication techniques for lightweight, inexpensive, and potentially long life hydridemore » electrodes for a Ni/MHx cell. Utilizing Hughes extensive experiences in development of advanced Ni/Cd and Ni/H{sub 2} cells, we plan to develop a first generation space Ni/MHx cell design by 1995 and have the cell flight ready by 1997.« less

Advanced Metal-Hydrides-Based Thermal Battery: A New Generation of High Density Thermal Battery Based on Advanced Metal Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

HEATS Project: The University of Utah is developing a compact hot-and-cold thermal battery using advanced metal hydrides that could offer efficient climate control system for EVs. The team’s innovative designs of heating and cooling systems for EVs with high energy density, low-cost thermal batteries could significantly reduce the weight and eliminate the space constraint in automobiles. The thermal battery can be charged by plugging it into an electrical outlet while charging the electric battery and it produces heat and cold through a heat exchanger when discharging. The ultimate goal of the project is a climate-controlling thermal battery that can lastmore » up to 5,000 charge and discharge cycles while substantially increasing the driving range of EVs, thus reducing the drain on electric batteries.« less

Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems

NASA Astrophysics Data System (ADS)

Ward, Patrick A.; Corgnale, Claudio; Teprovich, Joseph A.; Motyka, Theodore; Hardy, Bruce; Sheppard, Drew; Buckley, Craig; Zidan, Ragaiy

2016-04-01

Recently, there has been increasing interest in thermal energy storage (TES) systems for concentrated solar power (CSP) plants, which allow for continuous operation when sunlight is unavailable. Thermochemical energy storage materials have the advantage of much higher energy densities than latent or sensible heat materials. Furthermore, thermochemical energy storage systems based on metal hydrides have been gaining great interest for having the advantage of higher energy densities, better reversibility, and high enthalpies. However, in order to achieve higher efficiencies desired of a thermal storage system by the US Department of Energy, the system is required to operate at temperatures >600 °C. Operation at temperatures >600 °C presents challenges including material selection, hydrogen embrittlement and permeation of containment vessels, appropriate selection of heat transfer fluids, and cost. Herein, the technical difficulties and proposed solutions associated with the use of metal hydrides as TES materials in CSP applications are discussed and evaluated.

Development of a nickel/metal hydride battery (Ni/MH) system for EV application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikoma, M.; Hamada, S.; Morishita, N.

1994-12-31

In order to satisfy basic battery characteristics for electric vehicles (EV) such as specific energy, specific power and cycle life that are required for driving on urban streets, the authors have selected the valve-regulated lead acid battery as a conventional battery and the nickel/metal-hydride battery as an advanced battery, and have been studying their development in order to put them into practical use by 1998. Regarding the nickel/metal-hydride battery, excellent nickel positive electrode with high temperature charge efficiency accomplished with additives such as Ca compounds, and an exceedingly good hydrogen absorbing alloy negative electrode with high capacity and long cyclemore » life, achieved by adjustment of alloy composition, surface treatment, and control of binder and conductive additive have been developed to overcome difficulties in the scale-up of battery size. Modular batteries using this technology possess specific energy twice (70 Wh/kg) that of the lead-acid battery, and have superior specific power (160 Wh/kg) and cycle life. 5 refs.« less

Accelerated cycle life performance for ovonic nickel-metal hydride cells

NASA Technical Reports Server (NTRS)

Otzinger, Burton M.

1991-01-01

Nickel-Metal Hydride (Ni-MH) rechargeable batteries have emerged as the leading candidate for commercial replacement of nickel-cadmium (Ni-Cd) batteries. An important incentive is that the Ni-MH cell provides approximately twice the capacity of a Ni-Cd cell for a given size. A six-cell battery was committed to an accelerated cycle life test to determine the effect of separation type on performance. Results of the test may also show the Ni-MH battery to be a replacement candidate for the aerospace Ni-Cd battery.

On the thermodynamics of phase transitions in metal hydrides

NASA Astrophysics Data System (ADS)

di Vita, Andrea

2012-02-01

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE PAGES

d'Entremont, A.; Corgnale, C.; Sulic, M.; ...

2017-08-31

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

d'Entremont, A.; Corgnale, C.; Sulic, M.

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Hydrogen storage in the form of metal hydrides

NASA Technical Reports Server (NTRS)

Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

1984-01-01

Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

NASA Astrophysics Data System (ADS)

Carnes, Corrie Leigh

The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

Formation of nanocrystalline SiGe in Polycrystalline-Ge/Si thin film without any metal induced crystallization

NASA Astrophysics Data System (ADS)

Tah, Twisha; Singh, Ch. Kishan; Madapu, K. K.; Polaki, S. R.; Ilango, S.; David, C.; Dash, S.; Panigrahi, B. K.

2017-05-01

The formation of nanocrystalline SiGe without the aid of metal induced crystallization is reported. Re-crystallization of the as-deposited poly-Ge film (deposited at 450 °C) leads to development of regions with depleted Ge concentration upon annealing at 500 °C. Clusters with crystalline facet containing both nanocrystalline SiGe and crystalline Ge phase starts appearing at 600 °C. The structural phase characteristics were investigated by X-ray diffraction (XRD) and Raman spectroscopy. The stoichiometry of the SiGe phase was estimated from the positions of the Raman spectral peaks.

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sato, T.; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.

2016-08-31

Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4] – was investigated using inelastic neutron scattering viewed from vibrational dynamics. Here, the hydrogen release followed the softening of translational and [AlH4] – librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

Self-discharge mechanism of sealed-type nickel/metal-hydride battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikoma, Munehisa; Hoshina, Yasuko; Matsumoto, Isao

1996-06-01

Factors affecting the self-discharge rate of a nickel/metal-hydride (Ni-MH) battery, generally much higher than that of nickel/cadmium (Ni-Cd) battery, are investigated, and the self-discharge mechanism is discussed. Ammonia and amine participate in the shuttle reaction like nitrate ion in the Ni-Cd battery, resulting in acceleration of the self-discharge. When nonwoven fabric made of sulfonated-polypropylene is used as a separator instead of conventional polyamide separator, the self-discharge rate of the Ni-MH battery is strongly depressed, to the same level as that of Ni-Cd battery.

Ovonic nickel metal hydride batteries for space applications

NASA Technical Reports Server (NTRS)

Venkatesan, S.; Corrigan, D. A.; Fetcenko, M. A.; Gifford, P. R.; Dhar, S. K.; Ovshinsky, S. R.

1993-01-01

Ovonic nickel-metal hydride (NiMH) rechargeable batteries are easily adaptable to a variety of applications. Small consumer NiMH cells were developed and are now being manufactured by licensees throughout the world. This technology was successfully scaled up in larger prismatic cells aimed at electric vehicle applications. Sealed cells aimed at satellite power applications were also built and cycle tested by OBC and other outside agencies. Prototype batteries with high specific energy (over 80 Wh/kg), high energy density (245 Wh/L), and excellent power capability (400 W/kg) were produced. Ovonic NiMH batteries demonstrated an excellent cycle life of over 10,000 cycles at 30 percent DOD. Presently, Ovonic Battery Company is working on an advanced version of this battery for space applications as part of an SBIR contract from NASA.

Capture of liquid hydrogen boiloff with metal hydride absorbers

NASA Technical Reports Server (NTRS)

Rosso, M. J.; Golben, P. M.

1984-01-01

A procedure which uses metal hydrides to capture some of this low pressure (,1 psig) hydrogen for subsequent reliquefaction is described. Of the five normally occurring sources of boil-off vapor the stream associated with the off-loading of liquid tankers during dewar refill was identified as the most cost effective and readily recoverable. The design, fabrication and testing of a proof-of-concept capture device, operating at a rate that is commensurate with the evolution of vapor by the target stream, is described. Liberation of the captured hydrogen gas at pressure .15 psig at normal temperatures (typical liquefier compressor suction pressure) are also demonstrated. A payback time of less than three years is projected.

Use of reversible hydrides for hydrogen storage

NASA Technical Reports Server (NTRS)

Darriet, B.; Pezat, M.; Hagenmuller, P.

1980-01-01

The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

LaNi{sub 5}-based metal hydride electrode in Ni-MH rechargeable cells

DOEpatents

Bugga, R.V.; Fultz, B.; Bowman, R.; Surampudi, S.R.; Witham, C.K.; Hightower, A.

1999-03-30

An at least ternary metal alloy of the formula AB{sub (Z-Y)}X{sub (Y)} is disclosed. In this formula, A is selected from the rare earth elements, B is selected from the elements of Groups 8, 9, and 10 of the Periodic Table of the Elements, and X includes at least one of the following: antimony, arsenic, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. Ternary or higher-order substitutions to the base AB{sub 5} alloys that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption. 16 figs.

Sub-millimeter Spectroscopy of Astrophysically Important Molecules and Ions: Metal Hydrides, Halides, and Cyanides

NASA Technical Reports Server (NTRS)

Ziurys, L. M.; Flory, M. A.; Halfen, D. T.

2006-01-01

With the advent of SOFIA, Herschel, and SAFIR, new wavelength regions will become routinely accessible for astronomical spectroscopy, particularly at submm frequencies (0.5-1.1 THz). Molecular emission dominates the spectra of dense interstellar gas at these wavelengths. Because heterodyne detectors are major instruments of these missions, accurate knowledge of transition frequencies is crucial for their success. The Ziurys spectroscopy laboratory has been focusing on the measurement of the pure rotational transitions of astrophysically important molecules in the sub-mm regime. Of particular interest have been metal hydride species and their ions, as well as metal halides and cyanides. A new avenue of study has included metal bearing molecular ions.

Development of Novel Metal Hydride-Carbon Nanomaterial Based Nanocomposites as Anode Electrode Materials for Lithium Ion Battery

DTIC Science & Technology

2014-06-30

The aim of this study is to develop metal hydride-carbon nanomaterial based nanocomposites as anode electrode materials for high capacity lithium ion battery and...henceforth to develop high energy density, and good cyclic stability lithium ion battery .

Phase I. Lanthanum-based Start Materials for Hydride Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gschneidner, K. A.; Schmidt, F. A.; Frerichs, A. E.

The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La 1-xR x)(Ni 1-yM y)(Si z), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

Metal Hydrides, MOFs, and Carbon Composites as Space Radiation Shielding Mitigators

NASA Technical Reports Server (NTRS)

Atwell, William; Rojdev, Kristina; Liang, Daniel; Hill, Matthew

2014-01-01

Recently, metal hydrides and MOFs (Metal-Organic Framework/microporous organic polymer composites - for their hydrogen and methane storage capabilities) have been studied with applications in fuel cell technology. We have investigated a dual-use of these materials and carbon composites (CNT-HDPE) to include space radiation shielding mitigation. In this paper we present the results of a detailed study where we have analyzed 64 materials. We used the Band fit spectra for the combined 19-24 October 1989 solar proton events as the input source term radiation environment. These computational analyses were performed with the NASA high energy particle transport/dose code HZETRN. Through this analysis we have identified several of the materials that have excellent radiation shielding properties and the details of this analysis will be discussed further in the paper.

METHOD AND APPARATUS FOR MAKING URANIUM-HYDRIDE COMPACTS

DOEpatents

Wellborn, W.; Armstrong, J.R.

1959-03-10

A method and apparatus are presented for making compacts of pyrophoric hydrides in a continuous operation out of contact with air. It is particularly useful for the preparation of a canned compact of uranium hydride possessing high density and purity. The metallic uranium is enclosed in a container, positioned in a die body evacuated and nvert the uranium to the hydride is admitted and the container sealed. Heat is applied to bring about the formation of the hydride, following which compression is used to form the compact sealed in a container ready for use.

LaNi{sub 5}-based metal hydride electrode in Ni-MH rechargeable cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bugga, R.V.; Fultz, B.; Bowman, R.

1999-03-30

An at least ternary metal alloy of the formula AB{sub (Z-Y)}X{sub (Y)} is disclosed. In this formula, A is selected from the rare earth elements, B is selected from the elements of Groups 8, 9, and 10 of the Periodic Table of the Elements, and X includes at least one of the following: antimony, arsenic, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. Ternary or higher-order substitutions to the base AB{sub 5} alloys that form strong kinetic interactions with themore » predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption. 16 figs.« less

In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

NASA Astrophysics Data System (ADS)

Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

2017-03-01

La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

Heat Transfer Enhancement of Metal Hydride Particle Bed for Heat Driven Type Refrigerator by Carbon Fiber

NASA Astrophysics Data System (ADS)

Bae, Sang-Chul; Tanae, Takayuki; Monde, Masanori; Katsuta, Masafumi

A series of study has been performed on the metal hydride particle beds of Ti0.15Zr0.85Cr0.9Fe0.6Ni0.2Mn0.3Cu0.05 (MH-1, using for heat source), Ti0.73Zr0.27Cr1.2Fe0.3Ni0.1Mn0.4Cu0.05 (MH-2, using for cooling load) to measure the effective thermal conductivities. The effective thermal conductivities of activated and oxidized MH particle bed in helium have been examined. Experiment results show that pressure has great influence on effective thermal conductivity in low pressure range (<0.5 MPa). And that influence decreases rapidly with increase of gas pressure. The reason of pressure dependence at low pressure range is that the mean free path of gas becomes greater than effective thickness of gas film which is important to the heat transfer mechanism of particle bed. In order to enhance the poor thermal conductivity of metal hydride particle bed, carbon fiber mixing method has been used in this study. Three types, two insert methods and five mass percentages of carbon fiber have been examined and compared. The highest effective thermal conductivity of MH particle bed has been reached with Type B carbon fiber which has second higher thermal conductivity, and 2 weight percentage. This method has acquired 5-6 times higher thermal conductivity than pure metal hydride particle beds with quite low quantity of additives, only 2 mass% of carbon fiber. This is a good result comparing to other method which can reach higher effective thermal conductivity but needs much higher percentage of additives too.

Enhancement of cold fusion in metal ``hydrides'' by screening of proton and deuteron charges

NASA Astrophysics Data System (ADS)

Burrows, Adam

1989-08-01

The production of fusion heat in a metal hydride (deuteride) lattice is problematic, since the reported ratio of power to neutron or γ-ray flux of some workers is much larger than that for any known conventional complement of fusion reactions. However, enhanced screening of the deuteron or proton charge in the lattice cages might enhance to modest levels the standard d+d-->3He+n,T+p and p+d-->3He+γ fusion reactions. By lowering the effective deuteron-deuteron and proton-deuteron Coulomb barriers, the effective Gamov penetration factor is increased substantially in metals in general, transition metals in particular, and perhaps enough to produce modest neutron fluxes and tritium yields.

Cesium Platinide Hydride 4Cs 2 Pt-CsH: An Intermetallic Double Salt Featuring Metal Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smetana, Volodymyr; Mudring, Anja-Verena

2016-10-24

With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs 9Pt 4H exhibits a complex crystal structure containing Cs + cations, Pt 2- and H - anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs 9Pt 4H≡4 Cs 2Pt∙CsH.

Heat exchanger selection and design analyses for metal hydride heat pump systems

DOE PAGES

Mazzucco, Andrea; Voskuilen, Tyler G.; Waters, Essene L.; ...

2016-01-01

This paper presents a design analysis for the development of highly efficient heat exchangers within stationary metal hydride heat pumps. The design constraints and selected performance criteria are applied to three representative heat exchangers. The proposed thermal model can be applied to select the most efficient heat exchanger design and provides outcomes generally valid in a pre-design stage. Heat transfer effectiveness is the principal performance parameter guiding the selection analysis, the results of which appear to be mildly (up to 13%) affected by the specific Nusselt correlation used. The thermo-physical properties of the heat transfer medium and geometrical parameters aremore » varied in the sensitivity analysis, suggesting that the length of independent tubes is the physical parameter that influences the performance of the heat exchangers the most. The practical operative regions for each heat exchanger are identified by finding the conditions over which the heat removal from the solid bed enables a complete and continuous hydriding reaction. The most efficient solution is a design example that achieves the target effectiveness of 95%.« less

LaNi.sub.5 is-based metal hydride electrode in Ni-MH rechargeable cells

DOEpatents

Bugga, Ratnakumar V.; Fultz, Brent; Bowman, Robert; Surampudi, Subra Rao; Witham, Charles K.; Hightower, Adrian

1999-01-01

An at least ternary metal alloy of the formula AB.sub.(Z-Y) X.sub.(Y) is disclosed. In this formula, A is selected from the rare earth elements, B is selected from the elements of Groups 8, 9, and 10 of the Periodic Table of the Elements, and X includes at least one of the following: antimony, arsenic, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. Ternary or higher-order substitutions to the base AB.sub.5 alloys that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

High energy density battery based on complex hydrides

DOEpatents

Zidan, Ragaiy

2016-04-26

A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

Hydrogen transmission/storage with a metal hydride/organic slurry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.; McClaine, A.

1998-08-01

Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits:more » it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.« less

Improvement of electrochemical properties and oxidation/reduction behavior of cobalt in positive electrode of Ni-metal hydride battery

NASA Astrophysics Data System (ADS)

Morimoto, Katsuya; Nagashima, Ikuo; Matsui, Masaki; Maki, Hideshi; Mizuhata, Minoru

2018-06-01

The deterioration mechanisms of a Ni-metal hydride (Ni-MH) battery system during operation is investigated. A decrease of the discharge voltage is observed at the early stage of the cycle, which indicates the possible occurrence of an unexpected system shutdown of the battery at low state of charge. Cyclic voltammetry and surface examination are used to investigate the causes of this phenomenon. The elution of elements such as Al and Mn from the metal hydride negative electrodes is shown to affect the oxidation/reduction behavior of Co, the conductive material of the positive electrode. Furthermore, the possible methods to strengthen the conductive network of Co, including pretreatment of the positive electrode, addition of conductive material, and precipitation of the elution elements as insoluble compounds to reduce their effect are also investigated. By combining these strategies, deterioration of the conductive network can be prevented in the early stage.

Development of nickel-metal hydride cell: An update

NASA Technical Reports Server (NTRS)

Kuwajima, S.; Kusawake, Hiroaki; Nakatani, Kensuke; Yano, Y.

1994-01-01

This paper presents in viewgraph format an overview of NASDA's evaluation of commercial nickel metal-hydride (Ni-MH) cells and the development and testing of Ni-MH cells for use in space. The commercial cells are concluded to be feasible and suitable for use in LEO; for GEO, the durability for overcharge is needed because long-term charge retention is required. For the aerospace Ni-MH cell design, two activation procedures are applied to evaluate the effect of the difference in the amount of overcharge protection and precharge. Specific energy of the Ni-MH cell is nearly accomplished at 50 Wh/kg. Initial characteristics indicate the effect derived from precharge. Thirty-five amp-hour class Ni-MH cells have good performance for LEO cycle of 25 and 40 percent DOD up to 3000 cycles as similar to commercial cells. The effect of the difference in the amount of overcharge protection will appear in life test.

Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries.

PubMed

Li, M M; Yang, C C; Wang, C C; Wen, Z; Zhu, Y F; Zhao, M; Li, J C; Zheng, W T; Lian, J S; Jiang, Q

2016-06-07

Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world's dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials-hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g(-1), which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

PubMed Central

Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

2016-01-01

Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g−1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles. PMID:27270184

Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

NASA Astrophysics Data System (ADS)

Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

2016-06-01

Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

Nickel-metal hydride (Ni-MH) batteries for aircraft power

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erbacher, J.K.; Kruchek, C.L.; Vukson, S.P.

1995-12-31

Commercial nickel metal hydride (Ni-MH) batteries are under evaluation for potential application as a replacement for existing Ni-Cd and Pb-Acid batteries currently used by the USAF. Replacement of these batteries is desirable due to the high cost of maintenance and acquisition, the environmental hazards associated with worker exposure to hazardous materials, and the high cost of reclamation programs for these existing batteries. Both cylindrical and prismatic AB5 cells show promise for this application, but will require alloy and single cell development to reduce self-discharge, increase discharge and charge rates, and expand the temperature range to meet austere military environments. Testedmore » AB{sub 2} cylindrical cell technology appear inadequate to meet military requirements although these cells show better charge capability at 71 C than AB{sub 5} cylindrical or prismatic cells.« less

Progress in the development of Ovonic nickel-metal hydride batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venkatesan, S.; Corrigan, D.A.; Gifford, P.R.

1993-05-01

Proprietary, multicomponent hydrogen storage alloys using the principles of atomic engineering form the heart of Ovonic Nickel-Metal Hydride (Ni/MH) battery technology. This battery system, in development for 10 years, has been licensed to several manufacturers both for consumer cells and electric vehicle batteries. These cells have achieved a specific energy of over 80 Wh/kg, a peak power in excess of 200 W/kg, and over 1000 cycles at 100% depth of discharge. They also have an intrinsic ability to withstand overcharge and overdischarge abuse. Ovonic Ni/MH batteries are environmentally friendly and can be recycled. Performance data will be presented showing themore » successful scale-up of this technology for electric vehicle applications.« less

Characterization of spent nickel-metal hydride batteries and a preliminary economic evaluation of the recovery processes.

PubMed

Lin, Sheng-Lun; Huang, Kuo-Lin; Wang, I-Ching; Chou, I-Cheng; Kuo, Yi-Ming; Hung, Chung-Hsien; Lin, Chitsan

2016-03-01

Valuable metal materials can be recovered from spent nickel-metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. The spent nickel-metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and

Gas atomization processing of tin and silicon modified LaNi 5 for nickel-metal hydride battery applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ting, Jason

1999-02-12

Numerous researchers have studied the relevant material properties of so-called AB 5 alloys for battery applications. These studies involved LaNi 5 substituted alloys which were prepared using conventional cast and crush alloying techniques. While valuable to the understanding of metal hydride effects, the previous work nearly ignored the potential for alternative direct powder production methods, like high pressure gas atomization (HPGA). Thus, there is a need to understand the relationship between gas atomization processes, powder particle solidification phases, and hydrogen absorption properties of ultra fine (< 25 μm) atomized powders with high surface area for enhanced battery performance. Concurrently, developmentmore » of a gas atomization nozzle that is more efficient than all current designs is needed to increase the yield of ultrafine AB 5 alloy powder for further processing advantage. Gas atomization processing of the AB 5 alloys was demonstrated to be effective in producing ultrafine spherical powders that were resilient to hydrogen cycling for the benefit of improving corrosion resistance in battery application. These ultrafine powders benefited from the rapid solidification process by having refined solute segregation in the microstructure of the gas atomized powders which enabled a rapid anneal treatment of the powders. The author has demonstrated the ability to produce high yields of ultrafine powder efficiently and cost effectively, using the new HPGA-III technology. Thus, the potential benefits of processing AB 5 alloys using the new HPGA technology could reduce manufacturing cost of nickel-metal hydride powder. In the near future, the manufacture of AB 5 alloy powders could become a continuous and rapid production process. The economic benefit of an improved AB 5 production process may thereby encourage the use of nickel-metal hydride rechargeable batteries in electrical vehicle applications in the foreseeable future.« less

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

PubMed

Bahl, Sumit; Shreyas, P; Trishul, M A; Suwas, Satyam; Chatterjee, Kaushik

2015-05-07

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

Neutron diffraction investigation of γ manganese hydride

NASA Astrophysics Data System (ADS)

Fedotov, V. K.; Antonov, V. E.; Kolesnikov, A. I.; Beskrovnyi, A. I.; Grosse, G.; Wagner, F. E.

1998-08-01

A profile analysis of the neutron diffraction spectrum of the fcc high pressure hydride λ-MnH 0.41 measured under ambient conditions showed that hydrogen is randomly distributed over the octahedral interstices of the fcc metal lattice and that the hydride is an antiferromagnet with the same collinear spin structure as pure λ-Mn, but with a smaller magnetic moment of about 1.9 Bohr magnetons per Mn atom.

Rotational frequencies of transition metal hydrides for astrophysical searches in the far-infrared

NASA Technical Reports Server (NTRS)

Brown, John M.; Beaton, Stuart P.; Evenson, Kenneth M.

1993-01-01

Accurate frequencies for the lowest rotational transitions of five transition metal hydrides (CrH, FeH, CoH, NiH, and CuH) in their ground electronic states are reported to help the identification of these species in astrophysical sources from their far-infrared spectra. Accurate frequencies are determined in two ways: for CuH, by calculation from rotational constants determined from higher J transitions with an accuracy of 190 kHz; for the other species, by extrapolation to zero magnetic field from laser magnetic resonance spectra with an accuracy of 0.7 MHz.

Metal hydride hydrogen compression: recent advances and future prospects

NASA Astrophysics Data System (ADS)

Yartys, Volodymyr A.; Lototskyy, Mykhaylo; Linkov, Vladimir; Grant, David; Stuart, Alastair; Eriksen, Jon; Denys, Roman; Bowman, Robert C.

2016-04-01

Metal hydride (MH) thermal sorption compression is one of the more important applications of the MHs. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units, are analyzed. The paper includes also a theoretical modelling of a two-stage compressor aimed at describing the performance of the experimentally studied systems, their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS and the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the MH compression in the overall development of the hydrogen-driven energy systems. The work is based on the analysis of the development of the technology in Europe, USA and South Africa.

Method for producing functionally graded nanocrystalline layer on metal surface

DOEpatents

Ajayi, Oyelayo O.; Hershberger, Jeffrey G.

2010-03-23

An improved process for the creation or formation of nanocrystalline layers on substrates' surfaces is provided. The process involves "prescuffing" the surface of a substrate such as a metal by allowing friction to occur on the surface by a load-bearing entity making rubbing contact and moving along and on the substrate's surface. The "prescuffing" action is terminated when the coefficient of friction between the surface and the noise is rising significantly. Often, the significant rise in the coefficient of friction is signaled by a change in pitch of the scuffing action sound emanating from the buffeted surface. The "prescuffing" gives rise to a harder and smoother surface which withstands better any inadequate lubrication that may take place when the "prescuffed" surface is contacted by other surfaces.

Key hydride vibrational modes in [NiFe] hydrogenase model compounds studied by resonance Raman spectroscopy and density functional calculations.

PubMed

Shafaat, Hannah S; Weber, Katharina; Petrenko, Taras; Neese, Frank; Lubitz, Wolfgang

2012-11-05

Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. While many enzymatic states of the [NiFe] hydrogenase have been studied extensively, there are multiple catalytically relevant EPR-silent states that remain poorly characterized. Analysis of model compounds using new spectroscopic techniques can provide a framework for the study of these elusive states within the protein. We obtained optical absorption and resonance Raman (RR) spectra of (dppe)Ni(μ-pdt)Fe(CO)(3) and [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)(3)][BF(4)], which are structural and functional model compounds for the EPR-silent Ni-SI and Ni-R states of the [NiFe] hydrogenase active site. The studies presented here use RR spectroscopy to probe vibrational modes of the active site, including metal-hydride stretching vibrations along with bridging ligand-metal and Fe-CO bending vibrations, with isotopic substitution used to identify key metal-hydride modes. The metal-hydride vibrations are essentially uncoupled and represent isolated, localized stretching modes; the iron-hydride vibration occurs at 1530 cm(-1), while the nickel-hydride vibration is observed at 945 cm(-1). The significant discrepancy between the metal-hydride vibrational frequencies reflects the slight asymmetry in the metal-hydride bond lengths. Additionally, time-dependent density functional theory (TD-DFT) calculations were carried out to obtain theoretical RR spectra of these compounds. On the basis of the detailed comparison of theory and experiment, the dominant electronic transitions and significant normal modes probed in the RR experiments were assigned; the primary transitions in the visible wavelengths represent metal-to-metal and metal-to-ligand charge transfer bands. Inherent properties of metal-hydride vibrational modes in resonance Raman spectra and DFT calculations are discussed together with the prospects of observing such vibrational modes in metal-hydride-containing proteins. Such a

Chemical Hydride Slurry for Hydrogen Production and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClaine, Andrew W

2008-09-30

The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH 2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at amore » time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston University

Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

PubMed

Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

2018-02-01

The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of superconducting platinum hydride under pressure: an ab initio approach

NASA Astrophysics Data System (ADS)

Kim, Duck Young; Scheicher, Ralph; Pickard, Chris; Needs, Richard; Ahuja, Rajeev

2012-02-01

Noble metals such as Pt, Au, or Re are commonly used for electrodes and gaskets in diamond anvil cells for high-pressure research because they are expected to rarely undergo structural transformation and possess simple equation of states. Specifically Pt has been used widely for high-pressure experiments and has been considered to resist hydride formation under pressure. Pressure-induced reactions of metals with hydrogen are in fact quite likely because hydrogen atoms can occupy interstitial positions in the metal lattice, which can lead to unexpected effects in experiments. In our study, PRL 107 117002 (2011), we investigated crystal structures using ab initio random structure searching (AIRSS) and predicted the formation of platinum mono-hydride above 22 GPa and superconductivity Tc was estimated to be 10 -- 25 K above around 80 GPa. Furthermore, we showed that the formation of fcc noble metal hydrides under pressure is common and examined the possibility of superconductivity in these materials.

Atom Probe Analysis of Ex Situ Gas-Charged Stable Hydrides.

PubMed

Haley, Daniel; Bagot, Paul A J; Moody, Michael P

2017-04-01

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200-500 kPa (2-5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide-metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

NASA Astrophysics Data System (ADS)

Kelly, Stephen Thomas

Hydrogen makes an attractive energy carrier for many reasons. It is an abundant chemical fuel that can be produced from a wide variety of sources and stored for very long periods of time. When used in a fuel cell, hydrogen emits only water at the point of use, making it very attractive for mobile applications such as in an automobile. Metal hydrides are promising candidates for on-board reversible hydrogen storage in mobile applications due to their very high volumetric storage capacities---in most cases exceeding even that of liquid hydrogen. The United States Department of Energy (DOE) has set fuel system targets for an automotive hydrogen storage system, but as of yet no single material meets all the requirements. In particular, slow reaction kinetics and/or inappropriate thermodynamics plague many metal hydride hydrogen storage materials. In order to engineer a practical material that meets the DOE targets, we need a detailed understanding of the kinetic and thermodynamic properties of these materials during the phase change. In this work I employed sputter deposited thin films as a platform to study materials with highly controlled chemistry, microstructure and catalyst placement using thin film characterization techniques such as in situ x-ray diffraction (XRD) and neutron reflectivity. I observed kinetic limitations in the destabilized Mg2Si system due to the slow diffusion of the host Mg and Si atoms while forming separate MgH2 and Si phases. Conversely, I observed that the presence of Al in the Mg/Al system inhibits hydrogen diffusion while the host Mg and Al atoms interdiffuse readily, allowing the material to fall into a kinetic and/or thermodynamic trap by forming intermetallic compounds such as Mg17Al 12. By using in situ XRD to analyze epitaxial Mg films grown on (001) oriented Al2O3 substrates I observed hydride growth consistent with a model of a planar hydride layer growing into an existing metal layer. Subsequent film cycling changes the hydrogen

Effects on the positive electrode of the corrosion of AB{sub 5} alloys in nickel-metal-hydride batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernard, P.

1998-02-01

Effects of corrosion of MmNi{sub 4.3{minus}x}Mn{sub 0.3}Al{sub 0.4}Co{sub x} alloys (where Mm = Ce 50%, La 30%, Nd 15%, Pr 5%) are evaluated in nickel-metal-hydride (Ni-MH) cells. Particularly, it is shown how Al released by the corroded alloys pollutes the positive electrode, which endures a loss of charging efficiency, due to the formation of a hydrotalcite-like phase stabilized with Al. Furthermore, since Al is eluted from the hydride electrode and is completely trapped in the positive active material, the titration of this element in the positive electrode is a powerful technique for quantification of the corrosion of AB{sub 5} alloysmore » in Ni-MH cells.« less

Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

NASA Technical Reports Server (NTRS)

Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

2006-01-01

The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2016-05-01

Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

Nanocrystalline High-Entropy Alloys: A New Paradigm in High-Temperature Strength and Stability.

PubMed

Zou, Yu; Wheeler, Jeffrey M; Ma, Huan; Okle, Philipp; Spolenak, Ralph

2017-03-08

Metals with nanometer-scale grains or nanocrystalline metals exhibit high strengths at ambient conditions, yet their strengths substantially decrease with increasing temperature, rendering them unsuitable for usage at high temperatures. Here, we show that a nanocrystalline high-entropy alloy (HEA) retains an extraordinarily high yield strength over 5 GPa up to 600 °C, 1 order of magnitude higher than that of its coarse-grained form and 5 times higher than that of its single-crystalline equivalent. As a result, such nanostructured HEAs reveal strengthening figures of merit-normalized strength by the shear modulus above 1/50 and strength-to-density ratios above 0.4 MJ/kg, which are substantially higher than any previously reported values for nanocrystalline metals in the same homologous temperature range, as well as low strain-rate sensitivity of ∼0.005. Nanocrystalline HEAs with these properties represent a new class of nanomaterials for high-stress and high-temperature applications in aerospace, civilian infrastructure, and energy sectors.

Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vassal, N.; Salmon, E.; Fauvarque, J.F.

1999-01-01

Sealed alkaline solid polymer electrolyte nickel/metal hydride laboratory cells have been constructed and tested to evaluate their properties. Studies of the cycle life, self-discharge, and behavior of cells at different temperatures were carried out. The first results on the electrochemical behavior of an alkaline solid polymer electrolyte [based on poly(ethylene oxide), potassium hydroxide, and water] medium are presented here and show good reversibility of this all-solid-state system for more than 500 cycles, without significant loss of capacity and with a reasonable average discharge efficiency (close to 80%). The temperature-dependence study allowed the determination of optimum operating conditions between 0 andmore » 40 C. Characteristics of the solid polymer electrolyte based Ni/MH cells are compared to those of several other rechargeable battery systems.« less

Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

NASA Technical Reports Server (NTRS)

Zollars, G. F.

1980-01-01

These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

Method for controlled hydrogen charging of metals

DOEpatents

Cheng, Bo-Ching; Adamson, Ronald B.

1984-05-29

A method for controlling hydrogen charging of hydride forming metals through a window of a superimposed layer of a non-hydriding metal overlying the portion of the hydride forming metals to be charged.

Mechanical process for enhancing metal hydride for the anode of a Ni-MH secondary battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikeya, T.; Kumai, K.; Iwahori, T.

1993-11-01

This study attempted to find a simpler method for modifying hydrogen storage alloys that are used as anodes in Ni-MH batteries to prolong their cycle life. The alloy was modified by mechanical grinding with cobalt metal powder. A short grinding time yielded samples with a higher discharge capacity and longer cycle life than those of the alloy which was mixed with the cobalt powder without the mechanical treatment. However, prolonged grinding caused a decrease in the discharge capacity because of amorphization of the alloy by mechanical stress. The authors believed the formation of a cobalt compound on the alloy surfacemore » plus closer contact between particle enhanced the cyclic durability and discharge capacity of metal hydride anodes.« less

Doping of AlH3 with alkali metal hydrides for enhanced decomposition kinetics

NASA Astrophysics Data System (ADS)

Sandrock, Gary; Reilly, James

2005-03-01

Aluminum hydride, AlH3, has inherently high gravimetric and volumetric properties for onboard vehiclular hydrogen storage (10 wt% H2 and 0.148 kg H2/L). Yet it has been widely neglected because of its kinetic limitations for low-temperature H2 desorption and the thermodynamic difficulties associated with recharging. This paper considers a scenario whereby doped AlH3 is decomposed onboard and recharged offboard. In particular, we show that particle size control and doping with small levels of alkali metal hydrides (e.g., LiH) results in accelerated H2 desorption rates nearly high enough to supply fuel-cell and ICE vehicles. The mechanism of enhanced H2 desorption is associated with the formation of alanate windows (e.g., LiAlH4) between the AlH3 particles and the external gas phase. These alanate windows can be doped with Ti to further enhance transparency, even to the point of accomplishing slow decomposition of AlH3 at room temperature. It is highly likely 2010 gravimetric and volumetric vehicular system targets (6 wt% H2 and 0.045 kg/L) can be met with AlH3. But a new, low-cost method of offboard regeneration of spent Al back to AlH3 is yet needed.

Low-valent group 14 element hydride chemistry: towards catalysis.

PubMed

Hadlington, Terrance J; Driess, Matthias; Jones, Cameron

2018-06-05

The chemistry of group 14 element(ii) hydride complexes has rapidly expanded since the first stable example of such a compound was reported in 2000. Since that time it has become apparent that these systems display remarkable reactivity patterns, in some cases mimicking those of late transition-metal (TM) hydride compounds. This is especially so for the hydroelementation of unsaturated organic substrates. Recently, this aspect of their reactivity has been extended to the use of group 14 element(ii) hydrides as efficient, "TM-like" catalysts in organic synthesis. This review will detail how the chemistry of these hydride compounds has advanced since their early development. Throughout, there is a focus on the importance of ligand effects in these systems, and how ligand design can greatly modify a coordinated complex's electronic structure, reactivity, and catalytic efficiency.

Hydrogen interactions with metals

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Harkins, C. G.

1975-01-01

Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

The numerical approach adopted in toba computer code for mass and heat transfer dynamic analysis of metal hydride hydrogen storage beds

DOE Office of Scientific and Technical Information (OSTI.GOV)

El Osery, I.A.

1983-12-01

Modelling studies of metal hydride hydrogen storage beds is a part of an extensive R and D program conducted in Egypt on hydrogen energy. In this context two computer programs; namely RET and RET1; have been developed. In RET computer program, a cylindrical conduction bed model is considered and an approximate analytical solution is used for solution of the associated mass and heat transfer problem. This problem is solved in RET1 computer program numerically allowing more flexibility in operating conditions but still limited to cylindrical configuration with only two alternatives for heat exchange; either fluid is passing through tubes imbeddedmore » in the solid alloy matrix or solid rods are surrounded by annular fluid tubes. The present computer code TOBA is more flexible and realistic. It performs the mass and heat transfer dynamic analysis of metal hydride storage beds using a variety of geometrical and operating alternatives.« less

Mechanochemical processing for metals and metal alloys

DOEpatents

Froes, Francis H.; Eranezhuth, Baburaj G.; Prisbrey, Keith

2001-01-01

A set of processes for preparing metal powders, including metal alloy powders, by ambient temperature reduction of a reducible metal compound by a reactive metal or metal hydride through mechanochemical processing. The reduction process includes milling reactants to induce and complete the reduction reaction. The preferred reducing agents include magnesium and calcium hydride powders. A process of pre-milling magnesium as a reducing agent to increase the activity of the magnesium has been established as one part of the invention.

Reactivity of yttrium carboxylates toward alkylaluminum hydrides.

PubMed

Schädle, Christoph; Fischbach, Andreas; Herdtweck, Eberhardt; Törnroos, Karl W; Anwander, Reiner

2013-11-25

Yttrocene-carboxylate complex [Cp*2Y(OOCAr(Me))] (Cp*=C5Me5, Ar(Me) =C6H2Me3-2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare-earth-metal carboxylates. Equimolar reactions with bis-neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium-aluminum-hydride complex [{Cp*2Y(μ-H)AlMe2(μ-H)AlMe2(μ-CH3)}2] could be isolated, which features a 12-membered-ring structure. The adduct complexes [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] display identical (1)J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar (89)Y NMR shifts of δ=-88.1 ppm (R=CH2SiMe3) and δ=-86.3 ppm (R=Me) in the (89)Y DEPT45 NMR experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

DTIC Science & Technology

2016-01-04

AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT...of both Aluminum Hydride Cluster Anions and Boron Aluminum Hydride Cluster Anions with Oxygen: Anionic Products The anionic products of reactions

The role of nanocrystalline binder metallic coating into WC after additive manufacturing

NASA Astrophysics Data System (ADS)

Cavaleiro, A. J.; Fernandes, C. M.; Farinha, A. R.; Gestel, C. V.; Jhabvala, J.; Boillat, E.; Senos, A. M. R.; Vieira, M. T.

2018-01-01

Tungsten carbide with microsized particle powders are commonly used embedded in a tough binder metal. The application of these composites is not limited to cutting tools, WC based material has been increasingly used in gaskets and other mechanical parts with complex geometries. Consequently, additive manufacturing processes as Selective Laser Sintering (SLS) might be the solution to overcome some of the manufacturing problems. However, the use of SLS leads to resolve the problems resulting from difference of physical properties between tungsten carbide and the metallic binder, such as laser absorbance and thermal conductivity. In this work, an original approach of powder surface modification was considered to prepare WC-metal composite powders and overcome these constraints, consisting on the sputter-coating of the WC particle surfaces with a nanocrystalline thin film of metallic binder material (stainless steel). The coating improves the thermal behavior and rheology of the WC particles and, at the same time, ensures a binder homogenous distribution. The feasibility of the SLS technology as manufacturing process for WC powder sputter-coated with 13 wt% stainless steel AISI 304L was explored with different laser power and scanning speed parameters. The SLS layers were characterized regarding elemental distribution, phase composition and morphology, and the results are discussed emphasizing the role of the coating on the consolidation process.

Deformation-induced localized solid-state amorphization in nanocrystalline nickel.

PubMed

Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe

2012-01-01

Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification.

Deformation-induced localized solid-state amorphization in nanocrystalline nickel

PubMed Central

Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe

2012-01-01

Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification. PMID:22768383

Mössbauer studies of iron hydride at high pressure

NASA Astrophysics Data System (ADS)

Choe, I.; Ingalls, R.; Brown, J. M.; Sato-Sorensen, Y.; Mills, R.

1991-07-01

We have measured in situ Mössbauer spectra of iron hydride made in a diamond anvil cell at high pressure and room temperature. The spectra show a sudden change at 3.5+/-0.5 GPa from a single hyperfine pattern to a superposition of three. The former pattern results from normal α-iron with negligible hydrogen content, and the latter from residual α-iron plus newly formed iron hydride. Between 3.5 and 10.4 GPa, the extra hydride pattern have hyperfine fields for one ranging from 276 to 263 kOe, and the other, from 317 to 309 kOe. Both have isomer shifts of about 0.4 mm/sec, and negligible quadrupole splittings. X-ray studies on quenched samples have shown that iron hydride is of double hexagonal close-packed structure, whose two nonequivalent iron sites may account for the observation of two different patterns. Even allowing for the effect of volume expansion, the observed isomer shifts for the hydride are considerably more positive than those of other metallic phases of iron. At the same time, the hyperfine fields are slightly smaller than that of α-iron. As a possible explanation, one may expect a bonding of hydrogen with iron, which would result in a small reduction of 4s electrons, possibly accompanied by a small increase of 3d electrons compared with the neutral atom in metallic iron. The difference between the hyperfine fields in the two spectra are presumably due to the different symmetry at the two iron sites.

Integrated Cabin and Fuel Cell System Thermal Management with a Metal Hydride Heat Pump

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hovland, V.

2004-12-01

Integrated approaches for the heating and cooling requirements of both the fuel cell (FC) stack and cabin environment are critical to fuel cell vehicle performance in terms of stack efficiency, fuel economy, and cost. An integrated FC system and cabin thermal management system would address the cabin cooling and heating requirements, control the temperature of the stack by mitigating the waste heat, and ideally capture the waste heat and use it for useful purposes. Current work at the National Renewable Energy Laboratory (NREL) details a conceptual design of a metal hydride heat pump (MHHP) for the fuel cell system andmore » cabin thermal management.« less

Advanced chemical hydride-based hydrogen generation/storage system for fuel cell vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.

1998-08-01

Because of the inherent advantages of high efficiency, environmental acceptability, and high modularity, fuel cells are potentially attractive power supplies. Worldwide concerns over clean environments have revitalized research efforts on developing fuel cell vehicles (FCV). As a result of intensive research efforts, most of the subsystem technology for FCV`s are currently well established. These include: high power density PEM fuel cells, control systems, thermal management technology, and secondary power sources for hybrid operation. For mobile applications, however, supply of hydrogen or fuel for fuel cell operation poses a significant logistic problem. To supply high purity hydrogen for FCV operation, Thermomore » Power`s Advanced Technology Group is developing an advanced hydrogen storage technology. In this approach, a metal hydride/organic slurry is used as the hydrogen carrier and storage media. At the point of use, high purity hydrogen will be produced by reacting the metal hydride/organic slurry with water. In addition, Thermo Power has conceived the paths for recovery and regeneration of the spent hydride (practically metal hydroxide). The fluid-like nature of the spent hydride/organic slurry will provide a unique opportunity for pumping, transporting, and storing these materials. The final product of the program will be a user-friendly and relatively high energy storage density hydrogen supply system for fuel cell operation. In addition, the spent hydride can relatively easily be collected at the pumping station and regenerated utilizing renewable sources, such as biomass, natural, or coal, at the central processing plants. Therefore, the entire process will be economically favorable and environmentally friendly.« less

Current status of environmental, health, and safety issues of nickel metal-hydride batteries for electric vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corbus, D; Hammel, C J; Mark, J

1993-08-01

This report identifies important environment, health, and safety issues associated with nickel metal-hydride (Ni-MH) batteries and assesses the need for further testing and analysis. Among the issues discussed are cell and battery safety, workplace health and safety, shipping requirements, and in-vehicle safety. The manufacture and recycling of Ni-MH batteries are also examined. This report also overviews the ``FH&S`` issues associated with other nickel-based electric vehicle batteries; it examines venting characteristics, toxicity of battery materials, and the status of spent batteries as a hazardous waste.

Hydride compositions

DOEpatents

Lee, Myung, W.

1994-01-01

Disclosed are a composition for use in storing hydrogen and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the H equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to H, and then heating below the softening temperature of any of the constituents. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P{sub H}{sub 2} and determining H/M from the isothermic function of the composition.

Hydride compositions

DOEpatents

Lee, Myung W.

1995-01-01

A composition for use in storing hydrogen, and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the hydrogen equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to hydrogen and then heating at a temperature below the softening temperature of any of the. constituents so that their chemical and structural integrity is preserved. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P.sub.H.sbsb.2 and determining H/M from the isothermic function of the composition.

Effect of amorphous Mg{sub 50}Ni{sub 50} on hydriding and dehydriding behavior of Mg{sub 2}Ni alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guzman, D., E-mail: danny.guzman@uda.cl; Ordonez, S.; Fernandez, J.F.

Composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50} was prepared by mechanical milling starting with nanocrystalline Mg{sub 2}Ni and amorphous Mg{sub 50}Ni{sub 50} powders, by using a SPEX 8000 D mill. The morphological and microstructural characterization of the powders was performed via scanning electron microscopy and X-ray diffraction. The hydriding characterization of the composite was performed via a solid gas reaction method in a Sievert's-type apparatus at 363 K under an initial hydrogen pressure of 2 MPa. The dehydriding behavior was studied by differential thermogravimetry. On the basis of the results, it is possible to conclude that amorphous Mg{submore » 50}Ni{sub 50} improved the hydriding and dehydriding kinetics of Mg{sub 2}Ni alloy upon cycling. A tentative rationalization of experimental observations is proposed. - Research Highlights: {yields} First study of the hydriding behavior of composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50}. {yields} Microstructural characterization of composite material using XRD and SEM was obtained. {yields} An improved effect of Mg{sub 50}Ni{sub 50} on the Mg{sub 2}Ni hydriding behavior was verified. {yields} The apparent activation energy for the hydrogen desorption of composite was obtained.« less

Nanocrystalline copper films are never flat

NASA Astrophysics Data System (ADS)

Zhang, Xiaopu; Han, Jian; Plombon, John J.; Sutton, Adrian P.; Srolovitz, David J.; Boland, John J.

2017-07-01

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy.

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

Effects of oxide distributed in grain boundaries on microstructure stability of nanocrystalline metals

NASA Astrophysics Data System (ADS)

Zhou, Kai; Li, Hui; Biao Pang, Jin; Wang, Zhu

2013-06-01

Nanocrystalline copper and zinc prepared by high-pressure compaction method have been studied by positron lifetime spectroscopy associated with X-ray diffraction. For nanocrystalline Cu, mean grain sizes of the samples decrease after being annealed at 900 °C and increase during aging at 180 °C, revealing that the atoms exchange between the two regions. The positron lifetime results indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder the grain growth during the ageing at 180 °C, and the vacancy clusters inside the disorder regions which are related to Cu2O need longer aging time to decompose. In the case of nanocrystalline Zn, the open volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ1). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τav) during the annealing, which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. For both nanocrystalline copper and zinc, the oxides in grain boundaries enhance the thermal stability of the microstucture, in spite of their different crystal structures. This effect is very important for the nanocrystalline materials using as radiation resistant materials.

The reactivity of sodium alanates with O[2], H[2]O, and CO[2] : an investigation of complex metal hydride contamination in the context of automotive systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dedrick, Daniel E.; Bradshaw, Robert W.; Behrens, Richard, Jr.

2007-08-01

Safe and efficient hydrogen storage is a significant challenge inhibiting the use of hydrogen as a primary energy carrier. Although energy storage performance properties are critical to the success of solid-state hydrogen storage systems, operator and user safety is of highest importance when designing and implementing consumer products. As researchers are now integrating high energy density solid materials into hydrogen storage systems, quantification of the hazards associated with the operation and handling of these materials becomes imperative. The experimental effort presented in this paper focuses on identifying the hazards associated with producing, storing, and handling sodium alanates, and thus allowingmore » for the development and implementation of hazard mitigation procedures. The chemical changes of sodium alanates associated with exposure to oxygen and water vapor have been characterized by thermal decomposition analysis using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and X-ray diffraction methods. Partial oxidation of sodium alanates, an alkali metal complex hydride, results in destabilization of the remaining hydrogen-containing material. At temperatures below 70 C, reaction of sodium alanate with water generates potentially combustible mixtures of H{sub 2} and O{sub 2}. In addition to identifying the reaction hazards associated with the oxidation of alkali-metal containing complex hydrides, potential treatment methods are identified that chemically stabilize the oxidized material and reduce the hazard associated with handling the contaminated metal hydrides.« less

Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

PubMed

Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

2018-01-25

We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

Nanocrystalline CuNi alloys: improvement of mechanical properties and thermal stability

NASA Astrophysics Data System (ADS)

Nogues, Josep; Varea, A.; Pellicer, E.; Sivaraman, K. M.; Pane, S.; Nelson, B. J.; Surinach, S.; Baro, M. D.; Sort, J.

2014-03-01

Nanocrystalline metallic films are known to benefit from novel and enhanced physical and chemical properties. In spite of these outstanding properties, nanocrystalline metals typically show relatively poor thermal stability which leads to deterioration of the properties due to grain coarsening. We have studied nanocrystalline Cu1-xNix (0.56 < x < 1) thin films (3 μm-thick) electrodeposited galvanostatically onto Cu/Ti/Si (100) substrates. CuNi thin films exhibit large values of hardness (6.15 < H < 7.21 GPa), which can be tailored by varying the composition. However, pure Ni films (x = 1) suffer deterioration of their mechanical and magnetic properties after annealing during 3 h at relatively low temperatures (TANN > 475 K) due to significant grain growth. Interestingly, alloying Ni with Cu clearly improves the thermal stability of the material because grain coarsening is delayed due to segregation of a Cu-rich phase at grain boundaries, thus preserving both the mechanical and magnetic properties up to higher TANN.

Effect of hydrogenation conditions on the microstructure and mechanical properties of zirconium hydride

NASA Astrophysics Data System (ADS)

Muta, Hiroaki; Nishikane, Ryoji; Ando, Yusuke; Matsunaga, Junji; Sakamoto, Kan; Harjo, Stefanus; Kawasaki, Takuro; Ohishi, Yuji; Kurosaki, Ken; Yamanaka, Shinsuke

2018-03-01

Precipitation of brittle zirconium hydrides deteriorate the fracture toughness of the fuel cladding tubes of light water reactor. Although the hydride embrittlement has been studied extensively, little is known about physical properties of the hydride due to the experimental difficulties. In the present study, to elucidate relationship between mechanical properties and microstructure, two δ-phase zirconium hydrides and one ε-phase zirconium hydride were carefully fabricated considering volume changes at the metal-to-hydride transformation. The δ-hydride that was fabricated from α-zirconium exhibits numerous inner cracks due to the large volume change. Analyses of the neutron diffraction pattern and electron backscatter diffraction (EBSD) data show that the sample displays significant stacking faults in the {111} plane and in the pseudo-layered microstructure. On the other hand, the δ-hydride sample fabricated from β-zirconium at a higher temperature displays equiaxed grains and no cracks. The strong crystal orientation dependence of mechanical properties were confirmed by indentation test and EBSD observation. The δ-hydride hydrogenated from α-zirconium displays a lower Young's modulus than that prepared from β-zirconium. The difference is attributed to stacking faults within the {111} plane, for which the Young's modulus exhibits the highest value in the perpendicular direction. The strong influence of the crystal orientation and dislocation density on the mechanical properties should be considered when evaluating hydride precipitates in nuclear fuel cladding.

Complex hydrides for hydrogen storage

DOEpatents

Zidan, Ragaiy

2006-08-22

A hydrogen storage material and process of forming the material is provided in which complex hydrides are combined under conditions of elevated temperatures and/or elevated temperature and pressure with a titanium metal such as titanium butoxide. The resulting fused product exhibits hydrogen desorption kinetics having a first hydrogen release point which occurs at normal atmospheres and at a temperature between 50.degree. C. and 90.degree. C.

Simultaneous plate forming and hydriding of La(Fe, Si)13 magnetocaloric powders

NASA Astrophysics Data System (ADS)

Yang, Nannan; You, Caiyin; Tian, Na; Zhang, Yue; Leng, Haiyan; He, Jun

2018-04-01

In this work, we propose a way to simultaneously realize the plate forming and hydriding of La(Fe, Si)13 powders by mixing hydride MgNiYHx and solder powders Sn3.0Ag0.5Cu. Under the annealing of the green compact, the hydriding of La(Fe, Si)13 was realized through absorbing the released hydrogen from the metallic hydride MgNiYHx. The Curie temperature of La(Fe, Si)13 alloy increased from 213 K to 333 K and hysteresis reduced from 3.3 J/kg·K to 1.33 J/kg·K. Due to the bonding of Sn3.0Ag0.5Cu powders, the mechanical strength of the composite compact was highly improved in comparison to the compact of La(Fe, Si)13 powders alone.

Grain Size Threshold for Enhanced Irradiation Resistance in Nanocrystalline and Ultrafine Tungsten

DOE PAGES

El Atwani, Osman; Hinks, Jonathan; Greaves, Graeme; ...

2017-02-21

Nanocrystalline metals are considered highly radiation-resistant materials due to their large grain boundary areas. Here, the existence of a grain size threshold for enhanced irradiation resistance in high-temperature helium-irradiated nanocrystalline and ultrafine tungsten is demonstrated. Average bubble density, projected bubble area and the corresponding change in volume were measured via transmission electron microscopy and plotted as a function of grain size for two ion fluences. Nanocrystalline grains of less than 35 nm size possess ~10–20 times lower change in volume than ultrafine grains and this is discussed in terms of the grain boundaries defect sink efficiency.

Characterization of corrosion products of AB{sub 5}-type hydrogen storage alloys for nickel-metal hydride batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maurel, F.; Knosp, B.; Backhaus-Ricoult, M.

2000-01-01

To better understand the decrease in storage capacity of AB{sub 5}-type alloys in rechargeable Ni/MH batteries undergoing repeated charge/discharge cycles, the corrosion of a MnNi{sub 3.55}Co{sub 0.75}Mn{sub 0.4}Al{sub 0.3} alloy in aqueous KOH electrolyte was studied. The crystal structure, chemical composition, and distribution of corrosion products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Hollow and filed needles of a mixed rare earth hydroxide Mn(OH){sub 3} were found to cover a continuous nanocrystalline corrosion scale composed of metal (Ni, Co) solid solution, oxide (Ni,Co)O solid solution and rare earth hydroxide, and a Mn-depleted alloy subscale. Corrosionmore » kinetics were measured for three different temperatures. Growth kinetics of the continuous corrosion scale and of the Mm(OH){sub 3} needles obeyed linear and parabolic rate laws, respectively. Models for the corrosion mechanism were developed on the basis of diffusional transport of Mn and OH through the hydroxide needles and subsequent diffusion along grain boundaries through the nanocrystalline scale.« less

Bulk Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

DTIC Science & Technology

2014-05-13

nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and...the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta...approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are

Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

NASA Technical Reports Server (NTRS)

Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

1993-01-01

Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

"Bulk" Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

NASA Astrophysics Data System (ADS)

Tschopp, M. A.; Murdoch, H. A.; Kecskes, L. J.; Darling, K. A.

2014-06-01

It is a new beginning for innovative fundamental and applied science in nanocrystalline materials. Many of the processing and consolidation challenges that have haunted nanocrystalline materials are now more fully understood, opening the doors for bulk nanocrystalline materials and parts to be produced. While challenges remain, recent advances in experimental, computational, and theoretical capability have allowed for bulk specimens that have heretofore been pursued only on a limited basis. This article discusses the methodology for synthesis and consolidation of bulk nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta system, consolidated via equal channel angular extrusion, with properties rivaling that of nanocrystalline pure Ta. Moreover, modeling and simulation approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are briefly reviewed and discussed. Integrating experiments and computational materials science for synthesizing bulk nanocrystalline materials can bring about the next generation of ultrahigh strength materials for defense and energy applications.

Materials for Hydrogen Storage: From Nanostructures to Complex Hydrides

NASA Astrophysics Data System (ADS)

Jena, Puru

2006-03-01

The limited supply of fossil fuels, its adverse effect on the environment, and growing worldwide demand for energy has necessitated the search for new and clean sources of energy. The possibility of using hydrogen to meet this growing energy need has rekindled interest in the study of safe, efficient, and economical storage of hydrogen. This talk will discuss the issues and challenges in storing hydrogen in light complex hydrides and discuss the role of nanostructuring and catalysts that can improve the thermodynamics and kinetics of hydrogen. In particular, we will discuss how studies of clusters can help elucidate the fundamental mechanisms for hydrogen storage and how these can be applied in Boron Nitride and Carbon nanocages and how metallization of these nanostructures is necessary to store hydrogen with large gravimetric density. We will also discuss the properties of complex light metal hydrides such as alanates and magnesium hydrides that can store up to 18 wt % hydrogen, although the temperature where hydrogen desorbs is rather high. Using first principles calculations, we will provide a fundamental understanding of the electronic structure and stability of these systems and how it is affected due to catalysts. It is hoped that the understanding gained here can be useful in designing better catalysts as well as hosts for hydrogen storage.

Comparison of ``AA`` nickel metal hydride cells with ``AA`` Ni-Cd cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alminauskas, V.; Johnson, W.

1996-12-31

This paper compares ``AA`` size nickel metal hydride (Ni-HM) cells with comparable ``AA;; nickel cadmium (Ni-Cd) cells both of which were obtained in 1993. The Ni-MH cells were found to be a suitable substitute for conventional Ni-Cd cells. Both these cell types have similar voltages and discharge characteristics. The Ni-MH cells, though had nearly twice the capacity as comparable Ni-Cd cells. There was no significant difference in self discharge between the two types of cells. The Ni-MH cells also performed as well as Ni-Cd cells at rates lower than 5 amperes and at temperatures higher than 0 C (32 F).more » The most interesting finding is that the Ni-MH cells showed an irreversible decay of the discharge voltage with each cycle which was more noticeable during pulses. Eventually the Ni-MH packs fail, not because of loss of capacity, but because of low voltage during the pulse.« less

Hydride compressor

DOEpatents

Powell, James R.; Salzano, Francis J.

1978-01-01

Method of producing high energy pressurized gas working fluid power from a low energy, low temperature heat source, wherein the compression energy is gained by using the low energy heat source to desorb hydrogen gas from a metal hydride bed and the desorbed hydrogen for producing power is recycled to the bed, where it is re-adsorbed, with the recycling being powered by the low energy heat source. In one embodiment, the adsorption-desorption cycle provides a chemical compressor that is powered by the low energy heat source, and the compressor is connected to a regenerative gas turbine having a high energy, high temperature heat source with the recycling being powered by the low energy heat source.

Aging of Nanocrystalline Mackinawite (FeS): Mineralogical and Physicochemical Properties

NASA Astrophysics Data System (ADS)

Jeong, H. Y.; Lee, H.

2011-12-01

Due to the extraordinary physical properties and high surface areas, nanocrystalline minerals have been widely investigated for their potential uses in treating contaminated groundwaters and surface waters. Most previous studies in this field have focused on either preparation of nanocrystalline minerals or measurement of their reactivity with environmental contaminants. Nanocrystalline minerals, due to the inherent thermodynamic instability, tend to change the physicochemical and mineralogical properties over time, usually resulting in the decreased reactivity. Thus, to better assess the long-term effectiveness of nanocrystalline minerals in field applications, such "aging" effects should be clearly delineated. In the present work, we have investigated the aging impact on nanocrystalline mackinawite (FeS), the ubiquitous Fe-bearing mineral in anoxic sulfidic sediments. Mackinawite (FeS) is known to be an effective scavenger for metal pollutants and a strong reducing reagent for chromate and chlorinated organic compounds. Our preliminary results indicate that nanocrystalline FeS ages via Ostwald ripening, particle aggregation, or mineralogical transformation. By X-ray diffraction (XRD) analysis, aging of nanocrystalline FeS via Ostwald ripening is found to be dominant at acidic pH. Cryogenic transmission electron microscopy (TEM) shows that particle aggregation is most evident at neutral pH. Transformation of nanosized FeS into a more thermodynamically stable greigite (Fe3S4) is observed in the presence of folic acid at acidic pH. The pH-dependent aging process may be linked with changes in the apparent solubility and surface charge of FeS with pH. The Ostwald ripening or particle aggregation of nanocrystalline FeS leads to the decrease surface area, thus causing the decreased reactivity. Given the less reactivity of greigite, the transformation of nanocrystalline FeS to greigite is also expected to result in the decreased reactivity.

Charging/discharging stability of a metal hydride battery electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geng, M.; Han, J.; Feng, F.

1999-07-01

The metal hydride (MH) alloy powder for the negative electrode of the Ni/MH battery was first pulverized and oxidized by electrochemically charging and discharging for a number of cycles. The plate of the negative electrode of an experimental cell in this study was made from a mixture of a multicomponent AB{sub 5}-based alloy powder, nickel powder, and polytetra fluoroethylene (PTFE). The characteristics of the negative electrode, including discharge capacity, exchange current density, and hydrogen diffusivity, were studied by means of the electrochemical experiments and analysis in an experimental cell. The exchange current density of a Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{submore » 0.35}Al{sub 0.35} alloy electrode increases with increasing number of charge/discharge cycles and then remains almost constant after 20 cycles. A microcracking activation, resulting from an increase in reaction surface area and an improvement in the electrode surface activation, increases the hydrogen exchange current densities. Measurement of hydrogen diffusivities for Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} alloy powder shows that the ratio of D/a{sup 2} (D = hydrogen diffusivity; a = sphere radius) increases with increasing number of cycles but remains constant after 20 cycles.« less

Pyrophoric behaviour of uranium hydride and uranium powders

NASA Astrophysics Data System (ADS)

Le Guyadec, F.; Génin, X.; Bayle, J. P.; Dugne, O.; Duhart-Barone, A.; Ablitzer, C.

2010-01-01

Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (<0.5 wt.%) was obtained by heat treatment at low temperature in flowing Ar/5%H2. Pure uranium powder was obtained by dehydration in flowing pure argon. Those fine powders showed spontaneous ignition at room temperature in air. An in situ CCD-camera displayed ignition associated with powder temperature measurement. Characterization of powders before and after ignition was performed by XRD measurements and SEM observations. Oxidation mechanisms are proposed.

Optical hydrogen sensors based on metal-hydrides

NASA Astrophysics Data System (ADS)

Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

2012-06-01

For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

PubMed

Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

2016-02-01

Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Body centered cubic magnesium niobium hydride with facile room temperature absorption and four weight percent reversible capacity.

PubMed

Tan, XueHai; Wang, Liya; Holt, Chris M B; Zahiri, Beniamin; Eikerling, Michael H; Mitlin, David

2012-08-21

We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic destabilization relative to the baseline -77 kJ mol(-1) H(2) for rutile MgH(2). The hydrogenation cycling kinetics are remarkable. At room temperature and 1 bar hydrogen it takes 30 minutes to absorb a 1.5 μm thick film at sorption cycle 1, and 1 minute at cycle 5. Reversible desorption is achieved in about 60 minutes at 175 °C. Using ab initio calculations we have examined the thermodynamic stability of metallic alloys with hexagonal close packed (hcp) versus bcc crystal structure. Moreover we have analyzed the formation energies of the alloy hydrides that are bcc, rutile or fluorite.

Prototype design of a wearable metal hydride actuator using a soft bellows for motor rehabilitation.

PubMed

Ino, Shuichi; Sato, Mitsuru; Hosono, Minako; Nakajima, Sawako; Yamashita, Kazuhiko; Tanaka, Toshiaki; Izumi, Takashi

2008-01-01

A bedside and home rehabilitation system for people with motor disabilities due to stroke or the aging process requires a human-compatible actuator with softness, low noise and a high power-to-weight ratio. To achieve these types of joint motor rehabilitation systems, we designed a wearable metal hydride (MH) actuator using a soft bellows. The purpose of the current study is the development the soft and light bellows made of a polymer laminate film for the MH actuator. As a result of experimental tests, this soft bellows weighs 20 times less and stretches 30 times longer than the metal bellows used in a conventional MH actuator, and it has hydrogen impermeability, flex durability and adequate compliance for human joints. The MH actuator using the soft bellows can drive at a slow and safe enough speed for motor rehabilitation of patients' limbs. These preliminary findings support the efficacy of an MH actuator with a soft bellows for the purpose of developing a system for motor rehabilitation or human power assist.

Multi-scale characterization of nanostructured sodium aluminum hydride

NASA Astrophysics Data System (ADS)

NaraseGowda, Shathabish

Complex metal hydrides are the most promising candidate materials for onboard hydrogen storage. The practicality of this class of materials is counter-poised on three critical attributes: reversible hydrogen storage capacity, high hydrogen uptake/release kinetics, and favorable hydrogen uptake/release thermodynamics. While a majority of modern metallic hydrides that are being considered are those that meet the criteria of high theoretical storage capacity, the challenges lie in addressing poor kinetics, thermodynamics, and reversibility. One emerging strategy to resolve these issues is via nanostructuring or nano-confinement of complex hydrides. By down-sizing and scaffolding them to retain their nano-dimensions, these materials are expected to improve in performance and reversibility. This area of research has garnered immense interest lately and there is active research being pursued to address various aspects of nanostructured complex hydrides. The research effort documented here is focused on a detailed investigation of the effects of nano-confinement on aspects such as the long range atomic hydrogen diffusivities, localized hydrogen dynamics, microstructure, and dehydrogenation mechanism of sodium alanate. A wide variety of microporous and mesoporous materials (metal organic frameworks, porous silica and alumina) were investigated as scaffolds and the synthesis routes to achieve maximum pore-loading are discussed. Wet solution infiltration technique was adopted using tetrahydrofuran as the medium and the precursor concentrations were found to have a major role in achieving maximum pore loading. These concentrations were optimized for each scaffold with varying pore sizes and confinement was quantitatively characterized by measuring the loss in specific surface area. This work is also aimed at utilizing neutron and synchrotron x-ray characterization techniques to study and correlate multi-scale material properties and phenomena. Some of the most advanced

Nanostructured Mg 2Ni materials prepared by cold rolling and used as negative electrode for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Pedneault, Sylvain; Huot, Jacques; Roué, Lionel

In the present work, cold rolling has been investigated as a new means of producing Mg-based metal hydrides for nickel-metal hydride (Ni-MH) batteries. Structure and electrochemical evolution of 2Mg-Ni cold-rolled samples were investigated as a function of the number of rolling passes as well as heat treatment. It was found that nanocrystalline Mg 2Ni alloy can be obtained by an appropriate three step process involving rolling, heat treatment and rolling again. It was shown that the number of primary and secondary rolling passes must be carefully optimized in order to favour the complete formation of Mg 2Ni alloy having a nanocrystalline structure (∼10 nm in crystallite size) without excessive sample oxidation. Actually, the best result was obtained by first rolling 90 times, followed by a heat treatment at 400 °C for 4 h and roll again 20 times. The resulting material displayed an initial discharge capacity of 205 mAh g -1, which is quite similar to that obtained with ball-milled Mg 2Ni alloy.

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

Nanocrystalline copper films are never flat.

PubMed

Zhang, Xiaopu; Han, Jian; Plombon, John J; Sutton, Adrian P; Srolovitz, David J; Boland, John J

2017-07-28

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride.

PubMed

Cammarota, Ryan C; Vollmer, Matthew V; Xie, Jing; Ye, Jingyun; Linehan, John C; Burgess, Samantha A; Appel, Aaron M; Gagliardi, Laura; Lu, Connie C

2017-10-11

Large-scale CO 2 hydrogenation could offer a renewable stream of industrially important C 1 chemicals while reducing CO 2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO 2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h -1 ), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d 10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

Probing the chemistry of nickel/metal hydride battery cells using electrochemical impedance spectroscopy

NASA Technical Reports Server (NTRS)

Isaac, Bryan J.

1994-01-01

Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for investigating the chemical and physical processes occurring at electrode surfaces. It offers information about electron transfer at interfaces, kinetics of reactions, and diffusion characteristics of the bulk phase between the electrodes. For battery cells, this technique offers another advantage in that it can be done without taking the battery apart. This non-destructive analysis technique can thus be used to gain a better understanding of the processes occurring within a battery cell. This also raises the possibility of improvements in battery design and identification or prediction of battery characteristics useful in industry and aerospace applications. EIS as a technique is powerful and capable of yielding significant information about the cell, but it also requires that the many parameters under investigation can be resolved. This implies an understanding of the processes occurring in a battery cell. Many battery types were surveyed in this work, but the main emphasis was on nickel/metal hydride batteries.

Metal hydride and pyrophoric fuel additives for dicyclopentadiene based hybrid propellants

NASA Astrophysics Data System (ADS)

Shark, Steven C.

The purpose of this study is to investigate the use of reactive energetic fuel additives that have the potential to increase the combustion performance of hybrid rocket propellants in terms of solid fuel regression rate and combustion efficiency. Additives that can augment the combustion flame zone in a hybrid rocket motor by means of increased energy feedback to the fuel grain surface are of great interest. Metal hydrides have large volumetric hydrogen densities, which gives these materials high performance potential as fuel additives in terms of specifc impulse. The excess hydrogen and corresponding base metal may also cause an increase in the hybrid rocket solid fuel regression rate. Pyrophoric additives also have potential to increase the solid fuel regression rate by reacting more readily near the burning fuel surface providing rapid energy feedback. An experimental performance evaluation of metal hydride fuel additives for hybrid rocket motor propulsion systems is examined in this study. Hypergolic ignition droplet tests and an accelerated aging study revealed the protection capabilities of Dicyclopentadiene (DCPD) as a fuel binder, and the ability for unaided ignition. Static hybrid rocket motor experiments were conducted using DCPD as the fuel. Sodium borohydride (NabH4) and aluminum hydride (AlH3) were examined as fuel additives. Ninety percent rocket grade hydrogen peroxide (RGHP) was used as the oxidizer. In this study, the sensitivity of solid fuel regression rate and characteristic velocity (C*) efficiency to total fuel grain port mass flux and particle loading is examined. These results were compared to HTPB combustion performance as a baseline. Chamber pressure histories revealed steady motor operation in most tests, with reduced ignition delays when using NabH4 as a fuel additive. The addition of NabH4 and AlH3 produced up to a 47% and 85% increase in regression rate over neat DCPD, respectively. For all test conditions examined C* efficiency ranges

Boron hydride polymer coated substrates

DOEpatents

Pearson, R.K.; Bystroff, R.I.; Miller, D.E.

1986-08-27

A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

Boron hydride polymer coated substrates

DOEpatents

Pearson, Richard K.; Bystroff, Roman I.; Miller, Dale E.

1987-01-01

A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

Synthesis and structural study of Ti-rich Mg-Ti hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asano, Kohta; Kim, Hyunjeong; Sakaki, Kouji

2014-02-26

Mg xTi 1-x (x = 0.15, 0.25, 0.35) alloys were synthesized by means of ball milling. Under a hydrogen pressure of 8 MPa at 423 K these Mg–Ti alloys formed a hydride phase with a face centered cubic (FCC) structure. The hydride for x = 0.25 consisted of single Mg 0.25Ti 0.75H 1.62 FCC phase but TiH 2 and MgH 2 phases were also formed in the hydrides for x = 0.15 and 0.35, respectively. X-ray diffraction patterns and the atomic pair distribution function indicated that numbers of stacking faults were introduced. There was no sign of segregation between Mgmore » and Ti in Mg 0.25Ti 0.75H 1.62. Electronic structure of Mg 0.25Ti 0.75H 1.62 was different from those of MgH 2 and TiH 2, which was demonstrated by 1H nuclear magnetic resonance. This strongly suggested that stable Mg–Ti hydride phase was formed in the metal composition of Mg 0.25Ti 0.75 without disproportion into MgH 2 and TiH 2.« less

17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING SYSTEM WAS PART OF THE FAST ENRICHED URANIUM RECOVERY PROCESS. (11/11/59) - Rocky Flats Plant, General Manufacturing, Support, Records-Central Computing, Southern portion of Plant, Golden, Jefferson County, CO

Zirconium hydride containing explosive composition

DOEpatents

Walker, Franklin E.; Wasley, Richard J.

1981-01-01

An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising a non-explosive compound or mixture of non-explosive compounds which when subjected to an energy fluence of 1000 calories/cm.sup.2 or less is capable of releasing free radicals each having a molecular weight between 1 and 120. Exemplary donor additives are dibasic acids, polyamines and metal hydrides.

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Multiscale modeling of localized resistive heating in nanocrystalline metals subjected to electropulsing

NASA Astrophysics Data System (ADS)

Zhao, Jingyi; Wang, G.-X.; Dong, Yalin; Ye, Chang

2017-08-01

Many electrically assisted processes have been reported to induce changes in microstructure and metal plasticity. To understand the physics-based mechanisms behind these interesting phenomena, however, requires an understanding of the interaction between the electric current and heterogeneous microstructure. In this work, multiscale modeling of the electric current flow in a nanocrystalline material is reported. The cellular automata method was used to track the nanoscale grain boundaries in the matrix. Maxwell's electromagnetic equations were solved to obtain the electrical potential distribution at the macro scale. Kirchhoff's circuit equation was solved to obtain the electric current flow at the micro/nano scale. The electric current distribution at two representative locations was investigated. A significant electric current concentration was observed near the grain boundaries, particularly near the triple junctions. This higher localized electric current leads to localized resistive heating near the grain boundaries. The electric current distribution could be used to obtain critical information such as localized resistive heating rate and extra system free energy, which are critical for explaining many interesting phenomena, including microstructure evolution and plasticity enhancement in many electrically assisted processes.

Silver film on nanocrystalline TiO{sub 2} support: Photocatalytic and antimicrobial ability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vukoje, Ivana D., E-mail: ivanav@vinca.rs; Tomašević-Ilić, Tijana D., E-mail: tommashev@gmail.com; Zarubica, Aleksandra R., E-mail: zarubica2000@yahoo.com

Highlights: • Simple photocatalytic rout for deposition of Ag on nanocrystalline TiO{sub 2} films. • High antibactericidal efficiency of deposited Ag on TiO{sub 2} support. • Improved photocatalytic performance of TiO{sub 2} films in the presence of deposited Ag. - Abstract: Nanocrystalline TiO{sub 2} films were prepared on glass slides by the dip coating technique using colloidal solutions consisting of 4.5 nm particles as a precursor. Photoirradiation of nanocrystalline TiO{sub 2} film modified with alanine that covalently binds to the surface of TiO{sub 2} and at the same time chelate silver ions induced formation of metallic silver film. Optical andmore » morphological properties of thin silver films on nanocrystalline TiO{sub 2} support were studied by absorption spectroscopy and atomic force microscopy. Improvement of photocatalytic performance of nanocrystalline TiO{sub 2} films after deposition of silver was observed in degradation reaction of crystal violet. Antimicrobial ability of deposited silver films on nanocrystalline TiO{sub 2} support was tested in dark as a function of time against Escherichia coli, Staphylococcus aureus, and Candida albicans. The silver films ensured maximum cells reduction of both bacteria, while the fungi reduction reached satisfactory 98.45% after 24 h of contact.« less

Understanding the low temperature electrical properties of nanocrystalline tin oxide for gas sensor applications

NASA Astrophysics Data System (ADS)

Drake, Christina Hartsell

Nanocrystalline metal/metal oxide is an important class of transparent and electronic materials due to its potential use in many applications, including gas sensors. At the nanoscale, many of the phenomena observed that give nanocrystalline semiconducting oxide enhanced performance as a gas sensor material over other conventional engineering materials is still poorly understood. This study is aimed at understanding the low temperature electrical and chemical properties of nanocrystalline SnO2 that makes it suitable for room temperature gas detectors. Studies were carried out in order to understand how various synthesis methods affect the surfaces on the nano-oxides, interactions of a target gas (in this study hydrogen) with different surface species, and changes in the electrical properties as a function of dopants and grain size. A correlation between the surface reactions and the electrical response of doped nanocrystalline metal-oxide-semiconductors exposed to a reducing gas is established using Fourier Transform Infrared (FTIR) Spectroscopy attached to a specially built custom designed catalytic cell. First principle calculations of oxygen vacancy concentrations from absorbance spectra are presented. FTIR is used for effectively screening of these nanostructures for gas sensing applications. The effect of processing temperature on the microstructural evolution and on the electronic properties of nanocrystalline trivalent doped-SnO 2 is also presented. This study includes the effect of dopants (In and Ce) on the growth of nano-SnO2, as well as their effects on the electronic properties and gas sensor behavior of the nanomaterial at room temperature. Band bending affects are also investigated for this system and are related to enhanced low temperature gas sensing. The role and importance of oxygen vacancies in the electronic and chemical behavior of surface modified nanocrystalline SnO2 are explored in this study. A generalized explanation for the low temperature

Metal hydride heat pump engineering demonstration and evaluation model

NASA Technical Reports Server (NTRS)

Lynch, Franklin E.

1993-01-01

Future generations of portable life support systems (PLSS's) for space suites (extravehicular mobility units or EMU's) may require regenerable nonventing thermal sinks (RNTS's). For purposes of mobility, a PLSS must be as light and compact as possible. Previous venting PLSS's have employed water sublimators to reject metabolic and equipment heat from EMU's. It is desirable for long-duration future space missions to minimize the use of water and other consumables that need to be periodically resupplied. The emission of water vapor also interferes with some types of instrumentation that might be used in future space exploration. The test article is a type of RNTS based on a metal hydride heat pump (MHHP). The task of reservicing EMU's after use must be made less demanding in terms of time, procedures, and equipment. The capability for quick turnaround post-EVA servicing (30 minutes) is a challenging requirement for many of the RNTS options. The MHHP is a very simple option that can be regenerated in the airlock within the 30 minute limit by the application of a heating source and a cooling sink. In addition, advanced PLSS's must provide a greater degree of automatic control, relieving astronauts of the need to manually adjust temperatures in their liquid cooled ventilation garments (LCVG's). The MHHP includes automatic coolant controls with the ability to follow thermal load swings from minimum to maximum in seconds. The MHHP includes a coolant loop subsystem with pump and controls, regeneration equipment for post-EVA servicing, and a PC-based data acquisition and control system (DACS).

Mechanical properties of nanocrystalline cobalt

NASA Astrophysics Data System (ADS)

Karimpoor, Amir A.; Erb, Uwe

2006-05-01

Due to their excellent wear and corrosion properties, nanocrystalline cobalt and several cobalt alloys made by electrodeposition are currently being developed as environmentally benign replacement coatings for hard chromium electrodeposits. The focus of this study is on the mechanical properties of nanocrystalline cobalt, which are currently not well understood. A comparison is presented for hardness, tensile properties, Charpy impact properties and fracture surface analysis of both nanocrystalline (grain size: 12 nm) and conventional polycrystalline (grain size: 4.8 m) cobalt. It is shown that the hardness and tensile strength of nanocrystalline cobalt is 2-3 times higher than for polycrystalline cobalt. However, in contrast to other nanocrystalline materials tested previously, nanocrystalline cobalt retains considerable ductility with elongation to fracture values up to 7%.

Thick-film nickel-metal-hydride battery based on porous ceramic substrates

NASA Astrophysics Data System (ADS)

Do, Jing-Shan; Yu, Sen-Hao; Cheng, Suh-Fen

Nickel-metal-hydride (Ni-MH) batteries are prepared with thick-film and thin-film technologies based on porous ceramic substrates. The porosity and the mean pore diameter of BP ceramic substrates prepared from the argils increases from 19.81% and 0.0432 μm to 29.81% and 0.224 μm, respectively, upon increasing the ethyl cellulose content in the BP argil from 0 to 0.79%. The pore diameter of Al 2O 3 substrates prepared from Al 2O 3 powder is mainly distributed in the range 0.01-0.5 μm. The distribution of the pore diameters of BP ceramic substrates lies in two ranges, namely: 0.04-2 μm and 10-300 μm. Using BP ceramic plates and Al 2O 3 plates as substrates to fabricate thick-film Ni-MH batteries, the optimal electroactive material utilization in the batteries is 77.0 and 71.1%, respectively. On increasing the screen-printing number for preparing the cathode (Ni(OH) 2) from 1 to 3, the discharge capacity of the thick-film battery increases from 0.2917 to 0.7875 mAh, and the utilization in the battery decreases from 71.0 to 53.0%.

Fundamental experiments on hydride reorientation in zircaloy

NASA Astrophysics Data System (ADS)

Colas, Kimberly B.

In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and

SINTERING METAL OXIDES

DOEpatents

Roake, W.E.

1960-09-13

A process is given for producing uranium dioxide material of great density by preparing a compacted mixture of uranium dioxide and from 1 to 3 wt.% of calcium hydride, heating the mixture to at least 675 deg C for decomposition of the hydride and then for sintering, preferably in a vacuum, at from 1550 to 2000 deg C. Calcium metal is formed, some uranium is reduced by the calcium to the metal and a product of high density is obtained.

Disorder induced semiconductor to metal transition and modifications of grain boundaries in nanocrystalline zinc oxide thin film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Fouran; Kumar, Vinod; Chaudhary, Babloo

2012-10-01

This paper report on the disorder induced semiconductor to metal transition (SMT) and modifications of grain boundaries in nanocrystalline zinc oxide thin film. Disorder is induced using energetic ion irradiation. It eliminates the possibility of impurities induced transition. However, it is revealed that some critical concentration of defects is needed for inducing such kind of SMT at certain critical temperature. Above room temperature, the current-voltage characteristics in reverse bias attributes some interesting phenomenon, such as electric field induced charge transfer, charge trapping, and diffusion of defects. The transition is explained by the defects induced disorder and strain in ZnO crystallitesmore » created by high density of electronic excitations.« less

Advanced nickel-metal hydride cell development. Final report, September 1993--March 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, Hong S.

1996-03-01

Inert gas atomization using metal hydride alloys for a Ni/MH{sub x}cell was studied. Atomization of the alloys was demonstrated on a small production scale up to batch size of several kg. Relative performance of the atomized and nonatomized alloys was investigated for the electrode material in a Ni/MH{sub x} cell. The study included effects of charge-discharge rates, temperature, and particle size on cell voltage (polarization) and specific capacity. Results show that the specific capacity of the present atomized alloys was apprecialy smaller than that of the nonatomized powder, especially for initial cycles. Full activation of the atomized alloys oftentook severalmore » hundreds of cycles. However, no appreciable difference in discharge rate capability was observed with R10 and R12 alloys. Chemical compositions were indistinguishable, although the oxygen contents of the atomized alloys were always higher. Effects of Ni and Cu coating on alloy performance were studied after electroless coating; the coatings noticeably improved the electrode rate capability for all the alloys. The electrode polarization was esecially improved, but not the cycle life. Further studies are needed.« less

Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

NASA Astrophysics Data System (ADS)

Jiang, Yin-ju; Deng, Yong-chun; Bu, Wen-gang

2015-10-01

Gas selective reduction-oxidation (redox) and melting separation were consecutively applied to electrode materials of AB5-type Ni-metal hydride batteries leading to the production of a Ni-Co alloy and slag enriched with rare earth oxides (REO). In the selective redox process, electrode materials were treated with H2/H2O at 1073 K and 1173 K (800 °C and 900 °C). Active elements such as REs, Al, and Mn were oxidized whereas relatively inert elements such as Ni and Co were transformed into their elemental states in the treated materials. SiO2 and Al2O3 powders were added into the treated materials as fluxes which were then melted at 1823 K (1550 °C) to yield a Ni-Co alloy and a REO-SiO2-Al2O3-MnO slag. The high-purity Ni-Co alloy produced can be used as a raw material for AB5-type hydrogen-storage alloy. The REO content in slag was very high, i.e., 48.51 pct, therefore it can be used to recycle rare earth oxides.

Exploring hydride-π interactions and their tuning by σ-hole bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Asadollahi, Soheila; Mousavian, Parisasadat

2018-01-01

In the present work, ab initio calculations are performed to investigate the geometry, interaction energy and bonding properties of binary complexes formed between metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CH3) and a series of π-acidic heteroaromatic rings. In all the resulting complexes, the heteroaromatic ring acts as a Lewis acid (electron acceptor), while the H atom of the HMX molecule acts as a Lewis base (electron donor). The nature of this interaction, called 'hydride-π' interaction, is explored in terms of molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. The results show that the interaction energies of these hydride-π interactions are between -1.24 and -2.72 kcal/mol. Furthermore, mutual influence between the hydride-π and halogen- or pnicogen-bonding interactions is studied in complexes in which these interactions coexist. For a given π-acidic ring, the formation of the pnicogen-bonding induces a larger enhancing effect on the strength of hydride-π bond than the halogen-bonding.

A Ti-V-based bcc phase alloy for use as metal hydride electrode with high discharge capacity

NASA Astrophysics Data System (ADS)

Yu, X. B.; Wu, Z.; Xia, B. J.; Xu, N. X.

2004-07-01

The electrochemical characteristics of single bcc phase Ti-30V-15Cr-15Mn alloy were investigated. It was demonstrated that the single bcc phase alloy has high electrochemical discharge performance at high temperature. Its discharge capacity is closely related with temperature and discharge current. The first discharge capacities of 580-814 mAh g-1 of the alloy powder were obtained at discharge current of 45-10 mA g-1 in 6 M KOH solution at 353 K. Although the electrochemical cycle life of the alloy is unsatisfactory at present, it opens up prospects for developing a new hydrogen storage alloy with high hydrogen capacity for use as high performance metal hydride electrodes in rechargeable Ni-MH battery.

A Ti-V-based bcc phase alloy for use as metal hydride electrode with high discharge capacity.

PubMed

Yu, X B; Wu, Z; Xia, B J; Xu, N X

2004-07-08

The electrochemical characteristics of single bcc phase Ti-30V-15Cr-15Mn alloy were investigated. It was demonstrated that the single bcc phase alloy has high electrochemical discharge performance at high temperature. Its discharge capacity is closely related with temperature and discharge current. The first discharge capacities of 580-814 mAh g(-1) of the alloy powder were obtained at discharge current of 45-10 mA g(-1) in 6 M KOH solution at 353 K. Although the electrochemical cycle life of the alloy is unsatisfactory at present, it opens up prospects for developing a new hydrogen storage alloy with high hydrogen capacity for use as high performance metal hydride electrodes in rechargeable Ni-MH battery.

Recovery of rare metal compounds from nickel-metal hydride battery waste and their application to CH4 dry reforming catalyst.

PubMed

Kanamori, Tomohiro; Matsuda, Motohide; Miyake, Michihiro

2009-09-30

The recovery of valuable components such as nickel from nickel-metal hydride (Ni-MH) battery waste by chemical processes and their applications to CH(4) dry reforming catalysts were investigated. Three types of compound, identified by XRD analysis as NiO, CeO(2) and LaCoO(3) phases, were successfully separated from the waste by a series of chemical processes at room temperature using aqueous solutions of HCl, NaOH and NH(3), and Ni component of approximately 70% in Ni-MH battery waste was recovered. The separated NiO, CeO(2) and LaCoO(3) showed catalytic activities for CH(4) dry reforming. In particular, the separated NiO easily reduced to Ni(0) at an initial stage, and exhibited excellent catalytic activity in terms of CH(4) conversion and stability. Furthermore, it was found that the resulting Ni from separated NiO exhibited an anomalous catalysis from the comparison with that from regent NiO.

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster.

PubMed

Kang, Xiaohui; Luo, Gen; Luo, Lun; Hu, Shaowei; Luo, Yi; Hou, Zhaomin

2016-09-14

Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

Superconductivity in Hydrides Doped with Main Group Elements Under Pressure

NASA Astrophysics Data System (ADS)

Shamp, Andrew; Zurek, Eva

2017-01-01

A priori crystal structure prediction techniques have been used to explore the phase diagrams of hydrides of main group elements under pressure. A number of novel phases with the chemical formulas MHn, n > 1 and M = Li, Na, K, Rb, Cs; MHn, n > 2 and M= Mg, Ca, Sr, Ba; HnI with n > 1 and PH, PH2, PH3 have been predicted to be stable at pressures achievable in diamond anvil cells. The hydrogenic lattices within these phases display a number of structural motifs including H2δ- , H-, H-3 , as well as one-dimensional and three-dimensional extended structures. A wide range of superconducting critical temperatures, Tcs, are predicted for these hydrides. The mechanism of metallization and the propensity for superconductivity are dependent upon the structural motifs present in these phases, and in particular on their hydrogenic sublattices. Phases that are thermodynamically unstable, but dynamically stable, are accessible experimentally. The observed trends provide insight on how to design hydrides that are superconducting at high temperatures.

Structure and Thermodynamical Properties of Zirconium Hydrides from First-Principle

NASA Astrophysics Data System (ADS)

Blomqvist, Jakob; Olofsson, Johan; Alvarez, Anna-Maria; Bjerkén, Christina

Zirconium alloys are used as nuclear fuel cladding material due to their mechanical and corrosion resistant properties together with their favorable cross-section for neutron scattering. At running conditions, however, there will be an increase of hydrogen in the vicinity of the cladding surface at the water side of the fuel. The hydrogen will diffuse into the cladding material and at certain conditions, such as lower temperatures and external load, hydrides will precipitate out in the material and cause well known embrittlement, blistering and other unwanted effects. Using phase-field methods it is now possible to model precipitation buildup in metals, for example as a function of hydrogen concentration, temperature and external load, but the technique relies on input of parameters, such as the formation energy of the hydrides and matrix. To that end, we have computed, using the density functional theory (DFT) code GPAW, the latent heat of fusion as well as solved the crystal structure for three zirconium hydride polymorphs: δ-ZrH1.6, γ-ZrH, and Є-ZrH2.

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, Leslie D.

1982-01-01

A pressure controlled vanadium hydride gas generator to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

PREPARATION OF METAL POWDER COMPACTS PRIOR TO PRESSING

DOEpatents

Mansfield, H.

1958-08-26

A method of fabricating uranium by a powder metallurgical technique is described. It consists in introducing powdered uranium hydride into a receptacle shaped to coincide with the coatour of the die cavity and heating the hydride so that it decomposes to uranium metal. The metal particles cohere in the shapw of the receptacle and thereafter the prefurmed metal powder is pressed and sintered to obtain a dense compact.

Physics of hydride fueled PWR

NASA Astrophysics Data System (ADS)

Ganda, Francesco

The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages.

PubMed

Stitt, C A; Harker, N J; Hallam, K R; Paraskevoulakos, C; Banos, A; Rennie, S; Jowsey, J; Scott, T B

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

Size effects of nano-spaced basal stacking faults on the strength and deformation mechanisms of nanocrystalline pure hcp metals

NASA Astrophysics Data System (ADS)

Wang, Wen; Jiang, Ping; Yuan, Fuping; Wu, Xiaolei

2018-05-01

The size effects of nano-spaced basal stacking faults (SFs) on the tensile strength and deformation mechanisms of nanocrystalline pure cobalt and magnesium have been investigated by a series of large-scale 2D columnar and 3D molecular dynamics simulations. Unlike the strengthening effect of basal SFs on Mg alloys, the nano-spaced basal SFs are observed to have no strengthening effect on the nanocrystalline pure cobalt and magnesium from MD simulations. These observations could be attributed to the following two reasons: (i) Lots of new basal SFs are formed before (for cobalt) or simultaneously with (for magnesium) the other deformation mechanisms (i.e. the formation of twins and the < c + a > edge dislocations) during the tensile deformation; (ii) In hcp alloys, the segregation of alloy elements and impurities at typical interfaces, such as SFs, can stablilise them for enhancing the interactions with dislocation and thus elevating the strength. Without such segregation in pure hcp metals, the < c + a > edge dislocations can cut through the basal SFs although the interactions between the < c + a > dislocations and the pre-existing SFs/newly formed SFs are observed. The nano-spaced basal SFs are also found to have no restriction effect on the formation of deformation twins.

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, L.D.

1980-03-13

A pressure controlled vanadium hydride gas generator was designed to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

Extreme creep resistance in a microstructurally stable nanocrystalline alloy

NASA Astrophysics Data System (ADS)

Darling, K. A.; Rajagopalan, M.; Komarasamy, M.; Bhatia, M. A.; Hornbuckle, B. C.; Mishra, R. S.; Solanki, K. N.

2016-09-01

Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation. Here we show that nanocrystalline copper-tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10-6 per second—six to eight orders of magnitude lower than most nanocrystalline metals—at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of

In situ Raman cell for high pressure and temperature studies of metal and complex hydrides.

PubMed

Domènech-Ferrer, Roger; Ziegs, Frank; Klod, Sabrina; Lindemann, Inge; Voigtländer, Ralf; Dunsch, Lothar; Gutfleisch, Oliver

2011-04-15

A novel cell for in situ Raman studies at hydrogen pressures up to 200 bar and at temperatures as high as 400 °C is presented. This device permits in situ monitoring of the formation and decomposition of chemical structures under high pressure via Raman scattering. The performance of the cell under extreme conditions is stable as the design of this device compensates much of the thermal expansion during heating which avoids defocusing of the laser beam. Several complex and metal hydrides were analyzed to demonstrate the advantageous use of this in situ cell. Temperature calibration was performed by monitoring the structural phase transformation and melting point of LiBH(4). The feasibility of the cell in hydrogen atmosphere was confirmed by in situ studies of the decomposition of NaAlH(4) with added TiCl(3) at different hydrogen pressures and the decomposition and rehydrogenation of MgH(2) and LiNH(2). © 2011 American Chemical Society

Preparation and X-ray diffraction studies of curium hydrides

NASA Astrophysics Data System (ADS)

Gibson, J. K.; Haire, R. G.

1985-10-01

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a0 = 0.3769(8) nm and c0 = 0.6732(12) nm. These products are considered to be CmH 3-δ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a0 = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH 2+ x (B. M. Bansal and D. Damien, Inorg. Nucl. Chem. Lett., 6, 603, 1970). The present results established a continuation of typical heavy trivalent lanthanide-like behavior of the transuranium actinide-hydrogen systems through curium.

New chemistry of transition metal oxyhydrides

PubMed Central

Kobayashi, Yoji; Hernandez, Olivier; Tassel, Cédric; Kageyama, Hiroshi

2017-01-01

Abstract In this review we describe recent advances in transition metal oxyhydride chemistry obtained by topochemical routes, such as low temperature reduction with metal hydrides, or high-pressure solid-state reactions. Besides the crystal chemistry, magnetic and transport properties of the bulk powder and epitaxial thin film samples, the remarkable lability of the hydride anion is particularly highlighted as a new strategy to discover unprecedented mixed anion materials. PMID:29383042

Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J

UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. Themore » assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of

Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

PubMed

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2017-10-05

We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increased Oxygen Recovery from Sabatier Systems Using Plasma Pyrolysis Technology and Metal Hydride Separation

NASA Technical Reports Server (NTRS)

Greenwood, Zachary W.; Abney, Morgan B.; Perry, Jay L.; Miller, Lee A.; Dahl, Roger W.; Hadley, Neal M.; Wambolt, Spencer R.; Wheeler, Richard R.

2015-01-01

State-of-the-art life support carbon dioxide (CO2) reduction technology is based on the Sabatier reaction where less than 50% of the oxygen required for the crew is recovered from metabolic CO2. The reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by the limited availability of reactant hydrogen. This is further exacerbated when Sabatier methane (CH4) is vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover hydrogen has the potential to dramatically increase oxygen recovery and thus drastically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. Due to the highly unstable nature of acetylene, a separation system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of a full-scale Third Generation PPA is reported and investigations into metal hydride hydrogen separation technology is discussed.

An experimental survey of additives for improving dehydrogenation properties of magnesium hydride

NASA Astrophysics Data System (ADS)

Zhou, Chengshang; Fang, Zhigang Zak; Sun, Pei

2015-03-01

The use of a wide range of additives has been known as an important method for improving hydrogen storage properties of MgH2. There is a lack of a standard methodology, however, that can be used to select or compare the effectiveness of different additives. A systematic experimental survey was carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. MgH2 with various additives were prepared by using a high-energy-high-pressure planetary ball milling method and characterized by using thermogravimetric analysis (TGA) techniques. The results showed that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Additives such as Al, In, Sn, Si showed minor effects on the kinetics of the dehydrogenation of MgH2, while exhibiting moderate thermodynamic destabilizing effects. In combination, MgH2 with both kinetic and thermodynamic additives, such as the MgH2-In-TiMn2 system, exhibited a drastically decreased dehydrogenation temperature.

Development of nickel/metal-hydride batteries for EVs and HEVs

NASA Astrophysics Data System (ADS)

Taniguchi, Akihiro; Fujioka, Noriyuki; Ikoma, Munehisa; Ohta, Akira

This paper is to introduce the nickel/metal-hydride (Ni/MH) batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs) developed and mass-produced by our company. EV-95 for EVs enables a vehicle to drive approximately 200 km per charge. As the specific power is extremely high, more than 200 W/kg at 80% depth of discharge (DOD), the acceleration performance is equivalent to that of gasoline fuel automobiles. The life characteristic is also superior. This battery gives the satisfactory result of more than 1000 cycles in bench tests and approximately 4-year on-board driving. EV-28 developed for small EVs comprises of a compact and light battery module with high specific power of 300 W/kg at 80% DOD by introducing a new technology for internal cell connection. Meanwhile, our cylindrical battery for the HEV was adopted into the first generation Toyota Prius in 1997 which is the world's first mass-product HEV, and has a high specific power of 600 W/kg. Its life characteristic was found to be equivalent to more than 100,000 km driving. Furthermore, a new prismatic module in which six cells are connected internally was used for the second generation Prius in 2000. The prismatic battery comprises of a compact and light battery pack with a high specific power of 1000 W/kg, which is approximately 1.7 times that of conventional cylindrical batteries, as a consequence of the development of a new internal cell connection and a new current collection structure.

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides HnRhn[P(OR)3]2n

PubMed Central

Brown, R. K.; Williams, J. M.; Fredrich, M. F.; Day, V. W.; Sivak, A. J.; Muetterties, E. L.

1979-01-01

Crystallographic analyses of x-ray and neutron diffraction data have provided a definitive structural representation of {HRh[P(O-i-C3H7)3]2}2 and {HRh[P(OCH3)3]2}3. These polynuclear hydrides are generated from square planar H2Rh[P(OR)3]2 units by edge (hydrogen atom) sharing and by vertex (hydrogen atom) sharing to form the dimeric and trimeric structures, respectively. The square-planar units are held together through four-center and three-center two-electron Rh—H—Rh bonds in the dimer and trimer, respectively. The dimer and trimer molecules each add one molecule of hydrogen to form H[(i-C3H7O)3P]2RhH3Rh [P(O-i-C3H7)3]2 and H5Rh3[P(OCH3)3]6, respectively. NMR spectral information has served to define the stereochemical features of these polyhydrides. The significance of this chemistry in the metal cluster-metal surface analogy is described. PMID:16592645

Cyclopentadiene-mediated hydride transfer from rhodium complexes.

PubMed

Pitman, C L; Finster, O N L; Miller, A J M

2016-07-12

Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

Superconductivity of novel tin hydrides (Sn(n)H(m)) under pressure.

PubMed

Mahdi Davari Esfahani, M; Wang, Zhenhai; Oganov, Artem R; Dong, Huafeng; Zhu, Qiang; Wang, Shengnan; Rakitin, Maksim S; Zhou, Xiang-Feng

2016-03-11

With the motivation of discovering high-temperature superconductors, evolutionary algorithm USPEX is employed to search for all stable compounds in the Sn-H system. In addition to the traditional SnH4, new hydrides SnH8, SnH12 and SnH14 are found to be thermodynamically stable at high pressure. Dynamical stability and superconductivity of tin hydrides are systematically investigated. I4m2-SnH8, C2/m-SnH12 and C2/m-SnH14 exhibit higher superconducting transition temperatures of 81, 93 and 97 K compared to the traditional compound SnH4 with Tc of 52 K at 200 GPa. An interesting bent H3-group in I4m2-SnH8 and novel linear H in C2/m-SnH12 are observed. All the new tin hydrides remain metallic over their predicted range of stability. The intermediate-frequency wagging and bending vibrations have more contribution to electron-phonon coupling parameter than high-frequency stretching vibrations of H2 and H3.

Method of producing a chemical hydride

DOEpatents

Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

2007-11-13

A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

Properties of nanocrystalline Si layers embedded in structure of solar cell

NASA Astrophysics Data System (ADS)

Jurečka, Stanislav; Imamura, Kentaro; Matsumoto, Taketoshi; Kobayashi, Hikaru

2017-12-01

Suppression of spectral reflectance from the surface of solar cell is necessary for achieving a high energy conversion efficiency. We developed a simple method for forming nanocrystalline layers with ultralow reflectance in a broad range of wavelengths. The method is based on metal assisted etching of the silicon surface. In this work, we prepared Si solar cell structures with embedded nanocrystalline layers. The microstructure of embedded layer depends on the etching conditions. We examined the microstructure of the etched layers by a transmission electron microscope and analysed the experimental images by statistical and Fourier methods. The obtained results provide information on the applied treatment operations and can be used to optimize the solar cell forming procedure.

Porous metallic bodies

DOEpatents

Landingham, Richard L.

1985-01-01

Porous metallic bodies having a substantially uniform pore size of less than about 200 microns and a density of less than about 25 percent theoretical, as well as the method for making them, are disclosed. Group IIA, IIIB, IVB, VB, and rare earth metal hydrides are heated in a confining container at a controlled rate to a temperature of about greater than the temperature at which the hydride decomposes. Hydrogen is removed from the container and the remaining metal is heated during a second stage to a temperature greater than the temperature at which it was previously heated but not greater than the temperature of 1/2 to 2/3 the temperature at which the metal melts at a controlled rate. The resulting porous metallic body produced has a density less than about 25 percent theoretical and a pore size of less than about 200 microns. The metallic particles of the present invention have high inner surface area and possess minimum resistance to gas flow.

Evidence that abnormal grain growth precedes fatigue crack initiation in nanocrystalline Ni-Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furnish, Timothy A.; Bufford, Daniel C.; Ren, Fang

Prior studies on the high-cycle fatigue behavior of nanocrystalline metals have shown that fatigue fracture is associated with abnormal grain growth (AGG). However, those previous studies have been unable to determine if AGG precedes fatigue crack initiation, or vice-versa. The present study shows that AGG indeed occurs prior to crack formation in nanocrystalline Ni-Fe by using a recently developed synchrotron X-ray diffraction modality that has been adapted for in-situ analysis. The technique allows fatigue tests to be interrupted at the initial signs of the AGG process, and subsequent microscopy reveals the precursor damage state preceding crack initiation.

Evidence that abnormal grain growth precedes fatigue crack initiation in nanocrystalline Ni-Fe

DOE PAGES

Furnish, Timothy A.; Bufford, Daniel C.; Ren, Fang; ...

2018-09-06

Prior studies on the high-cycle fatigue behavior of nanocrystalline metals have shown that fatigue fracture is associated with abnormal grain growth (AGG). However, those previous studies have been unable to determine if AGG precedes fatigue crack initiation, or vice-versa. The present study shows that AGG indeed occurs prior to crack formation in nanocrystalline Ni-Fe by using a recently developed synchrotron X-ray diffraction modality that has been adapted for in-situ analysis. The technique allows fatigue tests to be interrupted at the initial signs of the AGG process, and subsequent microscopy reveals the precursor damage state preceding crack initiation.

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchangermore » optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.« less

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages

PubMed Central

Harker, N. J.; Hallam, K. R.; Paraskevoulakos, C.; Banos, A.; Rennie, S.; Jowsey, J.

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed. PMID:26176551

Lactate Racemase Nickel-Pincer Cofactor Operates by a Proton-Coupled Hydride Transfer Mechanism.

PubMed

Rankin, Joel A; Mauban, Robert C; Fellner, Matthias; Desguin, Benoît; McCracken, John; Hu, Jian; Varganov, Sergey A; Hausinger, Robert P

2018-03-09

Lactate racemase (LarA) of Lactobacillus plantarum contains a novel organometallic cofactor with nickel coordinated to a covalently tethered pincer ligand, pyridinium-3-thioamide-5-thiocarboxylic acid mononucleotide, but its function in the enzyme mechanism has not been elucidated. This study presents direct evidence that the nickel-pincer cofactor facilitates a proton-coupled hydride transfer (PCHT) mechanism during LarA-catalyzed lactate racemization. No signal was detected by electron paramagnetic resonance spectroscopy for LarA in the absence or presence of substrate, consistent with a +2 metal oxidation state and inconsistent with a previously proposed proton-coupled electron transfer mechanism. Pyruvate, the predicted intermediate for a PCHT mechanism, was observed in quenched solutions of LarA. A normal substrate kinetic isotope effect ( k H / k D of 3.11 ± 0.17) was established using 2-α- 2 H-lactate, further supporting a PCHT mechanism. UV-visible spectroscopy revealed a lactate-induced perturbation of the cofactor spectrum, notably increasing the absorbance at 340 nm, and demonstrated an interaction of the cofactor with the inhibitor sulfite. A crystal structure of LarA provided greater resolution (2.4 Å) than previously reported and revealed sulfite binding to the pyridinium C4 atom of the reduced pincer cofactor, mimicking hydride reduction during a PCHT catalytic cycle. Finally, computational modeling supports hydride transfer to the cofactor at the C4 position or to the nickel atom, but with formation of a nickel-hydride species requiring dissociation of the His200 metal ligand. In aggregate, these studies provide compelling evidence that the nickel-pincer cofactor acts by a PCHT mechanism.

Method and apparatus for regenerating cold traps within liquid-metal systems

DOEpatents

McKee, Jr., John M.

1976-01-01

Oxide and hydride impurities of a liquid metal such as sodium are removed from a cold trap by heating to a temperature at which the metal hydroxide is stable in a molten state. The partial pressure of hydrogen within the system is measured to determine if excess hydride or oxide is present. Excess hydride is removed by venting hydrogen gas while excess oxide can be converted to molten hydroxide through the addition of hydrogen. The resulting, molten hydroxide is drained from the trap which is then returned to service at cold trap temperatures within the liquid-metal system.

Neutron spectroscopy of γ manganese hydride

NASA Astrophysics Data System (ADS)

Antonov, V. E.; Cornell, K.; Dorner, B.; Fedotov, V. K.; Grosse, G.; Kolesnikov, A. I.; Wagner, F. E.; Wipf, H.

2000-02-01

The vibrational spectrum of fcc γ-MnH 0.41 synthesized under high pressure of gaseous hydrogen was studied by inelastic neutron scattering at 2 K in the range of energy transfers from 25 to 400 meV. The fundamental band of optical hydrogen vibrations consists of a peak at 111 meV with a broad shoulder towards higher energies, which extends up to about 140 meV. At higher energy transfers, the spectrum originates from multiphonon neutron scattering and exhibits approximately harmonic behaviour. The results are compared with the available data for other metal hydrides.

Metal Hydride Heat Storage Technology for Directed Energy Weapon Systems

DTIC Science & Technology

2007-11-16

high thermal conductivity materials for heat transfer enhancement. In addition, the PCMs ’ low heat storage density requires excessively large system...capacity as compared to the PCMs . For example, Ca0.2M0.8Ni5, a commercial hydride, has a heat storage density of 853.3MJ/m³ in raw material condition...Huston and Sandrock, 1980], while paraffin (Calwax 130), a common organic PCM has a heat storage capacity of 177.5MJ/m³ [Al-Hallaj and Selman, 2000]. The

Nanocrystalline films for gas-reactive applications

DOEpatents

Eastman, Jeffrey A.; Thompson, Loren J.

2004-02-17

A gas sensor for detection of oxidizing and reducing gases, including O.sub.2, CO.sub.2, CO, and H.sub.2, monitors the partial pressure of a gas to be detected by measuring the temperature rise of an oxide-thin-film-coated metallic line in response to an applied electrical current. For a fixed input power, the temperature rise of the metallic line is inversely proportional to the thermal conductivity of the oxide coating. The oxide coating contains multi-valent cation species that change their valence, and hence the oxygen stoichiometry of the coating, in response to changes in the partial pressure of the detected gas. Since the thermal conductivity of the coating is dependent on its oxygen stoichiometry, the temperature rise of the metallic line depends on the partial pressure of the detected gas. Nanocrystalline (<100 nm grain size) oxide coatings yield faster sensor response times than conventional larger-grained coatings due to faster oxygen diffusion along grain boundaries rather than through grain interiors.

Dendrite-Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn-Based Batteries.

PubMed

Liu, Zhen; Cui, Tong; Pulletikurthi, Giridhar; Lahiri, Abhishek; Carstens, Timo; Olschewski, Mark; Endres, Frank

2016-02-18

Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermally Stable Nanocrystalline Steel

NASA Astrophysics Data System (ADS)

Hulme-Smith, Christopher Neil; Ooi, Shgh Woei; Bhadeshia, Harshad K. D. H.

2017-10-01

Two novel nanocrystalline steels were designed to withstand elevated temperatures without catastrophic microstructural changes. In the most successful alloy, a large quantity of nickel was added to stabilize austenite and allow a reduction in the carbon content. A 50 kg cast of the novel alloy was produced and used to verify the formation of nanocrystalline bainite. Synchrotron X-ray diffractometry using in situ heating showed that austenite was able to survive more than 1 hour at 773 K (500 °C) and subsequent cooling to ambient temperature. This is the first reported nanocrystalline steel with high-temperature capability.

Pulse power 350 V nickel-metal hydride battery power-D-005-00181

NASA Astrophysics Data System (ADS)

Eskra, Michael D.; Ralston, Paula; Salkind, Alvin; Plivelich, Robert F.

Energy-storage devices are needed for applications requiring very high-power over short periods of time. Such devices have various military (rail guns, electromagnetic launchers, and DEW) and commercial applications, such as hybrid electric vehicles, vehicle starting (SLI), and utility peak shaving. The storage and delivery of high levels of burst power can be achieved with a capacitor, flywheel, or rechargeable battery. In order to reduce the weight and volume of many systems they must contain advanced state-of-the-art electrochemical or electromechanical power sources. There is an opportunity and a need to develop energy-storage devices that have improved high-power characteristics compared to existing ultra capacitors, flywheels or rechargeable batteries. Electro Energy, Inc. has been engaged in the development of bipolar nickel-metal hydride batteries, which may fulfil the requirements of some of these applications. This paper describes a module rated at 300 V (255 cells) (6 Ah). The volume of the module is 23 L and the mass is 56 kg. The module is designed to deliver 50 kW pulses of 10 s duration at 50% state-of-charge. Details of the mechanical design of the module, safety considerations, along with the results of initial electrical characterization testing by the customer will be discussed. Some discussion of the possibilities for design optimization is also included.

Selective Reduction of CO2 to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes.

PubMed

Hicken, Alexandra; White, Andrew J P; Crimmin, Mark R

2017-11-20

A series of heterobimetallic complexes containing three-center, two-electron Au-H-Cu bonds have been prepared from addition of a parent gold hydride to a bent d 10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu-H-Cu and M-H-M + moieties (M=Cu, Ag). The well-defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO 2 into HCO 2 Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

General predictive model of friction behavior regimes for metal contacts based on the formation stability and evolution of nanocrystalline surface films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argibay, Nicolas; Cheng, Shengfeng; Sawyer, W. G.

2015-09-01

The prediction of macro-scale friction and wear behavior based on first principles and material properties has remained an elusive but highly desirable target for tribologists and material scientists alike. Stochastic processes (e.g. wear), statistically described parameters (e.g. surface topography) and their evolution tend to defeat attempts to establish practical general correlations between fundamental nanoscale processes and macro-scale behaviors. We present a model based on microstructural stability and evolution for the prediction of metal friction regimes, founded on recently established microstructural deformation mechanisms of nanocrystalline metals, that relies exclusively on material properties and contact stress models. We show through complementary experimentalmore » and simulation results that this model overcomes longstanding practical challenges and successfully makes accurate and consistent predictions of friction transitions for a wide range of contact conditions. This framework not only challenges the assumptions of conventional causal relationships between hardness and friction, and between friction and wear, but also suggests a pathway for the design of higher performance metal alloys.« less

Characterization of pulsed metallic hydride vacuum arc discharge plasmas by optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Tang, Jian; Deng, Chunfeng; Wu, Chunlei; Lu, Biao; Hu, Yonghong

2017-12-01

The characteristics of plasmas in a titanium hydride vacuum arc ion source were experimentally investigated by a temporally- and spatially-integrated optical emission spectroscopy method. A plasma emission spectral fitting model was developed to calculate the plasmas temperature and relative density of each particle component, assuming plasmas were in local thermodynamic equilibrium state and optical thin in this study. The good agreement was founded between the predicted and measured spectra in the interesting regions of 330-340 nm and 498-503 nm for Ti+ ion and Ti atom respectively, while varying the plasma temperature and density. Compared with conventional Boltzmann plot method, this method, therefore, made a significant improvement on the plasma diagnosis in dealing with the spectral profile with many lines overlapped. At the same time, to understand the mechanism of the occluded-gas vacuum arc discharge plasmas, the plasmas emission spectra, ion relative density, and temperature with different discharge conditions were studied. The results indicated that the rate of Ti metal evaporation and H desorption from the electrode would be enhanced with arc current, and the ionization temperature increased with the feed-in power of arc discharge, leading more H+ and Ti+ ions, but reducing the H+ proportion in arc discharged plasmas.

Coexistence of colossal stress and texture gradients in sputter deposited nanocrystalline ultra-thin metal films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuru, Yener; Welzel, Udo; Mittemeijer, Eric J.

2014-12-01

This paper demonstrates experimentally that ultra-thin, nanocrystalline films can exhibit coexisting colossal stress and texture depth gradients. Their quantitative determination is possible by X-ray diffraction experiments. Whereas a uniform texture by itself is known to generally cause curvature in so-called sin{sup 2}ψ plots, it is shown that the combined action of texture and stress gradients provides a separate source of curvature in sin{sup 2}ψ plots (i.e., even in cases where a uniform texture does not induce such curvature). On this basis, the texture and stress depth profiles of a nanocrystalline, ultra-thin (50 nm) tungsten film could be determined.

Preparation and X-Ray diffraction studies of curium hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, J.K.; Maire, R.G.

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a/sub 0/ = 0.3769(8) nm and c/sub 0/ = 0.6732(12) nm. These products are considere to be CmH/sub 3//sup -//sub 8/ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a/sub 0/ = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH /SUB 2-x/more » (B.M. Bansal and D. Damien. Inorg. Nucl. Chem. Lett. 6 603, 1970). The present results established a continuation of typical heavy trivalent lanthanidelike behavior of the transuranium actinide-hydrogen systems through curium.« less

Frequency-dependent failure mechanisms of nanocrystalline gold interconnect lines under general alternating current

NASA Astrophysics Data System (ADS)

Luo, X. M.; Zhang, B.; Zhang, G. P.

2014-09-01

Thermal fatigue failure of metallization interconnect lines subjected to alternating currents (AC) is becoming a severe threat to the long-term reliability of micro/nanodevices with increasing electrical current density/power. Here, thermal fatigue failure behaviors and damage mechanisms of nanocrystalline Au interconnect lines on the silicon glass substrate have been investigated by applying general alternating currents (the pure alternating current coupled with a direct current (DC) component) with different frequencies ranging from 0.05 Hz to 5 kHz. We observed both thermal fatigue damages caused by Joule heating-induced cyclic strain/stress and electromigration (EM) damages caused by the DC component. Besides, the damage formation showed a strong electrically-thermally-mechanically coupled effect and frequency dependence. At lower frequencies, thermal fatigue damages were dominant and the main damage forms were grain coarsening with grain boundary (GB) cracking/voiding and grain thinning. At higher frequencies, EM damages took over and the main damage forms were GB cracking/voiding of smaller grains and hillocks. Furthermore, the healing effect of the reversing current was considered to elucidate damage mechanisms of the nanocrystalline Au lines generated by the general AC. Lastly, a modified model was proposed to predict the lifetime of the nanocrystalline metal interconnect lines, i.e., that was a competing drift velocity-based approach based on the threshold time required for reverse diffusion/healing to occur.

The inverse hall-petch relation in nanocrystalline metals: A discrete dislocation dynamics analysis

NASA Astrophysics Data System (ADS)

Quek, Siu Sin; Chooi, Zheng Hoe; Wu, Zhaoxuan; Zhang, Yong Wei; Srolovitz, David J.

2016-03-01

When the grain size in polycrystalline materials is reduced to the nanometer length scale (nanocrystallinity), observations from experiments and atomistic simulations suggest that the yield strength decreases (softening) as the grain size is decreased. This is in contrast to the Hall-Petch relation observed in larger sized grains. We incorporated grain boundary (GB) sliding and dislocation emission from GB junctions into the classical DDD framework, and recovered the smaller is weaker relationship observed in nanocrystalline materials. This current model shows that the inverse Hall-Petch behavior can be obtained through a relief of stress buildup at GB junctions from GB sliding by emitting dislocations from the junctions. The yield stress is shown to vary with grain size, d, by a d 1 / 2 relationship when grain sizes are very small. However, pure GB sliding alone without further plastic accomodation by dislocation emission is grain size independent.

In-situ study of the cracking of metal hydride electrodes by acoustic emission technique

NASA Astrophysics Data System (ADS)

Didier-Laurent, S.; Idrissi, H.; Roué, L.

Pulverisation phenomena occurring during the charge/discharge cycling of metal hydride materials were studied by acoustic emission coupled to electrochemical measurements. Two kinds of materials were studied: a commercial LaNi 5-based alloy and a ball-milled MgNi alloy. In both alloys, two populations of acoustic signals were detected during charging steps: P1, showing peak frequencies between 230 and 260 kHz, high energy and low rise time, and P2 with peak frequencies between 150 and 180 kHz, lower energy and longer rise time. Population P2 is related to the hydrogen evolution reaction whereas P1 is associated with pulverisation phenomena. No acoustic activity was detected during discharge. We also investigated pulverisation phenomena through cycles by monitoring the P1 population. It appears that pulverisation occurs mainly during the five first cycles for LaNi 5 with a maximum at the second cycle, while pulverisation takes place all along the cycling for MgNi, but at a decreasing rate. By comparing the P1 activities, it appears that the pulverization phenomenon is less intensive on the MgNi electrode than on the LaNi 5-based electrode.

Photocatalytic degradation of Orange G dye under solar light using nanocrystalline semiconductor metal oxide.

PubMed

Thennarasu, G; Kavithaa, S; Sivasamy, A

2011-08-01

The photocatalytic degradation of Orange G (OG) dye has been investigated using synthesised nanocrystalline ZnO as a photocatalyst and sunlight as the irradiation source. The formation of ZnO prepared from its precursor was confirmed through FT-IR and powder X-ray diffraction analyses. Surface morphology was characterised by scanning electron microscope and transmission electron microscope analysis. Band gap energy of synthesised nanocrystalline ZnO was calculated using diffuse reflectance spectroscopy (DRS). Different experimental parameters such as effects of pH, dye concentrations and mass of catalyst were standardised in order to achieve complete degradation of the dye molecules under solar light irradiation. The kinetics of oxidation of OG was also studied. The complete degradation of OG was evident after 90 min of irradiation at an initial pH of 6.86. The degradation of OG was confirmed by UV-Visible spectrophotometer, high-pressure liquid chromatography, ESI-Mass and chemical oxygen demand analyses. The adsorption of dye onto catalytic surface was analysed employing model equations such as Langmuir and Freundlich isotherms, and it was found that the Langmuir isotherm model best fitted the adsorption data. The solar photodegradation of OG followed pseudo-first-order kinetics. HPLC and ESI-Mass analyses of the degraded samples suggested that the dye molecules were readily degraded under solar irradiation with nanocrystalline ZnO.

Porous metallic bodies

DOEpatents

Landingham, R.L.

1984-03-13

Porous metallic bodies having a substantially uniform pore size of less than about 200 microns and a density of less than about 25 percent theoretical, as well as the method for making them, are disclosed. Group IIA, IIIB, IVB, VB, and rare earth metal hydrides a

Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction

PubMed Central

Muckerman, James T.; Achord, Patrick; Creutz, Carol; Polyansky, Dmitry E.; Fujita, Etsuko

2012-01-01

We have developed a correlation between experimental and density functional theory-derived results of the hydride-donating power, or “hydricity”, of various ruthenium, rhenium, and organic hydride donors. This approach utilizes the correlation between experimental hydricity values and their corresponding calculated free-energy differences between the hydride donors and their conjugate acceptors in acetonitrile, and leads to an extrapolated value of the absolute free energy of the hydride ion without the necessity to calculate it directly. We then use this correlation to predict, from density functional theory-calculated data, hydricity values of ruthenium and rhenium complexes that incorporate the pbnHH ligand—pbnHH = 1,5-dihydro-2-(2-pyridyl)-benzo[b]-1,5-naphthyridine—to model the function of NADPH. These visible light-generated, photocatalytic complexes produced by disproportionation of a protonated-photoreduced dimer of a metal-pbn complex may be valuable for use in reducing CO2 to fuels such as methanol. The excited-state lifetime of photoexcited [Ru(bpy)2(pbnHH)]2+ is found to be about 70 ns, and this excited state can be reductively quenched by triethylamine or 1,4-diazabicyclo[2.2.2]octane to produce the one-electron-reduced [Ru(bpy)2(pbnHH)]+ species with half-life exceeding 50 μs, thus opening the door to new opportunities for hydride-transfer reactions leading to CO2 reduction by producing a species with much increased hydricity. PMID:22826261

Mechanically strong nanocrystalline Fe-Si-B-P-Cu soft magnetic powder cores utilizing magnetic metallic glass as a binder

NASA Astrophysics Data System (ADS)

Luan, Jian; Sharma, Parmanand; Yodoshi, Noriharu; Zhang, Yan; Makino, Akihiro

2016-05-01

We report on the fabrication and properties of soft magnetic powder cores with superior mechanical strength as well as low core loss (W). Development of such cores is important for applications in automobiles/devices operating in motion. High saturation magnetic flux density (Bs) Fe-Si-B-P-Cu powder was sintered with Fe55C10B5P10Ni15Mo5 metallic glass (MG) powder in its supercooled liquid state by spark plasma sintering. The sintered cores are made from the nanocrystalline powder particles of Fe-Si-B-P-Cu alloy, which are separated through a magnetic Fe55C10B5P10Ni15Mo5 MG alloy. Low W of ˜ 2.2 W/kg (at 1T and 50 Hz), and high fracture strength (yielding stress ˜500 MPa), which is an order of magnitude higher than the conventional powder cores, were obtained. Stronger metal-metal bonding and magnetic nature of MG binder (which is very different than the conventional polymer based binders) are responsible for the superior mechanical and magnetic properties. The MG binder not only helps in improving the mechanical properties but it also enhances the overall Bs of the core.

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

Ferroelectric Polarization in Nanocrystalline Hydroxyapatite Thin Films on Silicon

PubMed Central

Lang, S. B.; Tofail, S. A. M.; Kholkin, A. L.; Wojtaś, M.; Gregor, M.; Gandhi, A. A.; Wang, Y.; Bauer, S.; Krause, M.; Plecenik, A.

2013-01-01

Hydroxyapatite nanocrystals in natural form are a major component of bone- a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics. PMID:23884324

Ferroelectric Polarization in Nanocrystalline Hydroxyapatite Thin Films on Silicon

NASA Astrophysics Data System (ADS)

Lang, S. B.; Tofail, S. A. M.; Kholkin, A. L.; Wojtaś, M.; Gregor, M.; Gandhi, A. A.; Wang, Y.; Bauer, S.; Krause, M.; Plecenik, A.

2013-07-01

Hydroxyapatite nanocrystals in natural form are a major component of bone- a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics.

Ferroelectric polarization in nanocrystalline hydroxyapatite thin films on silicon.

PubMed

Lang, S B; Tofail, S A M; Kholkin, A L; Wojtaś, M; Gregor, M; Gandhi, A A; Wang, Y; Bauer, S; Krause, M; Plecenik, A

2013-01-01

Hydroxyapatite nanocrystals in natural form are a major component of bone--a known piezoelectric material. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic pyroelectric coatings as it binds strongly with natural bone. Nanocrystalline synthetic hydroxyapatite films have recently been found to exhibit strong piezoelectricity and pyroelectricity. While a spontaneous polarization in hydroxyapatite has been predicted since 2005, the reversibility of this polarization (i.e. ferroelectricity) requires experimental evidence. Here we use piezoresponse force microscopy to demonstrate that nanocrystalline hydroxyapatite indeed exhibits ferroelectricity: a reversal of polarization under an electrical field. This finding will strengthen investigations on the role of electrical polarization in biomineralization and bone-density related diseases. As hydroxyapatite is one of the most common biocompatible materials, our findings will also stimulate systematic exploration of lead and rare-metal free ferroelectric devices for potential applications in areas as diverse as in vivo and ex vivo energy harvesting, biosensing and electronics.

Effects of outgassing of loader chamber walls on hydriding of thin films for commercial applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provo, James L., E-mail: jlprovo@verizon.net

2014-07-01

chamber (1)–Cu(1.83 wt. %)Be as a standard, the peak intensity from chamber (4)—stainless-steel (air-fired) was 7.1× higher, indicating that the surface of stainless-steel had a larger concentration of reactive oxygen and/or water than hydrogen. The (D{sub 2}O{sup +}) peak intensity from chamber (3)—Cu (interior Al coating) was 1.55× larger and chamber (2)—alumina(99.8%) was 1.33× higher than Cu(1.83 wt. %)Be. Thus copper–(1.83 wt. %)beryllium was the best hydriding chamber material studied followed closely by the alumina (99.8 wt. %) chamber. Gas take-up by Er occluder targets processed in Cu(1.83 wt. %)Be hydriding chambers (i.e., gas/metal atomic ratios) correlate with the dynamic RGA data.« less

Formation and mechanism of nanocrystalline AZ91 powders during HDDR processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yafen; Fan, Jianfeng, E-mail: fanjianfeng@tyu

2017-03-15

Grain sizes of AZ91 alloy powders were markedly refined to about 15 nm from 100 to 160 μm by an optimized hydrogenation-disproportionation-desorption-recombination (HDDR) process. The effect of temperature, hydrogen pressure and processing time on phase and microstructure evolution of AZ91 alloy powders during HDDR process was investigated systematically by X-ray diffraction, optical microscopy, scanning electron microscopy and transmission electron microscopy, respectively. The optimal HDDR process for preparing nanocrystalline Mg alloy powders is hydriding at temperature of 350 °C under 4 MPa hydrogen pressure for 12 h and dehydriding at 350 °C for 3 h in vacuum. A modified unreacted coremore » model was introduced to describe the mechanism of grain refinement of during HDDR process. - Highlights: • Grain size of the AZ91 alloy powders was significantly refined from 100 μm to 15 nm. • The optimal HDDR technology for nano Mg alloy powders is obtained. • A modified unreacted core model of grain refinement mechanism was proposed.« less

Ultrasonic Emission from Nanocrystalline Porous Silicon

NASA Astrophysics Data System (ADS)

Shinoda, Hiroyuki; Koshida, Nobuyoshi

A simple layer structure composed of a metal thin film and a porous silicon layer on a silicon substrate generates intense and wide-band airborne ultrasounds. The large-bandwidth and the fidelity of the sound reproduction are leveraged in applications varying from sound-based measurement to a scientific study of animal ecology. This chapter describes the basic principle of the ultrasound generation. The macroscopic properties of the low thermal conductivity and the small heat capacity of nanocrystalline porous silicon thermally induce ultrasonic emission. The state-of-the-art of the achievable sound pressure and sound signal properties is introduced, with the technological and scientific applications of the devices.

Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.

2012-04-19

Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 releasemore » properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.« less

Probing nanocrystalline grain dynamics in nanodevices

PubMed Central

Yeh, Sheng-Shiuan; Chang, Wen-Yao; Lin, Juhn-Jong

2017-01-01

Dynamical structural defects exist naturally in a wide variety of solids. They fluctuate temporally and hence can deteriorate the performance of many electronic devices. Thus far, the entities of these dynamic objects have been identified to be individual atoms. On the other hand, it is a long-standing question whether a nanocrystalline grain constituted of a large number of atoms can switch, as a whole, reversibly like a dynamical atomic defect (that is, a two-level system). This is an emergent issue considering the current development of nanodevices with ultralow electrical noise, qubits with long quantum coherence time, and nanoelectromechanical system sensors with ultrahigh resolution. We demonstrate experimental observations of dynamic nanocrystalline grains that repeatedly switch between two or more metastable coordinate states. We study temporal resistance fluctuations in thin ruthenium dioxide (RuO2) metal nanowires and extract microscopic parameters, including relaxation time scales, mobile grain sizes, and the bonding strengths of nanograin boundaries. These material parameters are not obtainable by other experimental approaches. When combined with previous in situ high-resolution transmission electron microscopy, our electrical method can be used to infer rich information about the structural dynamics of a wide variety of nanodevices and new two-dimensional materials. PMID:28691094

A classical but new kinetic equation for hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Deng, Fei-Huang; Yang, Jin-Dong; Li, Xiu-Tao; Chen, Qiang; Lei, Nan-Ping; Meng, Fan-Kun; Zhao, Xiao-Peng; Han, Su-Hui; Hao, Er-Jun; Mu, Yuan-Yuan

2013-09-28

A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions.

Inhibited solid propellant composition containing beryllium hydride

NASA Technical Reports Server (NTRS)

Thompson, W. W. (Inventor)

1978-01-01

An object of this invention is to provide a composition of beryllium hydride and carboxy-terminated polybutadiene which is stable. Another object of this invention is to provide a method for inhibiting the reactivity of beryllium hydride toward carboxy-terminated polybutadiene. It was found that a small amount of lecithin inhibits the reaction of beryllium hydride with the acid groups in carboxy terminated polybutadiene.

Development of battery management system for nickel-metal hydride batteries in electric vehicle applications

NASA Astrophysics Data System (ADS)

Jung, Do Yang; Lee, Baek Haeng; Kim, Sun Wook

Electric vehicle (EV) performance is very dependent on traction batteries. For developing electric vehicles with high performance and good reliability, the traction batteries have to be managed to obtain maximum performance under various operating conditions. Enhancement of battery performance can be accomplished by implementing a battery management system (BMS) that plays an important role in optimizing the control mechanism of charge and discharge of the batteries as well as monitoring the battery status. In this study, a BMS has been developed for maximizing the use of Ni-MH batteries in electric vehicles. This system performs several tasks: the control of charging and discharging, overcharge and over-discharge protection, the calculation and display of state-of-charge (SOC), safety, and thermal management. The BMS is installed in and tested in a DEV5-5 electric vehicle developed by Daewoo Motor Co. and the Institute for Advanced Engineering in Korea. Eighteen modules of a Panasonic nickel-metal hydride (Ni-MH) battery, 12 V, 95 A h, are used in the DEV5-5. High accuracy within a range of 3% and good reliability are obtained. The BMS can also improve the performance and cycle-life of the Ni-MH battery peak, as well as the reliability and the safety of the electric vehicles.

Application of metal hydride paper to simple pressure generator for use in soft actuator systems.

PubMed

Ino, Shuichi; Sakaki, Kouji; Hosono, Minako; Doi, Kouki; Shimada, Shigenobu; Chikai, Manabu

2015-01-01

Metal hydride (MH) actuators have a simple structure and a number of features that make them attractive for use in rehabilitation engineering and assistive technology. The MH actuator provides a high power-to-weight ratio, high-strain actuation, human-compatible softness, and noiseless operation, while being environmentally benign. On the other hand, there remain technical challenges to be overcome to improve the MH actuator regarding its speed of operation and energy efficiency, given the low heat conductivity of the MH powder that is used as the pressure generator for soft actuation. To overcome the issues of low heat conductivity and the handling of MH powder, we developed an MH paper, which is a special paper incorporating MH powder and carbon fiber, for use as a new pressure-generating element for a soft MH actuator system. In addition, the basic properties and structure of the proposed MH paper were investigated through scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and several thermodynamic experiments. The results of these experiments showed that the hydrogen absorption and desorption rates of the MH paper were significantly higher than those of the MH powder around room temperature.

Acanthite–argentite transformation in nanocrystalline silver sulfide and the Ag{sub 2}S/Ag nanoheterostructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gusev, A. I., E-mail: gusev@ihim.uran.ru; Sadovnikov, S. I.

Nanocrystalline acanthite-structured silver sulfide of the monoclinic structure and a Ag{sub 2}S/Ag nanoheterostructure are produced. The high-temperature X-ray diffraction technique is applied to the in situ study of the (acanthite α-Ag{sub 2}S)–(argentite β-Ag{sub 2}S) phase transformation in nanocrystalline silver sulfide. The crystal structure of argentite is refined, and it is found that the content of vacant sites in the metal sublattice of argentite exceeds 92%. A model of a resistive switch, whose operation is based on the reversible acanthite–argentite transformation in a Ag{sub 2}S/Ag heterostructure, is considered.

Interferences in electrochemical hydride generation of hydrogen selenide

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Belarra, M. A.; Castillo, J. R.

2001-12-01

Interferences from Cu(II), Zn(II), Pt(IV), As(III) and nitrate on electrochemical hydride generation of hydrogen selenide were studied using a tubular flow-through generator, flow injection sample introduction and quartz tube atomic absorption spectrometry. Comparison with conventional chemical generation using tetrahydroborate was also performed. Lead and reticulated vitreous carbon (RVC), both in particulate form, were used as cathode materials. Signal supressions up to 60-75%, depending on the cathode material, were obtained in the presence of up to 200 mg l-1 of nitrate due to the competitive reduction of the anion. Interference from As(III) was similar in electrochemical and chemical generation, being related to the quartz tube atomization process. Zinc did not interfere up to Se/Zn ratios 1:100, whereas copper and platinum showed suppression levels up to 50% for Se/interferent ratios 1:100. Total signal suppression was observed in presence of Se/Cu ratios 1:100 when RVC cathodes were used. No memory effects were observed in any case. Scanning electron microscopy and squared wave voltametry studies supported the interference mechanism based on the decomposition of the hydride on the dispersed particles of the reduced metal.

High Resolution Neutron Radiography and Tomography of Hydrided Zircaloy-4 Cladding Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Tyler S; Bilheux, Hassina Z; Ray, Holly B

2015-01-01

Neutron radiography for hydrogen analysis was performed with several Zircaloy-4 cladding samples with controlled hydrogen concentrations up to 1100 ppm. Hydrogen charging was performed in a process tube that was heated to facilitate hydrogen absorption by the metal. A correlation between the hydrogen concentration in the hydrided tubes and the neutron intensity was established, by which hydrogen content can be determined precisely in a small area (55 m x 55 m). Radiography analysis was also performed to evaluate the heating rate and its correlation with the hydrogen distribution through hydrided materials. In addition to radiography analysis, tomography experiments were performedmore » on Zircaloy-4 tube samples to study the local hydrogen distribution. Through tomography analysis a 3D reconstruction of the tube was evaluated in which an uneven hydrogen distribution in the circumferential direction can be observed.« less

Formation and electronic properties of palladium hydrides and palladium-rhodium dihydride alloys under pressure.

PubMed

Yang, Xiao; Li, Huijian; Ahuja, Rajeev; Kang, Taewon; Luo, Wei

2017-06-14

We present the formation possibility for Pd-hydrides and Pd-Rh hydrides system by density functional theory (DFT) in high pressure upto 50 GPa. Calculation confirmed that PdH 2 in face-centered cubic (fcc) structure is not stable under compression that will decomposition to fcc-PdH and H 2 . But it can be formed under high pressure while the palladium is involved in the reaction. We also indicate a probably reason why PdH 2 can not be synthesised in experiment due to PdH is most favourite to be formed in Pd and H 2 environment from ambient to higher pressure. With Rh doped, the Pd-Rh dihydrides are stabilized in fcc structure for 25% and 75% doping and in tetragonal structure for 50% doping, and can be formed from Pd, Rh and H 2 at high pressure. The electronic structural study on fcc type Pd x Rh 1-x H 2 indicates the electronic and structural transition from metallic to semi-metallic as Pd increased from x = 0 to 1.

Enhanced Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg₂Ni-type Alloy by Melt Spinning.

PubMed

Zhang, Yang-Huan; Li, Bao-Wei; Ren, Hui-Ping; Li, Xia; Qi, Yan; Zhao, Dong-Liang

2011-01-18

Mg₂Ni-type Mg₂Ni 1-x Co x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were fabricated by melt spinning technique. The structures of the as-spun alloys were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys was tested by an automatic galvanostatic system. The results show that the as-spun (x = 0.1) alloy exhibits a typical nanocrystalline structure, while the as-spun (x = 0.4) alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni notably intensifies the glass forming ability of the Mg₂Ni-type alloy. The melt spinning treatment notably improves the hydriding and dehydriding kinetics as well as the high rate discharge ability (HRD) of the alloys. With an increase in the spinning rate from 0 (as-cast is defined as spinning rate of 0 m/s) to 30 m/s, the hydrogen absorption saturation ratio () of the (x = 0.4) alloy increases from 77.1 to 93.5%, the hydrogen desorption ratio () from 54.5 to 70.2%, the hydrogen diffusion coefficient (D) from 0.75 × 10 - 11 to 3.88 × 10 - 11 cm²/s and the limiting current density I L from 150.9 to 887.4 mA/g.

Results of NDE Technique Evaluation of Clad Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kunerth, Dennis C.

2014-09-01

This report fulfills the M4 milestone, M4FT-14IN0805023, Results of NDE Technique Evaluation of Clad Hydrides, under Work Package Number FT-14IN080502. During service, zirconium alloy fuel cladding will degrade via corrosion/oxidation. Hydrogen, a byproduct of the oxidation process, will be absorbed into the cladding and eventually form hydrides due to low hydrogen solubility limits. The hydride phase is detrimental to the mechanical properties of the cladding and therefore it is important to be able to detect and characterize the presence of this constituent within the cladding. Presently, hydrides are evaluated using destructive examination. If nondestructive evaluation techniques can be used tomore » detect and characterize the hydrides, the potential exists to significantly increase test sample coverage while reducing evaluation time and cost. To demonstrate the viability this approach, an initial evaluation of eddy current and ultrasonic techniques were performed to demonstrate the basic ability to these techniques to detect hydrides or their effects on the microstructure. Conventional continuous wave eddy current techniques were applied to zirconium based cladding test samples thermally processed with hydrogen gas to promote the absorption of hydrogen and subsequent formation of hydrides. The results of the evaluation demonstrate that eddy current inspection approaches have the potential to detect both the physical damage induced by hydrides, e.g. blisters and cracking, as well as the combined effects of absorbed hydrogen and hydride precipitates on the electrical properties of the zirconium alloy. Similarly, measurements of ultrasonic wave velocities indicate changes in the elastic properties resulting from the combined effects of absorbed hydrogen and hydride precipitates as well as changes in geometry in regions of severe degradation. However, for both approaches, the signal responses intended to make the desired measurement incorporate a number of

Hydride affinity scale of various substituted arylcarbeniums in acetonitrile.

PubMed

Zhu, Xiao-Qing; Wang, Chun-Hua

2010-12-23

Combined with the integral equation formalism polarized continuum model (IEFPCM), the hydride affinities of 96 various acylcarbenium ions in the gas phase and CH(3)CN were estimated by using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-311++G(2df,2p)//B3LYP/6-31+G(d), and BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) methods for the first time. The results show that the combination of the BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) method and IEFPCM could successfully predict the hydride affinities of arylcarbeniums in MeCN with a precision of about 3 kcal/mol. On the basis of the calculated results from the BLYP method, it can be found that the hydride affinity scale of the 96 arylcarbeniums in MeCN ranges from -130.76 kcal/mol for NO(2)-PhCH(+)-CN to -63.02 kcal/mol for p-(Me)(2)N-PhCH(+)-N(Me)(2), suggesting most of the arylcarbeniums are good hydride acceptors. Examination of the effect of the number of phenyl rings attached to the carbeniums on the hydride affinities shows that the increase of the hydride affinities takes place linearly with increasing number of benzene rings in the arylcarbeniums. Analyzing the effect of the substituents on the hydride affinities of arylcarbeniums indicates that electron-donating groups decrease the hydride affinities and electron-withdrawing groups show the opposite effect. The hydride affinities of arylcarbeniums are linearly dependent on the sum of the Hammett substituent parameters σ(p)(+). Inspection of the correlation of the solution-phase hydride affinities with gas-phase hydride affinities and aqueous-phase pK(R)(+) values reveals a remarkably good correspondence of ΔG(H(-)A)(R(+)) with both the gas-phase relative hydride affinities only if the α substituents X have no large electron-donating or -withdrawing properties and the pK(R)(+) values even though the media are dramatically different. The solution-phase hydride affinities also have a linear relationship with the electrophilicity parameter E, and this dependence can

Liquid metal hydrogen barriers

DOEpatents

Grover, George M.; Frank, Thurman G.; Keddy, Edward S.

1976-01-01

Hydrogen barriers which comprise liquid metals in which the solubility of hydrogen is low and which have good thermal conductivities at operating temperatures of interest. Such barriers are useful in nuclear fuel elements containing a metal hydride moderator which has a substantial hydrogen dissociation pressure at reactor operating temperatures.

Insight into destabilization mechanism of Mg-based hydrides interstitially co-doped with nonmetals: a DFT study

NASA Astrophysics Data System (ADS)

Wu, Zhen; Zhu, Luying; Yang, Fusheng; Zhang, Zaoxiao; Nyamsi, Serge N.

2018-04-01

Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom-1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg-Ni/NiH4 bonds, caused by criss-cross interactions between B-Ni and N-Mg bonds.

Analysis of Ni-HYDRIDE Thin Film after Surface Plasmon Generation by Laser Technique

NASA Astrophysics Data System (ADS)

Violante, V.; Castagna, E.; Sibilia, C.; Paoloni, S.; Sarto, F.

2005-12-01

A nickel hydride thin film was studied by the attenuated total reflection method. The differences in behavior between a "black" film, and a pure nickel film "blank," are shown. The black nickel hydride film has been obtained by a short electrolysis with 1 M Li2SO4 electrolyte in light water, A shift in the minimum of the observed reflected light occurs, together with a change in the minimum shape (i.e. its half-height width increases). These two phenomenon are due to the change in the electronic band structure of the metal induced by electrons added to the lattice by hydrogen. The change of the electronic structure, revealed by the laser coupling conditions, leads us to consider that a hydride phase was created. Both the blank (not hydrogenated) and black (hydrogenated) specimens were taken under He-Ne laser beam at the reflectance minimum angle for about three hours. A SIMS analysis was also implemented to reveal differences in the isotopic composition of Cu, as marker element between the blank and black films, in order to study the coupled effect of electrolysis and plasmon-polariton excitation on LENR processes in condensed matter.

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE PAGES

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang; ...

2017-08-02

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

The effect of stress state on zirconium hydride reorientation

NASA Astrophysics Data System (ADS)

Cinbiz, Mahmut Nedim

Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by

A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cammarota, Ryan C.; Vollmer, Matthew V.; Xie, Jing

Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminalmore » Ni-H, for which the hydride donor strength rivals those of precious metal-hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis. The work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award DE-SC0012702. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Hydride heat pump with heat regenerator

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor)

1991-01-01

A regenerative hydride heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system. A series of at least four canisters containing a lower temperature performing hydride and a series of at least four canisters containing a higher temperature performing hydride is provided. Each canister contains a heat conductive passageway through which a heat transfer fluid is circulated so that sensible heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

NASA Astrophysics Data System (ADS)

Soo Kim, Yeon; Wang, Wei-E.; Olander, D. R.; Yagnik, S. K.

1997-07-01

Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400°C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2/H 2O above which massive hydriding occurs at 400°C is ˜ 200. The critical H 2/H 20 ratio is shifted to ˜2.5 × 103 at 350°C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ˜5 h at a hydriding rate of ˜10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale.

Storing hydrogen in the form of light alloy hydrides

NASA Technical Reports Server (NTRS)

Freund, E.; Gillerm, C.

1981-01-01

Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. OPERATIONS IN THE GLOVE BOX IN THE BACKGROUND OF THE PHOTOGRAPH INCLUDED HYDRIDING OF PLUTONIUM AND HYDRIDE SEPARATION. IN THE FOREGROUND, THE VACUUM MONITOR CONTROL PANEL MEASURED TEMPERATURES WITHIN THE GLOVEBOX. THE CENTER CONTROL PANEL REGULATED THE FURNACE INSIDE THE GLOVE BOX USED IN THE HYDRIDING PROCESSES. THIS EQUIPMENT WAS ESSENTIAL TO THE HYDRIDING PROCESS, AS WELL AS OTHER GLOVE BOX OPERATIONS. - Rocky Flats Plant, Plutonium Laboratory, North-central section of industrial area at 79 Drive, Golden, Jefferson County, CO

Characteristics of the high-rate discharge capability of a nickel/metal hydride battery electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geng, M.; Han, J.; Feng, F.

1999-10-01

The high rate discharge capability of the negative electrode in a Ni/MH battery is mainly determined by the charge transfer process at the interface between the metal hydride (MH) alloy powder and the electrolyte, and the mass transfer process in the bulk MH alloy powder. In this study, the anodic polarization curves of a MH electrode were measured and analyzed. An alloy of nominal composition Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} was used as the negative electrode material. With increasing number of charge/discharge cycles, the MH alloy powders microcrack into particles several micrometers in diameter. The decrease in themore » MH alloy particle size results in an increase in both the activation surface area and the exchange current density of the MH alloy electrode. The electrode overpotentials of the MH electrode decreases with increasing number of cycles at a large value of anodic polarization current. The decrease in electrode overpotential leads to an increase in the high rate discharge capability of the MH electrode. By using the limiting current, the hydrogen diffusion coefficient in the MH alloy was estimated to be 1.2 x 10{sup {minus}11}cm{sup 2}s{sup {minus}1} assuming an average particle radius of 5 {micro}m.« less

Solar photovoltaic charging of high voltage nickel metal hydride batteries using DC power conversion

NASA Astrophysics Data System (ADS)

Kelly, Nelson A.; Gibson, Thomas L.

There are an increasing number of vehicle choices available that utilize batteries and electric motors to reduce tailpipe emissions and increase fuel economy. The eventual production of electricity and hydrogen in a renewable fashion, such as using solar energy, can achieve the long-term vision of having no tailpipe environmental impact, as well as eliminating the dependence of the transportation sector on dwindling supplies of petroleum for its energy. In this report we will demonstrate the solar-powered charging of the high-voltage nickel-metal hydride (NiMH) battery used in the GM 2-mode hybrid system. In previous studies we have used low-voltage solar modules to produce hydrogen via the electrolysis of water and to directly charge lithium-ion battery modules. Our strategy in the present work was to boost low-voltage PV voltage to over 300 V using DC-DC converters in order to charge the high-voltage NiMH battery, and to regulate the battery charging using software to program the electronic control unit supplied with the battery pack. A protocol for high-voltage battery charging was developed, and the solar to battery charging efficiency was measured under a variety of conditions. We believe this is the first time such high-voltage batteries have been charged using solar energy in order to prove the concept of efficient, solar-powered charging for battery-electric vehicles.

ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jy-An John; Yan, Yong; Wang, Hong

A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydridesmore » in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation

Agile Thermal Management STT-RX. Catalytic Influence of Ni-based Additives on the Dehydrogentation Properties of Ball Milled MgH2 (PREPRINT)

DTIC Science & Technology

2011-12-01

Wronski: Particle size, grain size and gamma-MgH2 effects on the desorption properties of nanocrystal- line commercial magnesium hydride processed...Catalytic effects of various forms of nickel on the synthesis rate and hydrogen desorption properties of nanocrystalline magnesium hydride (MgH2...dehydrogenation reaction. 15. SUBJECT TERMS magnesium hydride , MgH, thermal energy storage materials, endothermic reaction 16. SECURITY CLASSIFICATION

Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

PubMed

Pappas, Iraklis; Chirik, Paul J

2016-10-03

The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

Solvent- and catalyst-free mechanochemical synthesis of alkali metal monohydrides

DOE PAGES

Hlova, Ihor Z.; Castle, Andra; Goldston, Jennifer F.; ...

2016-07-06

Alkali metal monohydrides, AH (A = Li–Cs) have been synthesized in quantitative yields at room temperature by reactive milling of alkali metals in the presence of hydrogen gas at 200 bar or less. The mechanochemical approach reported here eliminates problems associated with the malleability of alkali metals — especially Li, Na, and K — and promotes effective solid–gas reactions, ensuring their completion. This is achieved by incorporating a certain volume fraction of the corresponding hydride powder as a process control agent, which allows continuous and efficient milling primarily by coating the surface of metal particles, effectively blocking cold welding. Formationmore » of high-purity crystalline monohydrides has been confirmed by powder X-ray diffraction, solid-state NMR spectroscopy, and volumetric analyses of reactively desorbed H 2 from as-milled samples. The proposed synthesis method is scalable and particularly effective for extremely air-sensitive materials, such as alkali and alkaline earth metal hydrides. Furthermore, the technique may also be favorable for production in continuous reactors operating at room temperature, thereby reducing the total processing time, energy consumption and, hence, the cost of production of these hydrides or their derivatives and composites.« less

Mixed metal films with switchable optical properties

NASA Astrophysics Data System (ADS)

Richardson, T. J.; Slack, J. L.; Farangis, B.; Rubin, M. D.

2002-02-01

Thin, Pd-capped metallic films containing magnesium and first-row transition metals (Mn, Fe, Co) switch reversibly from their initial reflecting state to visually transparent states when exposed to gaseous hydrogen or following cathodic polarization in an alkaline electrolyte. Reversion to the reflecting state is achieved by exposure to air or by anodic polarization. The films were prepared by cosputtering from one magnesium target and one manganese, iron, or cobalt target. Both the dynamic optical switching range and the speed of the transition depend on the magnesium-transition metal ratio. Infrared spectra of films in the transparent, hydrided (deuterided) states support the presence of the intermetallic hydride phases Mg3MnH7, Mg2FeH6, and Mg2CoH5.

In situ hydride formation in titanium during focused ion milling.

PubMed

Ding, Rengen; Jones, Ian P

2011-01-01

It is well known that titanium and its alloys are sensitive to electrolytes and thus hydrides are commonly observed in electropolished foils. In this study, focused ion beam (FIB) milling was used to prepare thin foils of titanium and its alloys for transmission electron microscopy. The results show the following: (i) titanium hydrides were observed in pure titanium, (ii) the preparation of a bulk sample in water or acid solution resulted in the formation of more hydrides and (iii) FIB milling aids the precipitation of hydrides, but there were never any hydrides in Ti64 and Ti5553.

Cavity evolution at grain boundaries as a function of radiation damage and thermal conditions in nanocrystalline nickel

DOE PAGES

Muntifering, Brittany; Blair, Sarah Jane; Gong, Cajer; ...

2015-12-30

Enhanced radiation tolerance of nanostructured metals is attributed to the high density of interfaces that can absorb radiation-induced defects. Here, cavity evolution mechanisms during cascade damage, helium implantation, and annealing of nanocrystalline nickel are characterized via in situ transmission electron microscopy (TEM). Films subjected to self-ion irradiation followed by helium implantation developed evenly distributed cavity structures, whereas films exposed in the reversed order developed cavities preferentially distributed along grain boundaries. Post-irradiation annealing and orientation mapping demonstrated uniform cavity growth in the nanocrystalline structure, and cavities spanning multiple grains. Furthermore, these mechanisms suggest limited ability to reduce swelling, despite the stabilitymore » of the nanostructure.« less

Method of making crack-free zirconium hydride

DOEpatents

Sullivan, Richard W.

1980-01-01

Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

Borophene hydride: a stiff 2D material with high thermal conductivity and attractive optical and electronic properties.

PubMed

Mortazavi, Bohayra; Makaremi, Meysam; Shahrokhi, Masoud; Raeisi, Mostafa; Singh, Chandra Veer; Rabczuk, Timon; Pereira, Luiz Felipe C

2018-02-22

Two-dimensional (2D) structures of boron atoms, so-called borophene, have recently attracted remarkable attention. In a recent exciting experimental study, a hydrogenated borophene structure was realized. Motivated by this success, we conducted extensive first-principles calculations to explore the mechanical, thermal conduction, electronic and optical responses of borophene hydride. The mechanical response of borophene hydride was found to be anisotropic, with an elastic modulus of 131 N m -1 and a high tensile strength of 19.9 N m -1 along the armchair direction. Notably, it was shown that by applying mechanical loading the metallic electronic character of borophene hydride can be altered to direct band-gap semiconducting, very appealing for application in nanoelectronics. The absorption edge of the imaginary part of the dielectric function was found to occur in the visible range of light for parallel polarization. Finally, it was estimated that this novel 2D structure at room temperature can exhibit high thermal conductivities of 335 W mK -1 and 293 W mK -1 along the zigzag and armchair directions, respectively. Our study confirms that borophene hydride shows an outstanding combination of interesting mechanical, electronic, optical and thermal conduction properties, which are promising for the design of novel nanodevices.

An optical method to determine the thermodynamics of hydrogen absorption and desorption in metals

NASA Astrophysics Data System (ADS)

Gremaud, R.; Slaman, M.; Schreuders, H.; Dam, B.; Griessen, R.

2007-12-01

Hydrogenography, an optical high-throughput combinatorial technique to find hydrogen storage materials, has so far been applied only to materials undergoing a metal-to-semiconductor transition during hydrogenation. We show here that this technique works equally well for metallic hydrides. Additionally, we find that the thermodynamic data obtained optically on thin Pd-H films agree very well with Pd-H bulk data. This confirms that hydrogenography is a valuable general method to determine the relevant parameters for hydrogen storage in metal hydrides.

Synthesis, characterization, and photocatalytic properties of nanocrystalline NZO thin films

NASA Astrophysics Data System (ADS)

Aryanto, D.; Hastuti, E.; Husniya, N.; Sudiro, T.; Nuryadin, B. W.

2018-03-01

Nanocrystalline Ni-doped ZnO (NZO) thin films were synthesized on glass substrate using sol-gel spin coating methods. The effect of annealing on the structural and optical properties of nanocrystalline thin film was studied using X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), UV-VIS spectrophotometry, and photoluminescence (PL). The results showed that the annealing temperature strongly influenced the physical properties of nanocrystalline NZO thin films. The photocatalytic properties of nanocrystalline NZO thin films were evaluated using an aqueous solution of Rhodamine-B. The photocatalytic activity of nanocrystalline NZO thin films increased with the increase of annealing temperature. The results indicated that the structure, morphology, and band gap energy of nanocrystalline NZO thin films played an important role in photocatalytic activity.

Nanocrystalline SnO2 formation by oxygen ion implantation in tin thin films

NASA Astrophysics Data System (ADS)

Kondkar, Vidya; Rukade, Deepti; Kanjilal, Dinakar; Bhattacharyya, Varsha

2018-03-01

Metallic tin thin films of thickness 100 nm are deposited on fused silica substrates by thermal evaporation technique. These films are implanted with 45 keV oxygen ions at fluences ranging from 5 × 1015 to 5 × 1016 ions cm-2. The energy of the oxygen ions is calculated using SRIM in order to form embedded phases at the film-substrate interface. Post-implantation, films are annealed using a tube furnace for nanocrystalline tin oxide formation. These films are characterized using x-ray diffraction, Raman spectroscopy, UV-vis spectroscopy and photoluminescence spectroscopy. XRD and Raman spectroscopy studies reveal the formation of single rutile phase of SnO2. The size of the nanocrystallites formed decreases with an increase in the ion fluence. The nanocrystalline SnO2 formation is also confirmed by UV-vis and photoluminescence spectroscopy.

High H⁻ ionic conductivity in barium hydride.

PubMed

Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

2015-01-01

With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

Water as probe molecule for midgap states in nanocrystalline strontium titanate by conventional and synchronous luminescence spectroscopy under ambient conditions

NASA Astrophysics Data System (ADS)

Taylor, Sean; Samokhvalov, Alexander

2017-03-01

Alkaline earth metal titanates are broad bandgap semiconductors with applications in electronic devices, as catalysts, photocatalysts, sorbents, and sensors. Strontium titanate SrTiO3 is of interest in electronic devices, sensors, in the photocatalytic hydrogen generation, as catalyst and sorbent. Both photocatalysis and operation of electronic devices rely upon the pathways of relaxation of excited charge in the semiconductor, including relaxation through the midgap states. We report characterization of nanocrystalline SrTiO3 at room temperature by "conventional" vs. synchronous luminescence spectroscopy and complementary methods. We determined energies of radiative transitions in the visible range through the two midgap states in the nanocrystalline SrTiO3. Further, adsorption and desorption of vapor of water as "probe molecule" for midgap states in the nanocrystalline SrTiO3 was studied, for the first time, by luminescence spectroscopy under ambient conditions. Emission of visible light from the nanocrystalline SrTiO3 is significantly increased upon desorption of water and decreased (quenched) upon adsorption of water vapor, due to interactions with the surface midgap states.

Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions.

PubMed

Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui

2017-04-03

The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C-H bond. Herein, we report that HCO 2 - and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH - . The FeH - anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO 2 - was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of ICP-MS as a multi-element detector for sulfur and metal hydride impurities in hydrocarbon matrices.

PubMed

Geiger, William M; McSheehy, Shona; Nash, Martin J

2007-01-01

Maturation of inductively coupled plasma-mass spectrometry (ICP-MS) in terms of size, reliability, and cost has had a significant impact on its consideration as a viable detector for gas chromatography. Its generally excellent sensitivity for those elements it can measure has been a contributing factor. A method for sulfur speciation in various hydrocarbon products is investigated, as well as sulfur and metal hydride contaminants in high purity hydrocarbon feed stocks. Detection limits for sulfur species in hydrocarbon liquids and gases are approximately 5 and 10 ppb, respectively, as sulfur. Lower detection limits on the order of 100 parts per trillion are achieved for arsine. The use of collision cell technology (CCT) is exploited to remove interferences. CCT has been described elsewhere (1) using helium or helium-hydrogen mixtures for suppression of (16)O(16)O(+) interference with (32)S. In this work, a novel approach is investigated which uses oxygen to remove this interference by shifting it in a comprehensive fashion. The advantage of operating the system at full power with a tandem gas and liquid interface is also discussed.

Method of making nanocrystalline alpha alumina

DOEpatents

Siegel, Richard W.; Hahn, Horst; Eastman, Jeffrey A.

1992-01-01

Method of making selected phases of nanocrystalline ceramic materials. Various methods of controlling the production of nanocrystalline alpha alumina and titanium oxygen phases are described. Control of the gas atmosphere and use of particular oxidation treatments give rise to the ability to control the particular phases provided in the aluminum/oxygen and titanium/oxygen system.

Malic enzyme: Tritium isotope effects with alternative dinucleotide substrates and divalent metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karsten, W.E.; Harris, B.G.; Cook, P.F.

1992-01-01

The NAD-malic enzyme from Ascaris suum catalyzes the divalent metal ion dependent oxidative decarboxylation of L-malate to yield pyruvate, carbon dioxide and NADH. Multiple isotope effect studies suggest a stepwise chemical mechanism with hydride transfer from L-malate to NAD occurring first to form oxalacetate, followed by decarboxylation. Utilizing L-malate-2-T, tritium V/K isotope effects have been determined for the hydride transfer step using a variety of alternative dinucleotide substrates and divalent metal ions. Combination of these data with deuterium isotope effects data and previously determined [sup 13]C isotope effects has allowed the calculation of intrinsic isotope effects for the malic enzymemore » catalyzed reaction. The identity of both the dinucleotide substrate and divalent metal ion has an effect of the size of the intrinsic isotope effect for hydride transfer.« less

Stacking faults and mechanisms strain-induced transformations of hcp metals (Ti, Mg) during mechanical activation in liquid hydrocarbons

NASA Astrophysics Data System (ADS)

Lubnin, A. N.; Dorofeev, G. A.; Nikonova, R. M.; Mukhgalin, V. V.; Lad'yanov, V. I.

2017-11-01

The evolution of the structure and substructure of metals Ti and Mg with hexagonal close-packed (hcp) lattice is studied during their mechanical activation in a planetary ball mill in liquid hydrocarbons (toluene, n-heptane) and with additions of carbon materials (graphite, fullerite, nanotubes) by X-ray diffraction, scanning electron microscopy, and chemical analysis. The temperature behavior and hydrogen-accumulating properties of mechanocomposites are studied. During mechanical activation of Ti and Mg, liquid hydrocarbons decay, metastable nanocrystalline titanium carbohydride Ti(C,H) x and magnesium hydride β-MgH2 are formed, respectively. The Ti(C,H) x and MgH2 formation mechanisms during mechanical activation are deformation ones and are associated with stacking faults accumulation, and the formation of face-centered cubic (fcc) packing of atoms. Metastable Ti(C,H)x decays at a temperature of 550°C, the partial reverse transformation fcc → hcp occurs. The crystalline defect accumulation (nanograin boundaries, stacking faults), hydrocarbon destruction, and mechanocomposite formation leads to the enhancement of subsequent magnesium hydrogenation in the Sieverts reactor.

Reaction Rate of Ti0.18Zr0.84Cr1.0Fe0.7Mn0.3Cu0.057 to Use for the Heat Driven Type Compact Metal Hydride Refrigerator

NASA Astrophysics Data System (ADS)

Bae, Sang-Chul; Katsuta, Masafumi

Our final goal of this study is to develop the heat driven type compact metal hydride (MH) refrigeration system for the vending machine and the show case, and to attain a refrigeration temperature of 243 K by using a heat source of about 423K. The reaction rate of the MH to use for the heat source, MH used for heat source is studied firstly because the MH refrigeration system consists of two MHs, one is used for the heat source and the other is used for the cooling load extracting. As for the reaction rate in the hydriding process, initially, a rapid surface reaction, governed by the relation 1-(1-F )1/3=kht . After the MH surface has been covered by hydride, the reaction becomes diffusion controlled with the relation 1-3(1-F ' )2/3+2(1-F ' )=k'ht . The reaction rates, kh and k'h , are exponentially proportional to the pressure difference and increase with temperature. And, as for the dehydriding process, it is found out that the rate-controlling step is uniquely diffusion reaction. The dehydriding reaction rate is exponentially proportional to the pressure difference and the initial reacted fraction, and increases with temperature. Finally, on the basis of these experimental results, the brand new rate correlations are reasonably derived. The predicted results for this correlation are in successfully agreement with the experimental ones.

Equivalent circuit parameters of nickel/metal hydride batteries from sparse impedance measurements

NASA Astrophysics Data System (ADS)

Nelatury, Sudarshan Rao; Singh, Pritpal

In a recent communication, a method for extracting the equivalent circuit parameters of a lead acid battery from sparse (only three) impedance spectroscopy observations at three different frequencies was proposed. It was based on an equivalent circuit consisting of a bulk resistance, a reaction resistance and a constant phase element (CPE). Such a circuit is a very appropriate model of a lead-acid cell at high state of charge (SOC). This paper is a sequel to it and presents an application of it in case of nickel/metal hydride (Ni/MH) batteries, which also at high SOC are represented by the same circuit configuration. But when the SOC of a Ni/MH battery under interrogation goes low, The EIS curve has a positive slope at the low frequency end and our technique yields complex values for the otherwise real circuit parameters, suggesting the need for additional elements in the equivalent circuit and a definite relationship between parameter consistency and SOC. To improvise the previous algorithm, in order that it works reasonably well at both high and low SOCs, we propose three more measurements—two at very low frequencies to include the Warburg response and one at a high frequency to model the series inductance, in addition to the three in the mid frequency band—totally six measurements. In most of the today's instrumentation, it is the user who should choose the circuit configuration and the number of frequencies where impedance should be measured and the accompanying software performs data fitting by complex nonlinear least squares. The proposed method has built into it an SOC-based decision-making capability—both to choose the circuit configuration and to estimate the values of the circuit elements.

Feasibility of a nickel-metal hydride battery for totally implantable artificial hearts.

PubMed

Okamoto, E; Yoshida, T; Fujiyoshi, M; Shimanaka, M; Takeuchi, A; Mitamura, Y; Mikami, T

1996-01-01

An implantable rechargeable battery is one of the key technologies for totally implantable artificial hearts. The nickel-metal hydride (Ni-MH) battery is promising for its high energy density of 1.5-2.0 times that of a nickel-cadmium battery. In this study, the effects of pulsatile discharge loads on the operating time and cycle life of Ni-MH batteries at 39 degrees C were studied. Two battery cells (TH-3M, 1,200 mAh, phi 14.5 x 49 mm; Toshiba, Tokyo, Japan) in series were charge/discharge cycled at 39 degrees C using a charge current of 1CA (1,200 mA) and then were fully discharged to 1.0 V/cell under either pulsatile discharge loads, which mimicked a systole (1 A for 0.3 sec) and a diastole (0.4 A for 0.3 sec), or a non pulsatile discharge load equivalent to the average of the pulsatile loads (0.7 A). Each cycle life test was interrupted on the 482nd cycle under pulsatile load, and on the 423rd cycle under non pulsatile load, because of malfunction of each battery charger. The tests showed that the pulsatile discharge cells had significantly (p < 0.001) less operating time (74.0 +/- 7.15 min) throughout the test period (up to 482 days) compared to the cells under equivalent non pulsatile discharge loads (93.7 +/- 7.74 min). The pulsatile-discharged Ni-MH cells provide significantly less operating time than the constantly discharged cells; the Ni-MH battery has an operating time of over 78 min and a cycle life of almost 500 cycles at 39 degrees C. In conclusion, the Ni-MH battery is feasible as an implantable back-up battery for a totally implantable artificial heart system.

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

PubMed

Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

2017-06-01

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg 2 NiH 4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg 2 NiH 4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol -1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uranium Hydride Nucleation and Growth Model FY'16 ESC Annual Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Mary Ann; Richards, Andrew Walter; Holby, Edward F.

2016-12-20

Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

Production of Hydrogen by Electrocatalysis: Making the H-H Bond by Combining Protons and Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.

2014-03-25

Generation of hydrogen by reduction of two protons by two electrons can be catalysed by molecular electrocatalysts. Determination of the thermodynamic driving force for elimination of H2 from molecular complexes is important for the rational design of molecular electrocatalysts, and allows the design of metal complexes of abundant, inexpensive metals rather than precious metals (“Cheap Metals for Noble Tasks”). The rate of H2 evolution can be dramatically accelerated by incorporating pendant amines into diphosphine ligands. These pendant amines in the second coordination sphere function as protons relays, accelerating intramolecular and intermolecular proton transfer reactions. The thermodynamics of hydride transfer frommore » metal hydrides and the acidity of protonated pendant amines (pKa of N-H) contribute to the thermodynamics of elimination of H2; both of the hydricity and acidity can be systematically varied by changing the substituents on the ligands. A series of Ni(II) electrocatalysts with pendant amines have been developed. In addition to the thermochemical considerations, the catalytic rate is strongly influenced by the ability to deliver protons to the correct location of the pendant amine. Protonation of the amine endo to the metal leads to the N-H being positioned appropriately to favor rapid heterocoupling with the M-H. Designing ligands that include proton relays that are properly positioned and thermodynamically tuned is a key principle for molecular electrocatalysts for H2 production as well as for other multi-proton, multi-electron reactions important for energy conversions. The research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

The Bulk Nanocrystalline zn Produced by Mechanical Attrition

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Zhao, K. Y.; Li, C. J.; Tao, J. M.; Chan, T. L.; Koch, C. C.

The purpose of experiment was to produce bulk nanocrystalline Zn by mechanical attrition. The bulk nanocrystalline Zn produced by mechanical attrition was studied. The microstructural evolution during cryomilling and subsequent room temperature milling was characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). In this paper, Nanocrystalline Zn was produced by insitu consolidation of Zn elemental powder using mechanical attrition at liquid nitrogen and room temperature. For the samples studied, the longest elongation of 65% and highest stress of 200 MPa is obtained in nanocrystalline Zn during tensile testing at the condition of strain rate (10-3 sec-1) and 20°C which is equal to 0.43 Tm (Tm is the melting temperature of pure Zn).

Light-induced metal-insulator transition in a switchable mirror.

PubMed

Hoekstra, A F; Roy, A S; Rosenbaum, T F; Griessen, R; Wijngaarden, R J; Koeman, N J

2001-06-04

Rare earth hydride films can be converted reversibly from metallic mirrors to insulating windows simply by changing the surrounding hydrogen gas pressure at room temperature. At low temperatures, in situ doping is not possible in this way as hydrogen cannot diffuse. However, our finding of persistent photoconductivity under ultraviolet illumination offers an attractive possibility to tune yttrium hydride through the T = 0 metal-insulator transition. Conductivity and Hall measurements are used to determine critical exponents. The unusually large value for the product of the static and dynamical critical exponents appears to signify the important role played by electron-electron interactions.

Identification of a new pseudo-binary hydroxide during calendar corrosion of (La, Mg)2Ni7-type hydrogen storage alloys for Nickel-Metal Hydride batteries

NASA Astrophysics Data System (ADS)

Monnier, J.; Chen, H.; Joiret, S.; Bourgon, J.; Latroche, M.

2014-11-01

To improve the performances of Nickel-Metal Hydride batteries, an important step is the understanding of the corrosion processes that take place in the electrode material. In particular, the present study focuses for the first time on the model (La, Mg)2Ni7 system. The calendar corrosion in 8.7 M KOH medium was investigated from 6 h to 16 weeks immersion. By a unique combination of structural and elemental characterisations, the corrosion products are evidenced in those systems. In particular, we demonstrate that Ni and Mg combine in a pseudo-binary hydroxide Mg1-xNix(OH)2 whereas La corrodes into nanoporous La(OH)3 needles with inner hollow nanochannels.

Life cycle environmental assessment of lithium-ion and nickel metal hydride batteries for plug-in hybrid and battery electric vehicles.

PubMed

Majeau-Bettez, Guillaume; Hawkins, Troy R; Strømman, Anders Hammer

2011-05-15

This study presents the life cycle assessment (LCA) of three batteries for plug-in hybrid and full performance battery electric vehicles. A transparent life cycle inventory (LCI) was compiled in a component-wise manner for nickel metal hydride (NiMH), nickel cobalt manganese lithium-ion (NCM), and iron phosphate lithium-ion (LFP) batteries. The battery systems were investigated with a functional unit based on energy storage, and environmental impacts were analyzed using midpoint indicators. On a per-storage basis, the NiMH technology was found to have the highest environmental impact, followed by NCM and then LFP, for all categories considered except ozone depletion potential. We found higher life cycle global warming emissions than have been previously reported. Detailed contribution and structural path analyses allowed for the identification of the different processes and value-chains most directly responsible for these emissions. This article contributes a public and detailed inventory, which can be easily be adapted to any powertrain, along with readily usable environmental performance assessments.

Supercapacitors of nanocrystalline metal-organic frameworks.

PubMed

Choi, Kyung Min; Jeong, Hyung Mo; Park, Jung Hyo; Zhang, Yue-Biao; Kang, Jeung Ku; Yaghi, Omar M

2014-07-22

The high porosity of metal-organic frameworks (MOFs) has been used to achieve exceptional gas adsorptive properties but as yet remains largely unexplored for electrochemical energy storage devices. This study shows that MOFs made as nanocrystals (nMOFs) can be doped with graphene and successfully incorporated into devices to function as supercapacitors. A series of 23 different nMOFs with multiple organic functionalities and metal ions, differing pore sizes and shapes, discrete and infinite metal oxide backbones, large and small nanocrystals, and a variety of structure types have been prepared and examined. Several members of this series give high capacitance; in particular, a zirconium MOF exhibits exceptionally high capacitance. It has the stack and areal capacitance of 0.64 and 5.09 mF cm(-2), about 6 times that of the supercapacitors made from the benchmark commercial activated carbon materials and a performance that is preserved over at least 10000 charge/discharge cycles.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

NASA Astrophysics Data System (ADS)

El-Atwani, O.; Taylor, C. N.; Frishkoff, J.; Harlow, W.; Esquivel, E.; Maloy, S. A.; Taheri, M. L.

2018-01-01

Microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed helium was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

DOE PAGES

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James; ...

2017-11-09

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

Grain boundary phase transformations in PtAu and relevance to thermal stabilization of bulk nanocrystalline metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

O’Brien, C. J.; Barr, C. M.; Price, P. M.

There has recently been a great deal of interest in employing immiscible solutes to stabilize nanocrystalline microstructures. Existing modeling efforts largely rely on mesoscale Monte Carlo approaches that employ a simplified model of the microstructure and result in highly homogeneous segregation to grain boundaries. However, there is ample evidence from experimental and modeling studies that demonstrates segregation to grain boundaries is highly non-uniform and sensitive to boundary character. This work employs a realistic nanocrystalline microstructure with experimentally relevant global solute concentrations to illustrate inhomogeneous boundary segregation. Furthermore, experiments quantifying segregation in thin films are reported that corroborate the prediction thatmore » grain boundary segregation is highly inhomogeneous. In addition to grain boundary structure modifying the degree of segregation, the existence of a phase transformation between low and high solute content grain boundaries is predicted. In order to conduct this study, new embedded atom method interatomic potentials are developed for Pt, Au, and the PtAu binary alloy.« less

Grain boundary phase transformations in PtAu and relevance to thermal stabilization of bulk nanocrystalline metals

DOE PAGES

O’Brien, C. J.; Barr, C. M.; Price, P. M.; ...

2017-10-31

There has recently been a great deal of interest in employing immiscible solutes to stabilize nanocrystalline microstructures. Existing modeling efforts largely rely on mesoscale Monte Carlo approaches that employ a simplified model of the microstructure and result in highly homogeneous segregation to grain boundaries. However, there is ample evidence from experimental and modeling studies that demonstrates segregation to grain boundaries is highly non-uniform and sensitive to boundary character. This work employs a realistic nanocrystalline microstructure with experimentally relevant global solute concentrations to illustrate inhomogeneous boundary segregation. Furthermore, experiments quantifying segregation in thin films are reported that corroborate the prediction thatmore » grain boundary segregation is highly inhomogeneous. In addition to grain boundary structure modifying the degree of segregation, the existence of a phase transformation between low and high solute content grain boundaries is predicted. In order to conduct this study, new embedded atom method interatomic potentials are developed for Pt, Au, and the PtAu binary alloy.« less

The free-energy barrier to hydride transfer across a dipalladium complex

DOE PAGES

Ramirez-Cuesta, Anibal J.

2015-01-01

We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)(2)CH2}(2)Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model formore » the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.« less

Micro-macroscopic coupled modeling of batteries and fuel cells. 2: Application to nickel-cadmium and nickel-metal hydride cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, W.B.; Wang, C.Y.; Liaw, B.Y.

1998-10-01

The micro-macroscopic coupled model developed in a companion paper is applied to predict the discharge and charge behaviors of nickel-cadmium (Ni-Cd) and nickel-metal hydride (Ni-MH) cells. The model integrates important microscopic phenomena such as proton or hydrogen diffusion and conduction of electrons in active materials into the macroscopic calculations of species and charge transfer. Simulation results for a full Ni-Cd cell and single MH electrode are presented and validated against the pseudo two-dimensional numerical model in the literature. In good agreement with the previous results, the present family of models is computationally more efficient and is particularly suitable for simulationsmore » of complex test conditions, such as the dynamic stress test and pulse charging for electric vehicles. In addition, a mathematical model for full Ni-MH cells is presented and sample simulations are performed for discharge and recharge with oxygen generation and recombination taken into account. These gas reactions represent an important mechanism for battery overcharge in the electric vehicle application.« less

Destabilisation of complex hydrides through size effects.

PubMed

Christian, Meganne; Aguey-Zinsou, Kondo-Francois

2010-12-01

Nanoparticles of NaAlH4, LiAlH4 and LiBH4 were prepared by encapsulating their respective hydrides within carbon nanotubes by a wet chemical approach. The resulting confinement had a profound effect on the overall hydrogen storage properties of these hydrides, with NaAlH4 and LiAlH4 releasing hydrogen from room temperature, for example.

Preparation of high-quality ultrathin transmission electron microscopy specimens of a nanocrystalline metallic powder.

PubMed

Riedl, Thomas; Gemming, Thomas; Mickel, Christine; Eymann, Konrad; Kirchner, Alexander; Kieback, Bernd

2012-06-01

This article explores the achievable transmission electron microscopy specimen thickness and quality by using three different preparation methods in the case of a high-strength nanocrystalline Cu-Nb powder alloy. Low specimen thickness is essential for spatially resolved analyses of the grains in nanocrystalline materials. We have found that single-sided as well as double-sided low-angle Ar ion milling of the Cu-Nb powders embedded into epoxy resin produced wedge-shaped particles of very low thickness (<10 nm) near the edge. By means of a modified focused ion beam lift-out technique generating holes in the lamella interior large micrometer-sized electron-transparent regions were obtained. However, this lamella displayed a higher thickness at the rim of ≥30 nm. Limiting factors for the observed thicknesses are discussed including ion damage depths, backscattering, and surface roughness, which depend on ion type, energy, current density, and specimen motion. Finally, sections cut by ultramicrotomy at low stroke rate and low set thickness offered vast, several tens of square micrometers uniformly thin regions of ∼10-nm minimum thickness. As major drawbacks, we have detected a thin coating on the sections consisting of epoxy deployed as the embedding material and considerable nanoscale thickness variations. Copyright © 2011 Wiley Periodicals, Inc.

Fine structure of the K X-ray absorption spectra of titanium in some hydrides, borides, and silicides (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vainshtein, �. E.; Zhurakovskii, E. A.

1959-08-01

X-ray spectral analyses confirmed the hypothesis on the metal-like state of hydrogen in tithnium hydrides. Experiments with titunium borides and silicides indicate the special character and degree of the 3d--level participation in the metallic'' bond between the atoms of various complexes. The structure of metalloid elements becomes more complicated with an increase in the specific number of boron and silicon atoms and the bond between the atoms tends to become covalent. (R.V.J.)

Lead detection using micro/nanocrystalline boron-doped diamond by square-wave anodic stripping voltammetry.

PubMed

Arantes, Tatiane M; Sardinha, André; Baldan, Mauricio R; Cristovan, Fernando H; Ferreira, Neidenei G

2014-10-01

Monitoring heavy metal ion levels in water is essential for human health and safety. Electroanalytical techniques have presented important features to detect toxic trace heavy metals in the environment due to their high sensitivity associated with their easy operational procedures. Square-wave voltammetry is a powerful electrochemical technique that may be applied to both electrokinetic and analytical measurements, and the analysis of the characteristic parameters of this technique also enables the mechanism and kinetic evaluation of the electrochemical process under study. In this work, we present a complete optimized study on the heavy metal detection using diamond electrodes. It was analyzed the influence of the morphology characteristics as well as the doping level on micro/nanocrystalline boron-doped diamond films by means of square-wave anodic stripping voltammetry (SWASV) technique. The SWASV parameters were optimized for all films, considering that their kinetic response is dependent on the morphology and/or doping level. The films presented reversible results for the Lead [Pb (II)] system studied. The Pb (II) analysis was performed in ammonium acetate buffer at pH 4.5, varying the lead concentration in the range from 1 to 10 μg L(-1). The analytical responses were obtained for the four electrodes. However, the best low limit detection and reproducibility was found for boron doped nanocrystalline diamond electrodes (BDND) doped with 2000 mg L(-1) in B/C ratio. Copyright © 2014 Elsevier B.V. All rights reserved.

Solid State NMR Studies of the Aluminum Hydride Phases

NASA Technical Reports Server (NTRS)

Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

2006-01-01

Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

Regenerative Hydride Heat Pump

NASA Technical Reports Server (NTRS)

Jones, Jack A.

1992-01-01

Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

On the Chemistry of Hydrides of N Atoms and O+ Ions

NASA Astrophysics Data System (ADS)

Awad, Zainab; Viti, Serena; Williams, David A.

2016-08-01

Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

Calcium metaborate as a cathode additive to improve the high-temperature properties of nickel hydroxide electrodes for nickel-metal hydride batteries

NASA Astrophysics Data System (ADS)

Li, Jing; Shangguan, Enbo; Guo, Dan; Li, Quanmin; Chang, Zhaorong; Yuan, Xiao-Zi; Wang, Haijiang

2014-10-01

In this paper, a novel additive, calcium metaborate (CMB), is proposed to improve the high-temperature characteristics of the nickel electrodes for nickel-metal hydride batteries. As a soluble calcium salt, CMB can easily and uniformly be dispersed in the nickel electrodes. The effects of CMB on the nickel electrode are investigated via a combination of cyclability, capacity retention, electrochemical impedance spectroscopy, scanning electron microscope and X-ray diffraction. Compared with conventional nickel electrodes, the electrode containing 0.5 wt.% CMB exhibits superior electrode properties including enhanced discharge capacity, improved high-rate discharge ability and excellent cycle stability at an elevated temperature (70 °C). The improved cell performance of the nickel electrode containing CMB additives can be attributable to the increased oxygen evolution overvoltage and slower oxygen evolution rate. Compared with insoluble calcium salts, such as Ca(OH)2, CaCO3, and CaF2, CMB is more effective as a cathode additive to improve the high-temperature performance of Ni-MH batteries.

Durability of nickel-metal hydride (Ni-MH) battery cathode using nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite

NASA Astrophysics Data System (ADS)

Béléké, Alexis Bienvenu; Higuchi, Eiji; Inoue, Hiroshi; Mizuhata, Minoru

2014-02-01

We report the durability of the optimized nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite prepared by liquid phase deposition (LPD) as cathode active materials in nickel metal hydride (Ni-MH) secondary battery. The positive electrode was used for charge-discharge measurements under two different current: 5 mA for 300 cycles in half-cell conditions, and 5.8 mA for 569 cycles in battery regime, respectively. The optimized Ni-Al LDH/C composite exhibits a good lifespan and stability with the capacity retention above 380 mA h gcomp-1 over 869 cycles. Cyclic voltammetry shows that the α-Ni(OH)2/γ-NiOOH redox reaction is maintained even after 869 cycles, and the higher current regime is beneficial in terms of materials utilization. X-ray diffraction (XRD) patterns of the cathode after charge and discharge confirms that the α-Ni(OH)2/γ-NiOOH redox reaction occurs without any intermediate phase.

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

DOE PAGES

Maity, Niladri; Barman, Samir; Callens, Emmanuel; ...

2015-11-30

The well-defined single-site silica-supported tungsten complex [(Si–O–)W(Me) 5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si–O–)WH 3(Me) 2], as the predominant species at -78more » °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si–O–)WH 3(CH 2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.« less

The onset and evolution of fatigue-induced abnormal grain growth in nanocrystalline Ni–Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furnish, T. A.; Mehta, A.; Van Campen, D.

Conventional structural metals suffer from fatigue-crack initiation through dislocation activity which forms persistent slip bands leading to notch-like extrusions and intrusions. Ultrafine-grained and nanocrystalline metals can potentially exhibit superior fatigue-crack initiation resistance by suppressing these cumulative dislocation activities. Prior studies on these metals have confirmed improved high-cycle fatigue performance. In the case of nano-grained metals, analyses of subsurface crack initiation sites have indicated that the crack nucleation is associated with abnormally large grains. But, these post-mortem analyses have led to only speculation about when abnormal grain growth occurs (e.g., during fatigue, after crack initiation, or during crack growth). In thismore » study, a recently developed synchrotron X-ray diffraction technique was used to detect the onset and progression of abnormal grain growth during stress-controlled fatigue loading. Our study provides the first direct evidence that the grain coarsening is cyclically induced and occurs well before final fatigue failure—our results indicate that the first half of the fatigue life was spent prior to the detectable onset of abnormal grain growth, while the second half was spent coarsening the nanocrystalline structure and cyclically deforming the abnormally large grains until crack initiation. Post-mortem fractography, coupled with cycle-dependent diffraction data, provides the first details regarding the kinetics of this abnormal grain growth process during high-cycle fatigue testing. Finally, precession electron diffraction images collected in a transmission electron microscope after the in situ fatigue experiment also confirm the X-ray evidence that the abnormally large grains contain substantial misorientation gradients and sub-grain boundaries.« less

The onset and evolution of fatigue-induced abnormal grain growth in nanocrystalline Ni–Fe

DOE PAGES

Furnish, T. A.; Mehta, A.; Van Campen, D.; ...

2016-10-11

Conventional structural metals suffer from fatigue-crack initiation through dislocation activity which forms persistent slip bands leading to notch-like extrusions and intrusions. Ultrafine-grained and nanocrystalline metals can potentially exhibit superior fatigue-crack initiation resistance by suppressing these cumulative dislocation activities. Prior studies on these metals have confirmed improved high-cycle fatigue performance. In the case of nano-grained metals, analyses of subsurface crack initiation sites have indicated that the crack nucleation is associated with abnormally large grains. But, these post-mortem analyses have led to only speculation about when abnormal grain growth occurs (e.g., during fatigue, after crack initiation, or during crack growth). In thismore » study, a recently developed synchrotron X-ray diffraction technique was used to detect the onset and progression of abnormal grain growth during stress-controlled fatigue loading. Our study provides the first direct evidence that the grain coarsening is cyclically induced and occurs well before final fatigue failure—our results indicate that the first half of the fatigue life was spent prior to the detectable onset of abnormal grain growth, while the second half was spent coarsening the nanocrystalline structure and cyclically deforming the abnormally large grains until crack initiation. Post-mortem fractography, coupled with cycle-dependent diffraction data, provides the first details regarding the kinetics of this abnormal grain growth process during high-cycle fatigue testing. Finally, precession electron diffraction images collected in a transmission electron microscope after the in situ fatigue experiment also confirm the X-ray evidence that the abnormally large grains contain substantial misorientation gradients and sub-grain boundaries.« less

Light metal explosives and propellants

DOEpatents

Wood, Lowell L.; Ishikawa, Muriel Y.; Nuckolls, John H.; Pagoria, Phillip F.; Viecelli, James A.

2005-04-05

Disclosed herein are light metal explosives, pyrotechnics and propellants (LME&Ps) comprising a light metal component such as Li, B, Be or their hydrides or intermetallic compounds and alloys containing them and an oxidizer component containing a classic explosive, such as CL-20, or a non-explosive oxidizer, such as lithium perchlorate, or combinations thereof. LME&P formulations may have light metal particles and oxidizer particles ranging in size from 0.01 .mu.m to 1000 .mu.m.

Precipitation of hydrides in high purity niobium after different treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkov, F.; Romanenko, A.; Trenikhina, Y.

Precipitation of lossy non-superconducting niobium hydrides represents a known problem for high purity niobium in superconducting applications. Using cryogenic optical and laser confocal scanning microscopy we have directly observed surface precipitation and evolution of niobium hydrides in samples after different treatments used for superconducting RF cavities for particle acceleration. Precipitation is shown to occur throughout the sample volume, and the growth of hydrides is well described by the fast diffusion-controlled process in which almost all hydrogen is precipitated atmore » $T=140$~K within $$\\sim30$$~min. 120$$^{\\circ}$$C baking and mechanical deformation are found to affect hydride precipitation through their influence on the number of nucleation and trapping centers.« less

Multiple electron injection dynamics in linearly-linked two dye co-sensitized nanocrystalline metal oxide electrodes for dye-sensitized solar cells.

PubMed

Shen, Qing; Ogomi, Yuhei; Park, Byung-wook; Inoue, Takafumi; Pandey, Shyam S; Miyamoto, Akari; Fujita, Shinsuke; Katayama, Kenji; Toyoda, Taro; Hayase, Shuzi

2012-04-07

Understanding the electron transfer dynamics at the interface between dye sensitizer and semiconductor nanoparticle is very important for both a fundamental study and development of dye-sensitized solar cells (DSCs), which are a potential candidate for next generation solar cells. In this study, we have characterized the ultrafast photoexcited electron dynamics in a newly produced linearly-linked two dye co-sensitized solar cell using both a transient absorption (TA) and an improved transient grating (TG) technique, in which tin(IV) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (NcSn) and cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium) (N719) are molecularly and linearly linked and are bonded to the surface of a nanocrystalline tin dioxide (SnO(2)) electrode by a metal-O-metal linkage (i.e. SnO(2)-NcSn-N719). By comparing the TA and TG kinetics of NcSn, N719, and hybrid NcSn-N719 molecules adsorbed onto both of the SnO(2) and zirconium dioxide (ZrO(2)) nanocrystalline films, the forward and backward electron transfer dynamics in SnO(2)-NcSn-N719 were clarified. We found that there are two pathways for electron injection from the linearly-linked two dye molecules (NcSn-N719) to SnO(2). The first is a stepwise electron injection, in which photoexcited electrons first transfer from N719 to NcSn with a transfer time of 0.95 ps and then transfer from NcSn to the conduction band (CB) of SnO(2) with two timescales of 1.6 ps and 4.2 ps. The second is direct photoexcited electron transfer from N719 to the CB of SnO(2) with a timescale of 20-30 ps. On the other hand, back electron transfer from SnO(2) to NcSn is on a timescale of about 2 ns, which is about three orders of magnitude slower compared to the forward electron transfer from NcSn to SnO(2). The back electron transfer from NcSn to N719 is on a timescale of about 40 ps, which is about one order slower compared to the forward electron transfer from N719 to Nc

Nanocrystalline heterojunction materials

DOEpatents

Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

2003-07-15

Mesoporous nanocrystalline titanium dioxide heterojunction materials are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

Reductive alkylation of active methylene compounds with carbonyl derivatives, calcium hydride and a heterogeneous catalyst.

PubMed

Guyon, Carole; Duclos, Marie-Christine; Sutter, Marc; Métay, Estelle; Lemaire, Marc

2015-07-07

A one-pot two-step reaction (Knoevenagel condensation - reduction of the double bond) has been developed using calcium hydride as a reductant in the presence of a supported noble metal catalyst. The reaction between carbonyl compounds and active methylene compounds such as methylcyanoacetate, 1,3-dimethylbarbituric acid, dimedone and the more challenging dimethylmalonate, affords the corresponding monoalkylated products in moderate to good yields (up to 83%) with minimal reduction of the starting carbonyl compounds.

Expanding Thorium Hydride Chemistry Through Th²⁺, Including the Synthesis of a Mixed-Valent Th⁴⁺/Th³⁺ Hydride Complex.

PubMed

Langeslay, Ryan R; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2016-03-30

The reactivity of the recently discovered Th(2+) complex [K(18-crown-6)(THF)2][Cp″3Th], 1 [Cp'' = C5H3(SiMe3)2-1,3], with hydrogen reagents has been investigated and found to provide syntheses of new classes of thorium hydride compounds. Complex 1 reacts with [Et3NH][BPh4] to form the terminal Th(4+) hydride complex Cp″3ThH, 2, a reaction that formally involves a net two-electron reduction. Complex 1 also reacts in the solid state and in solution with H2 to form a mixed-valent bimetallic product, [K(18-crown-6)(Et2O)][Cp″2ThH2]2, 3, which was analyzed by X-ray crystallography, electron paramagnetic resonance and optical spectroscopy, and density functional theory. The existence of 3, which formally contains Th(3+) and Th(4+), suggested that KC8 could reduce [(C5Me5)2ThH2]2. In the presence of 18-crown-6, this reaction forms an analogous mixed-valent product formulated as [K(18-crown-6)(THF)][(C5Me5)2ThH2]2, 4. A similar complex with (C5Me4H)(1-) ligands was not obtained, but reaction of (C5Me4H)3Th with H2 in the presence of KC8 and 2.2.2-cryptand at -45 °C produced two monometallic hydride products, namely, (C5Me4H)3ThH, 5, and [K(2.2.2-cryptand)]{(C5Me4H)2[η(1):η(5)-C5Me3H(CH2)]ThH]}, 6. Complex 6 contains a metalated tetramethylcyclopentadienyl dianion, [C5Me3H(CH2)](2-), that binds in a tuck-in mode.

Synthesis of Nano-Crystalline Gamma-TiAl Materials

NASA Technical Reports Server (NTRS)

Hales, Stephen J.; Vasquez, Peter

2003-01-01

One of the principal problems with nano-crystalline materials is producing them in quantities and sizes large enough for valid mechanical property evaluation. The purpose of this study was to explore an innovative method for producing nano-crystalline gamma-TiAl bulk materials using high energy ball milling and brief secondary processes. Nano-crystalline powder feedstock was produced using a Fritsch P4(TM) vario-planetary ball mill recently installed at NASA-LaRC. The high energy ball milling process employed tungsten carbide tooling (vials and balls) and no process control agents to minimize contamination. In a collaborative effort, two approaches were investigated, namely mechanical alloying of elemental powders and attrition milling of pre-alloyed powders. The objective was to subsequently use RF plasma spray deposition and short cycle vacuum hot pressing in order to effect consolidation while retaining nano-crystalline structure in bulk material. Results and discussion of the work performed to date are presented.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current

Quantifying the stress fields due to a delta-hydride precipitate in alpha-Zr matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tummala, Hareesh; Capolungo, Laurent; Tome, Carlos N.

This report is a preliminary study on δ-hydride precipitate in zirconium alloy performed using 3D discrete dislocation dynamics simulations. The ability of dislocations in modifying the largely anisotropic stress fields developed by the hydride particle in a matrix phase is addressed for a specific dimension of the hydride. The influential role of probable dislocation nucleation at the hydride-matrix interface is reported. Dislocation nucleation around a hydride was found to decrease the shear stress (S 13) and also increase the normal stresses inside the hydride. We derive conclusions on the formation of stacks of hydrides in zirconium alloys. The contribution ofmore » mechanical fields due to dislocations was found to have a non-negligible effect on such process.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE PAGES

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.; ...

2017-05-31

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Transition Metal Switchable Mirror

ScienceCinema

None

2017-12-09

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft.

Transition Metal Switchable Mirror

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2009-08-21

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft.

Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium.

PubMed

Pitman, Catherine L; Brereton, Kelsey R; Miller, Alexander J M

2016-02-24

Aqueous hydride transfer is a fundamental step in emerging alternative energy transformations such as H2 evolution and CO2 reduction. "Hydricity," the hydride donor ability of a species, is a key metric for understanding transition metal hydride reactivity, but comprehensive studies of aqueous hydricity are scarce. An extensive and self-consistent aqueous hydricity scale is constructed for a family of Ru and Ir hydrides that are key intermediates in aqueous catalysis. A reference hydricity is determined using redox potentiometry and spectrophotometric titration for a particularly water-soluble species. Then, relative hydricity values for a range of species are measured using hydride transfer equilibria, taking advantage of expedient new synthetic procedures for Ru and Ir hydrides. This large collection of hydricity values provides the most comprehensive picture so far of how ligands impact hydricity in water. Strikingly, we also find that hydricity can be viewed as a continuum in water: the free energy of hydride transfer changes with pH, buffer composition, and salts present in solution.

An elasto-plastic fracture mechanics based model for assessment of hydride embrittlement in zircaloy cladding tubes

NASA Astrophysics Data System (ADS)

Nilsson, Karl-Fredrik; Jakšić, Nikola; Vokál, Vratko

2010-01-01

This paper describes a finite element based fracture mechanics model to assess how hydrides affect the integrity of zircaloy cladding tubes. The hydrides are assumed to fracture at a low load whereas the propagation of the fractured hydrides in the matrix material and failure of the tube is controlled by non-linear fracture mechanics and plastic collapse of the ligaments between the hydrides. The paper quantifies the relative importance of hydride geometrical parameters such as size, orientation and location of individual hydrides and interaction between adjacent hydrides. The paper also presents analyses for some different and representative multi-hydride configurations. The model is adaptable to general and complex crack configurations and can therefore be used to assess realistic hydride configurations. The mechanism of cladding failure is by plastic collapse of ligaments between interacting fractured hydrides. The results show that the integrity can be drastically reduced when several radial hydrides form continuous patterns.

Application of micro- and nanocrystalline cellulose

NASA Astrophysics Data System (ADS)

Sotnikova, Yu S.; Demina, T. S.; Istomin, A. V.; Goncharuk, G. P.; Grandfils, Ch; Akopova, T. A.; Zelenetskii, A. N.; Babayevsky, P. G.

2018-04-01

Micro- and nanocrystalline forms of cellulose were extracted from flax stalks and evaluated in terms of their applicability for various materials science tasks. It was revealed that both form of cellulose had anisometric morphology with length of 27.1 μm and 159 nm; diameter of 8.7 μm and 85 nm, respectively. They were used as reinforcing fillers for fabrication of composite films based on hydroxyethylcellulose. Film-forming and mechanical properties of the composite materials were significantly varied in dependence on filler content (0–10 wt.%) and size. As a second option of micro- and nanocrystalline cellulose application, a study of their effectiveness as stabilizing agents for oil/water Pickering emulsions was carried out. In contrast to micron-sized cellulose the nanocrystalline form appeared to be successful in the process of CH2Cl2/water interface stabilization and fabrication of polylactide microparticles via oil/water Pickering emulsion solvent evaporation technique.

Electrochemical hydride generation for the simultaneous determination of hydride forming elements by inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Castillo, J. R.; Sturgeon, R. E.

2004-04-01

Simultaneous measurements of As, Sb, Se, Sn and Ge were performed by inductively coupled plasma atomic emission spectrometry following their electrochemical hydride generation. An electrochemical hydride generator based on a concentric arrangement with a porous cathode, working in a continuous flow mode was used. The effects of sample flow rate, applied current and electrolytic solution concentration on response were studied and their influence on the mechanisms of hydride generation discussed. Four materials, particulate lead, reticulated vitreous carbon (RVC), silver and amalgamated silver were tested as cathode materials. The best results were achieved with particulate lead and RVC cathodes, wherein generation efficiencies higher than 80% were estimated for most of the analytes. In general, limits of detection between 0.1 and 3.6 ng ml -1 and a precision better than 5% were achieved using a lead cathode. The analysis of a marine sediment reference material (PACS-2, NRC) showed good agreement with the certified values for As and Se.

Comparative Photoemission Study of Actinide (Am, Pu, Np and U) Metals, Nitrides, and Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gouder, Thomas; Seibert, Alice; Rebizant, Jean

2007-07-01

Core-level and valence-band spectra of Pu and the other early actinide compounds show remarkable systematics, which can be understood in the framework of final state screening. We compare the early actinide (U, Np, Pu and Am) metals, nitrides and hydrides and a few other specific compounds (PuSe, PuS, PuCx, PuSix) prepared as thin films by sputter deposition. In choosing these systems, we combine inherent 5f band narrowing, due to 5f orbital contraction throughout the actinide series, with variations of the chemical environment in the compounds. Goal of this work was to learn more on the electronic structure of the earlymore » actinide systems and to achieve the correct interpretation of their photoemission spectra. The highly correlated nature of the 5f states in systems, which are on the verge to localization, makes this a challenging task, because of the peculiar interplay between ground state DOS and final-state effects. Their influence can be estimated by doing systematic studies on systems with different (5f) bandwidths. We conclude on the basis of such systematic experiments that final-state effects due to strong e-e correlations in narrow 5f-band systems lead to multiplet like structures, analogous to those observed in the case of systems with localized electron states. Such observations in essentially band-like 5f-systems was first surprising, but the astonishing similarity of photoemission spectra of very different chemical systems (e.g. PuSe, Pu{sub 2}C{sub 3}..) points to a common origin, relating them to atomic features rather than material dependent density of states (DOS) features. (authors)« less

Investigations of Nanocrystalline Alloy Electrospark Coating Made of Nanocrystalline Alloy Based on 5БДCP Ferrum

NASA Astrophysics Data System (ADS)

Kolomeichenko, A. V.; Kuznetsov, I. S.; Izmaylov, A. Yu; Solovyev, R. Yu; Sharifullin, S. N.

2017-09-01

The article describes the properties of wear resistant electrospark coating made of nanocrystalline alloy of type 5БДCP (Finemet). It is proved that electrospark coating has nanocrystalline structure which is like amorphous matrix with nanocrystals α - Fe. Coating thickness is 33 μm, micro-hardness is 8461 - 11357 MPa, wear resistance is 0,55×104s/g. Coating ofnanocrystalline alloy of type 5БДCP can be used to increase wear resistance of machinery working surfaces.

Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition

DTIC Science & Technology

2014-11-01

Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition by Tiffany Ngo ARL-TN-0643...November 2014 Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by Cryogenic Attrition Tiffany Ngo Weapons and...3. DATES COVERED (From - To) August 2014 4. TITLE AND SUBTITLE Characterization of Nanocrystalline Aluminum Alloy 5083 Powders Produced by

Processing and properties of Ti-6Al-4V hollow sphere foams from hydride powder

NASA Astrophysics Data System (ADS)

Hardwicke, Canan Uslu

Honeycomb structures currently used in aerospace systems are expensive to manufacture, limited to sheet form, and present joining problems and mechanical anisotropy that promotes shear failure at low stresses. Metallic foams produced by point contact bonding of monosized hollow spheres offer an alternative if they can be processed into strong, light-weight, and reasonably priced structural materials. In this work, technology has been established for fabricating good quality, Ti-6Al-4V hollow sphere foams using the coaxial nozzle powder slurry technique. It was shown that hydride form of Ti-ELI can be used as the starting precursor powder and processed into fine particles of 1-10 mum size range without increasing the impurity levels. Hydride dispersion in acetone was provided by the addition of polyester/polyamine copolymers through electrosteric stabilization. Addition of PMMA to the pseudoplastically dispersed organic slurries helped bind hydride powder spherical shells. Furthermore, monosized Ti-6Al-4V hollow spheres were sintered to 98% dense cell walls in Ar and point-contact bonded into closed-cell foams through solid-state diffusion. These findings suggest that near-net shape Ti-6Al-4V structures may be produced with isotropic properties, strength, toughness, and densities as low as 10% of the bulk. Findings concerning the optimum processing parameters and implications for future research are discussed.

Nanocrystalline cellulose from coir fiber: preparation, properties, and applications

USDA-ARS?s Scientific Manuscript database

Nanocrystalline cellulose derived from various botanical sources offers unique and potentially useful characteristics. In principle, any cellulosic material can be considered as a potential source of a nanocrystalline material, including crops, crop residues, and agroindustrial wastes. Because of t...

Self-ion irradiation effects on mechanical properties of nanocrystalline zirconium films

DOE PAGES

Wang, Baoming; Haque, M. A.; Tomar, Vikas; ...

2017-07-13

Zirconium thin films were irradiated at room temperature with an 800 keV Zr + beam using a 6 MV HVE Tandem accelerator to 1.36 displacement per atom damage. Freestanding tensile specimens, 100 nm thick and 10 nm grain size, were tested in-situ inside a transmission electron microscope. Significant grain growth (>300%), texture evolution, and displacement damage defects were observed. Here, stress-strain profiles were mostly linear elastic below 20 nm grain size, but above this limit the samples demonstrated yielding and strain hardening. Experimental results support the hypothesis that grain boundaries in nanocrystalline metals act as very effective defect sinks.

The processing of aluminum gasarites via thermal decomposition of interstitial hydrides

NASA Astrophysics Data System (ADS)

Licavoli, Joseph J.

Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

Nanocrystalline Heterojunction Materials

DOEpatents

Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

2004-02-03

Mesoporous nanocrystalline titanium dioxide heterojunction materials and methods of making the same are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

DISPERSION HARDENING OF URANIUM METAL

DOEpatents

Arbiter, W.

1963-01-15

A method of hardening U metal involves the forming of a fine dispersion of UO/sub 2/. This method consists of first hydriding the U to form a finely divided powder and then exposing the powder to a very dilute O gas in an inert atmosphere under such pressure and temperature conditions as to cause a thin oxide film to coat each particle of the U hydride, The oxide skin prevents agglomeration of the particles as the remaining H is removed, thus preserving the small particle size. The oxide skin coatings remain as an oxide dispersion. The resulting product may be workhardened to improve its physical characteristics. (AEC)

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, Gary L.

1988-08-16

A method for preparing highly hydrogen-reactive surfaces on metals which normally require substantial heating, high pressures, or an extended induction period, which involves pretreatment of said surfaces with either a non-oxidizing acid or hydrogen gas to form a hydrogen-bearing coating on said surfaces, and subsequently heating said coated metal in the absence of moisture and oxygen for a period sufficient to decompose said coating and cooling said metal to room temperature. Surfaces so treated will react almost instantaneously with hydrogen gas at room temperature and low pressure. The method is particularly applicable to uranium, thorium, and lanthanide metals.

Methods for preparation of nanocrystalline rare earth phosphates for lighting applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comanzo, Holly Ann; Manoharan, Mohan; Martins Loureiro, Sergio Paulo

Disclosed here are methods for the preparation of optionally activated nanocrystalline rare earth phosphates. The optionally activated nanocrystalline rare earth phosphates may be used as one or more of quantum-splitting phosphor, visible-light emitting phosphor, vacuum-UV absorbing phosphor, and UV-emitting phosphor. Also disclosed herein are discharge lamps comprising the optionally activated nanocrystalline rare earth phosphates provided by these methods.

In-Bed Accountability Development for a Passively Cooled, Electrically Heated Hydride (PACE) Bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.E.

A nominal 1500 STP-L PAssively Cooled, Electrically heated hydride (PACE) Bed has been developed for implementation into a new Savannah River Site tritium project. The 1.2 meter (four-foot) long process vessel contains on internal 'U-tube' for tritium In-Bed Accountability (IBA) measurements. IBA will be performed on six, 12.6 kg production metal hydride storage beds.IBA tests were done on a prototype bed using electric heaters to simulate the radiolytic decay of tritium. Tests had gas flows from 10 to 100 SLPM through the U-tube or 100 SLPM through the bed's vacuum jacket. IBA inventory measurement errors at the 95% confidence levelmore » were calculated using the correlation of IBA gas temperature rise, or (hydride) bed temperature rise above ambient temperature, versus simulated tritium inventory.Prototype bed IBA inventory errors at 100 SLPM were the largest for gas flows through the vacuum jacket: 15.2 grams for the bed temperature rise and 11.5 grams for the gas temperature rise. For a 100 SLPM U-tube flow, the inventory error was 2.5 grams using bed temperature rise and 1.6 grams using gas temperature rise. For 50 to 100 SLPM U-tube flows, the IBA gas temperature rise inventory errors were nominally one to two grams that increased above four grams for flows less than 50 SLPM. For 50 to 100 SLPM U-tube flows, the IBA bed temperature rise inventory errors were greater than the gas temperature rise errors, but similar errors were found for both methods at gas flows of 20, 30, and 40 SLPM.Electric heater IBA tests were done for six production hydride beds using a 45 SLPM U-tube gas flow. Of the duplicate runs performed on these beds, five of the six beds produced IBA inventory errors of approximately three grams: consistent with results obtained in the laboratory prototype tests.« less

In-Bed Accountability Development for a Passively Cooled, Electrically Heated Hydride (PACE) Bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

KLEIN, JAMES

A nominal 1500 STP-L PAssively Cooled, Electrically heated hydride (PACE) Bed has been developed for implementation into a new Savannah River Site tritium project. The 1.2 meter (four-foot) long process vessel contains an internal ''U-tube'' for tritium In-Bed Accountability (IBA) measurements. IBA will be performed on six, 12.6 kg production metal hydride storage beds. IBA tests were done on a prototype bed using electric heaters to simulate the radiolytic decay of tritium. Tests had gas flows from 10 to 100 SLPM through the U-tube or 100 SLPM through the bed's vacuum jacket. IBA inventory measurement errors at the 95 percentmore » confidence level were calculated using the correlation of IBA gas temperature rise, or (hydride) bed temperature rise above ambient temperature, versus simulated tritium inventory. Prototype bed IBA inventory errors at 100 SLPM were the largest for gas flows through the vacuum jacket: 15.2 grams for the bed temperature rise and 11.5 grams for the gas temperature rise. For a 100 SLPM U-tube flow, the inventory error was 2.5 grams using bed temperature rise and 1.6 grams using gas temperature rise. For 50 to 100 SLPM U-tube flows, the IBA gas temperature rise inventory errors were nominally one to two grams that increased above four grams for flows less than 50 SLPM. For 50 to 100 SLPM U-tube flows, the IBA bed temperature rise inventory errors were greater than the gas temperature rise errors, but similar errors were found for both methods at gas flows of 20, 30, and 40 SLPM. Electric heater IBA tests were done for six production hydride beds using a 45 SLPM U-tube gas flow. Of the duplicate runs performed on these beds, five of the six beds produced IBA inventory errors of approximately three grams: consistent with results obtained in the laboratory prototype tests.« less

Nanocrystalline cerium oxide materials for solid fuel cell systems

DOEpatents

Brinkman, Kyle S

2015-05-05

Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

Quantifying the influence of twin boundaries on the deformation of nanocrystalline copper using atomistic simulations

DOE PAGES

Tucker, Garritt J.; Foiles, Stephen Martin

2014-09-22

Over the past decade, numerous efforts have sought to understand the influence of twin boundaries on the behavior of polycrystalline materials. Early results suggested that twin boundaries within nanocrystalline face-centered cubic metals have a considerable effect on material behavior by altering the activated deformation mechanisms. In this work, we employ molecular dynamics simulations to elucidate the role of twin boundaries on the deformation of <100> columnar nanocrystalline copper at room temperature under uniaxial strain. We leverage non-local kinematic metrics, formulated from continuum mechanics theory, to compute atomically-resolved rotational and strain fields during plastic deformation. These results are then utilized tomore » compute the distribution of various nanoscale mechanisms during straining, and quantitatively resolve their contribution to the total strain accommodation within the microstructure, highlighting the fundamental role of twin boundaries. Our results show that nanoscale twins influence nanocrystalline copper by altering the cooperation of fundamental deformation mechanisms and their contributed role in strain accommodation, and we present new methods for extracting useful information from atomistic simulations. The simulation results suggest a tension–compression asymmetry in the distribution of deformation mechanisms and strain accommodation by either dislocations or twin boundary mechanisms. In highly twinned microstructures, twin boundary migration can become a significant deformation mode, in comparison to lattice dislocation plasticity in non-twinned columnar microstructures, especially during compression.« less

Transition Metal Switchable Mirror

ScienceCinema

None

2017-12-29

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

Transition Metal Switchable Mirror

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2009-08-21

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

Synthesis and hydriding properties of Li 2Mg(NH) 2

NASA Astrophysics Data System (ADS)

Markmaitree, Tippawan; Shaw, Leon L.

The phase pure Li 2Mg(NH) 2 has been synthesized via a dehydriding treatment of a ball milled 2LiNH 2 + MgH 2 mixture. This phase pure Li 2Mg(NH) 2 has been utilized to investigate its hydriding kinetics at the temperature range 180-220 °C. It is found that the hydriding process of Li 2Mg(NH) 2 is very sluggish even though it has favorable thermodynamic properties for near the ambient temperature operation. Holding at 200 °C for 10 h only results in 3.75 wt.% H 2 uptake. The detailed kinetic analysis reveals that the hydriding process of Li 2Mg(NH) 2 is diffusion-controlled. Thus, this study unambiguously indicates that the future direction to enhance the hydriding kinetics of this promising hydrogen storage material system should be to minimize the diffusion distance and increase the diffusion rate.

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface† †Electronic supplementary information (ESI) available. CCDC 1545735 and 1545736. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01846k

PubMed Central

Eleazer, Bennett J.; Smith, Mark D.

2017-01-01

In this work, we introduce a novel concept of a borane group vicinal to a metal boryl bond acting as a supporting hemilabile ligand in exohedrally metalated three-dimensional carborane clusters. The (POBOP)Ru(Cl)(PPh3) pincer complex (POBOP = 1,7-OP(i-Pr)2-m-2-carboranyl) features extreme distortion of the two-center-two-electron Ru–B bond due to the presence of a strong three-center-two-electron B–H···Ru vicinal interaction. Replacement of the chloride ligand with a hydride afforded the (POBOP)Ru(H)(PPh3) pincer complex, which possesses B–Ru, B–H···Ru, and Ru–H bonds. This complex was found to exhibit a rapid exchange between hydrogen atoms of the borane and the terminal hydride through metal center shuttling between two boron atoms of the carborane cage. This exchange process, which involves sequential cleavage and formation of strong covalent metal–boron and metal–hydrogen bonds, is unexpectedly facile at temperatures above –50 °C corresponding to an activation barrier of 12.2 kcal mol–1. Theoretical calculations suggested two equally probable pathways for the exchange process through formally Ru(0) or Ru(iv) intermediates, respectively. The presence of this hemilabile vicinal B–H···Ru interaction in (POBOP)Ru(H)(PPh3) was found to stabilize a latent coordination site at the metal center promoting efficient catalytic transfer dehydrogenation of cyclooctane under nitrogen and air at 170 °C. PMID:28970919

Plasma deposition of amorphous metal alloys

DOEpatents

Hays, Auda K.

1986-01-01

Amorphous metal alloy coatings are plasma-deposited by dissociation of vapors of organometallic compounds and metalloid hydrides in the presence of a reducing gas, using a glow discharge. Tetracarbonylnickel, phosphine, and hydrogen constitute a typical reaction mixture of the invention, yielding a NiPC alloy.

Plasma deposition of amorphous metal alloys

DOEpatents

Hays, A.K.

1979-07-18

Amorphous metal alloy coatings are plasma-deposited by dissociation of vapors of organometallic compounds and metalloid hydrides in the presence of a reducing gas, using a glow discharge. Tetracarbonylnickel, phosphine, and hydrogen constitute a typical reaction mixture of the invention, yielding a NiPC alloy.

Wear-triggered self-healing behavior on the surface of nanocrystalline nickel aluminum bronze/Ti3SiC2 composites

NASA Astrophysics Data System (ADS)

Zhai, Wenzheng; Lu, Wenlong; Zhang, Po; Wang, Jian; Liu, Xiaojun; Zhou, Liping

2018-04-01

Self-healing can protect materials from diverse damages, but is intrinsically difficult in metals. This paper demonstrates a potential method through a simultaneous decomposition and oxidation of Ti3SiC2 to achieve healing of stress cracking on the surface of nickel aluminum bronze (NAB)/Ti3SiC2 nanocrystalline composites during fretting wear. At the finest nanocrystalline materials, a crack recovery would be attained at 76.5%. The repetitive fretting wear leads to a modest amount of 'flowability' of Ti3SiC2 toward the crack, facilitating crack recovery. Along with the wear-triggered self-healing, the NAB/Ti3SiC2 shows an improved tribological performance with the stable decreased friction torque due to the formation of lubrication TiO2 oxide.

Super Hydrides.

DTIC Science & Technology

1988-03-01

enantioselective synthesis Of the clinically important anti-depressants, (-)Tomoxetine, Fluoxetine (Prozac, Eli Lilly), and Nisoxetine (Scheme 1 ). Schem I a I...Scheme 1 . Another salient feature of this synthesis is that it correlated for the first time the absolute configuration of the enantiomers of...RD-RI93 710 SUPER HYDRIDES(U) PURDUE UNIV LRFRYETTE IN H C BROWN 1 / 1 NAR 88 RRO-22302.2-CN DAR29-05-K-1662 UNCLSSIFIED F/G 7/3 NI. t2S 16, L,. 10 3

Molecular Line Lists for Scandium and Titanium Hydride Using the DUO Program

NASA Astrophysics Data System (ADS)

Lodi, Lorenzo; Yurchenko, Sergei N.; Tennyson, Jonathan

2015-06-01

Transition-metal-containing (TMC) molecules often have very complex electronic spectra because of their large number of low-lying, interacting electronic states, of the large multi-reference character of the electronic states and of the large magnitude of spin-orbit and relativistic effects. As a result, fully ab initio calculations of line positions and intensities of TMC molecules have an accuracy which is considerably worse than the one usually achievable for molecules made up by main-group atoms only. In this presentation we report on new theoretical line lists for scandium hydride ScH and titanium hydride TiH. Scandium and titanium are the lightest transition metal atoms and by virtue of their small number of valence electrons are amenable to high-level electronic-structure treatments and serve as ideal benchmark systems. We report for both systems energy curves, dipole curves and various coupling curves (including spin-orbit) characterising their electronic spectra up to about 20 000 cm-1. Curves were obtained using Internally-Contracted Multi Reference Configuration Interaction (IC-MRCI) as implemented in the quantum chemistry package MOLPRO. The curves where used for the solution of the coupled-surface ro-vibronic problem using the in-house program DUO. DUO is a newly-developed, general program for the spectroscopy of diatomic molecules and its main functionality will be described. The resulting line lists for ScH and TiH are made available as part of the Exomol project. L. Lodi, S. N. Yurchenko and J. Tennyson, Mol. Phys. (Handy special issue) in press. S. N. Yurchenko, L. Lodi, J. Tennyson and A. V. Stolyarov, Computer Phys. Comms., to be submitted.

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

Polyakov, B.; Petruhins, A.; Butikova, J.; Kuzmin, A.; Tale, I.

2009-11-01

Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed. in here

Non-noble metal based metallization systems

NASA Technical Reports Server (NTRS)

Garcia, A., III

1983-01-01

The results of efforts to produce a nonsilver metallization system for silicon photovoltaic cells are given. The system uses a metallization system based on molybdenum, tin, and titanium hydride. The initial work in this system was done using the MIDFILM process. The MIDFILM process attains a line resolution comparable to photoresist methods with a process related to screen printing. The surface to be processed is first coated with a thin layer of photopolymer material. Upon exposure to ultraviolet light through a suitable mask, the polymer in the non-pattern area crosslinks and becomes hard. The unexposed pattern areas remain tacky. The conductor material is then applied in the form of a dry mixture of metal which adheres to the tacky pattern area. The assemblage is then fired to ash the photopolymer and sinter the conductor powder.

Electrodeposition of Nanocrystalline Co-P Coatings as a Hard Chrome Alternative

DTIC Science & Technology

2009-09-02

Electrodeposition  of Nanocrystalline Co‐P  Coatings as a Hard Chrome Alternative Report Documentation Page Form ApprovedOMB No. 0704-0188 Public reporting burden...AND SUBTITLE Electrodeposition of Nanocrystalline Co‐P Coatings as a Hard Chrome Alternative 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...Defense Conference – 2 September 2009 Conventional  Electrodeposits Polycrystalline (10‐100 µm) Electrodeposited Nanocrystalline Materials Pulsed

Method of selective reduction of halodisilanes with alkyltin hydrides

DOEpatents

D'Errico, John J.; Sharp, Kenneth G.

1989-01-01

The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

Structural, optical and magnetic behaviour of nanocrystalline Volborthite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arvind, Hemant K., E-mail: hemantarvind@gmail.com; Kumar, Sudhish, E-mail: skmlsu@gmail.com; Kalal, Sangeeta

2016-05-06

Nanocrystalline sample of Volborthite (Copper Pyrovanadate: Cu{sub 3}V{sub 2} (OH){sub 2}O{sub 7}.2H{sub 2}O) has been synthesized using wet chemical route and characterized by XRD, SEM, FTIR, UV-Vis-NIR spectroscopic and magnetization measurements. Room temperature X-ray diffraction analysis confirms the single phase monoclinic structure and nanocrystalline nature of Volborthite. The UV-Visible optical absorption spectrum displays two broad absorption peaks in the range of 200-350 nm and 400-1000 nm. The direct band gap is found to be E{sub g}= ∼2.74 eV. Bulk Volborthite was reported to be a natural frustrated antiferromagnet, however our nanocrystalline Volborthite display week ferromagnetic hysteresis loop with very small coercivity andmore » retentivity at room temperature.« less

Hydride Molecules towards Nearby Galaxies

NASA Astrophysics Data System (ADS)

Monje, Raquel R.; La, Ngoc; Goldsmith, Paul

2018-06-01

Observations carried out by the Herschel Space Observatory revealed strong spectroscopic signatures from light hydride molecules within the Milky Way and nearby active galaxies. To better understand the chemical and physical conditions of the interstellar medium, we conducted the first comprehensive survey of hydrogen fluoride (HF) and water molecular lines observed through the SPIRE Fourier Transform Spectrometer. By collecting and analyzing the sub-millimeter spectra of over two hundred sources, we found that the HF J = 1 - 0 rotational transition which occurs at approximately 1232 GHz was detected in a total of 39 nearby galaxies both in absorption and emission. The analysis will determine the main excitation mechanism of HF in nearby galaxies and provide steady templates of the chemistry and physical conditions of the ISM to be used in the early universe, where observations of hydrides are more scarce.

Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes.

PubMed

Price, Jeffrey S; Emslie, David J H; Britten, James F

2017-05-22

Reaction of the ethylene hydride complex trans-[(dmpe) 2 MnH(C 2 H 4 )] (1) with Et 2 SiH 2 at 20 °C afforded the silylene hydride [(dmpe) 2 MnH(=SiEt 2 )] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph 2 SiH 2 at 60 °C afforded [(dmpe) 2 MnH(=SiPh 2 )] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn-H-Si interaction in the former. The reaction to form 2 b also yielded [(dmpe) 2 MnH 2 (SiHPh 2 )] (3 b); [(dmpe) 2 MnH 2 (SiHR 2 )] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H 2 , and the analogous reactions with D 2 afforded [(dmpe) 2 MnD 2 (SiHR 2 )] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe) 2 MnH(R 2 Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans-2 a, cis-2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

[Raman studies of nanocrystalline BaTiO3 ceramics].

PubMed

Xiao, Chang-jiang; Jin, Chang-qing; Wang, Xiao-hui

2008-12-01

High pressure can significantly increase the densification. Further, during the high pressure assisted sintering, the nucleation rate is increased due to reduced energy barrier and the growth rate is suppressed due to the decreased diffusivity. Thus high pressure enables the specimen to be fabricated with relatively lower temperature and shorter sintering period that assures to obtain dense nanocrystalline ceramics. Dense nanocrystalline BaTiO3 ceramics with uniform grain sizes of 60 and 30 nm, respectively, were obtained by pressure assisted sintering. The crystal structure and phase transitions were investigated by Raman scattering at temperatures ranging from -190 to 200 degrees C. The Raman results indicated that the evolution of Raman spectrum with grain size is characterized by an intensity decrease, a broadening of the line width, a frequency shift, and the disappearance of the Raman mode. With increasing temperature, similar to 3 mm BaTiO3 normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, and tetragonal to cubic were also observed in nanocrystalline BaTiO3 ceramics. In addition, when particle size is reduced to the nanoscale, one will find some unusual physical properties in nanocrystalline ceramics, compared with those of coarse-grained BaTiO3 ceramics. The different coexistences of multiphase were found at different temperature. Especially, the ferroelectric tetragonal and orthorhombic phase can coexist at room temperature in nanocrystalline BaTiO3 ceramics. The phenomenon can be explained by the internal stress. The coexistences of different ferroelectric phases at room temperature indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm.

Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride tanks: Thermodynamic and design considerations towards integrated systems

NASA Astrophysics Data System (ADS)

Yiotis, Andreas G.; Kainourgiakis, Michael E.; Kosmidis, Lefteris I.; Charalambopoulou, Georgia C.; Stubos, Athanassios K.

2014-12-01

We study the thermal coupling potential between a high temperature metal hydride (MH) tank and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources. Based on principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical expressions for both the thermal power produced during SOFC operation and the corresponding thermal power required for H2 desorption, as a function of the operating temperature, efficiency and fuel utilization ratio in the SOFC, and the MH enthalpy of desorption in the tank. Based on these calculations, we propose an integrated SOFC/MH design where heat is transferred primarily by radiation to the tank in order to maintain steady-state desorption conditions. We develop a mathematical model for this particular design that accounts for heat/mass transfer and desorption kinetics in the tank, and solve for the dynamics of the system assuming MgH2 as a storage material. Our results focus primarily on tank operating conditions, such as pressure, temperature and H2 saturation profiles vs operation time.

A prediction model based on artificial neural network for surface temperature simulation of nickel-metal hydride battery during charging

NASA Astrophysics Data System (ADS)

Fang, Kaizheng; Mu, Daobin; Chen, Shi; Wu, Borong; Wu, Feng

2012-06-01

In this study, a prediction model based on artificial neural network is constructed for surface temperature simulation of nickel-metal hydride battery. The model is developed from a back-propagation network which is trained by Levenberg-Marquardt algorithm. Under each ambient temperature of 10 °C, 20 °C, 30 °C and 40 °C, an 8 Ah cylindrical Ni-MH battery is charged in the rate of 1 C, 3 C and 5 C to its SOC of 110% in order to provide data for the model training. Linear regression method is adopted to check the quality of the model training, as well as mean square error and absolute error. It is shown that the constructed model is of excellent training quality for the guarantee of prediction accuracy. The surface temperature of battery during charging is predicted under various ambient temperatures of 50 °C, 60 °C, 70 °C by the model. The results are validated in good agreement with experimental data. The value of battery surface temperature is calculated to exceed 90 °C under the ambient temperature of 60 °C if it is overcharged in 5 C, which might cause battery safety issues.

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulte, Kevin L.; Braun, Anna; Simon, John

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

DOE PAGES

Schulte, Kevin L.; Braun, Anna; Simon, John; ...

2018-01-22

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

Hydrogen-storing hydride complexes

DOEpatents

Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

2012-04-10

A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

Mesoporous nanocrystalline film architecture for capacitive storage devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

Interaction of Light with Metallized Ultrathin Silicon Membrane

NASA Astrophysics Data System (ADS)

Shome, Krishanu

Freestanding metallized structures, a few tens of nanometer thick, show promise in creating flow-through sensors, single molecule detectors and novel solar cells. In this thesis we study test structures that are a step towards creating such devices. Finite- difference time-domain simulations have been used to understand and predict the interaction of light with such devices. Porous nanocrystalline silicon membrane is a novel freestanding layer structure that has been used as a platform to fabricate and study sensors and novel slot nanohole devices. Optical mode studies of the sensing structures, together with the method of fabrication inspired the creation of ultrathin freestanding hydrogenated amorphous silicon p-i-n junctions solar cells. All the freestanding structures used in this thesis are just a few tens of nanometers in thicknesses. In the first part of the thesis the sensing properties of the metallized porous nanocrystalline structure are studied. The surprising blueshift associated with the sensing peak is observed experimentally and predicted theoretically with the help of simulations. Polarization dependence of the membranes is predicted and confirmed for angled deposition of metal on the membranes. In the next part, a novel slot structure is fabricated and modeled to study the slot effect in nanohole metal-insulator-metal structures. Atomic layer deposition of alumina is used to conformally deposit alumina within the nanohole to create the slot structure. Simulation models were used to calculate the lowest modal volume of 4x10-5 mum3 for an optimized structure. In the last part of the thesis, freestanding solar cells are fabricated by effectively replacing the porous nanocrystalline silicon layer of the membranes with a hydrogenated amorphous silicon p-i-n junction with metal layers on both sides of the p-i-n junction. The metal layers act both as electrical contacts as well as mirrors for a Fabry Perot cavity resonator. This helps in tuning the

Production and characterization of thin film group IIIB, IVB and rare earth hydrides by reactive evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provo, James L., E-mail: jlprovo@verizon.net

2015-07-15

A recent short history of reactive evaporation by D. M. Mattox [History Corner—A Short History of Reactive Evaporation, SVC Bulletin (Society of Vacuum Coaters, Spring 2014), p. 50–51] describes various methods for producing oxides, nitrides, carbides, and some compounds, but hydrides were not mentioned. A study was performed in the mid-1970s at the General Electric Company Neutron Devices Department in Largo, FL, by the author to study preparation of thin film hydrides using reactive evaporation and to determine their unique characteristics and properties. Films were produced of scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), and the rare earth praseodymiummore » (Pr), neodymium (Nd), gadolinium (Gd), dysprosium (Dy), and erbium (Er) hydrides by hot crucible filament and electron beam evaporation in atmospheres of deuterium and tritium gases. All-metal vacuum systems were used and those used with tritium were dedicated for this processing. Thin film test samples 1000 nm thick were prepared on 1.27 cm diameter molybdenum disk substrates for each occluder (i.e., an element that can react with hydrogen to form a hydride) material. Loading characteristics as determined by gas-to-metal atomic ratios, oxidation characteristics as determined by argon–sputter Auger analysis, film structure as determined by scanning electron microscope analysis, and film stress properties as determined by a double resonator technique were used to define properties of interest. Results showed hydrogen-to-metal atomic ratios varied from 1.5 to 2.0 with near maximum loading for all but Pr and Nd occluders which correlated with the oxidation levels observed, with all occluder oxidation levels being variable due to vacuum system internal processing conditions and the materials used. Surface oxide levels varied from ∼80 Å to over 1000 Å. For most films studied, results showed that a maximum loading ratio of near 2.0 and a minimum surface oxide level of ∼80�

Method of selective reduction of polyhalosilanes with alkyltin hydrides

DOEpatents

Sharp, Kenneth G.; D'Errico, John J.

1989-01-01

The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

Method to produce nanocrystalline powders of oxide-based phosphors for lighting applications

DOEpatents

Loureiro, Sergio Paulo Martins; Setlur, Anant Achyut; Williams, Darryl Stephen; Manoharan, Mohan; Srivastava, Alok Mani

2007-12-25

Some embodiments of the present invention are directed toward nanocrystalline oxide-based phosphor materials, and methods for making same. Typically, such methods comprise a steric entrapment route for converting precursors into such phosphor material. In some embodiments, the nanocrystalline oxide-based phosphor materials are quantum splitting phosphors. In some or other embodiments, such nanocrystalline oxide based phosphor materials provide reduced scattering, leading to greater efficiency, when used in lighting applications.

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ball, James W.

2003-01-01

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using

Crack growth through the thickness of thin-sheet Hydrided Zircaloy-4

NASA Astrophysics Data System (ADS)

Raynaud, Patrick A. C.

In recent years, the limits on fuel burnup have been increased to allow an increase in the amount of energy produced by a nuclear fuel assembly thus reducing waste volume and allowing greater capacity factors. As a result, it is paramount to ensure safety after longer reactor exposure times in the case of design-basis accidents, such as reactivity-initiated accidents (RIA). Previously proposed failure criteria do not directly address the particular cladding failure mechanism during a RIA, in which crack initiation in brittle outer-layers is immediately followed by crack growth through the thickness of the thin-wall tubing. In such a case, the fracture toughness of hydrided thin-wall cladding material must be known for the conditions of through-thickness crack growth in order to predict the failure of high-burnup cladding. The fracture toughness of hydrided Zircaloy-4 in the form of thin-sheet has been examined for the condition of through-thickness crack growth as a function of hydride content and distribution at 25°C, 300°C, and 375°C. To achieve this goal, an experimental procedure was developed in which a linear hydride blister formed across the width of a four-point bend specimen was used to inject a sharp crack that was subsequently extended by fatigue pre-cracking. The electrical potential drop method was used to monitor the crack length during fracture toughness testing, thus allowing for correlation of the load-displacement record with the crack length. Elastic-plastic fracture mechanics were used to interpret the experimental test results in terms of fracture toughness, and J-R crack growth resistance curves were generated. Finite element modeling was performed to adapt the classic theories of fracture mechanics applicable to thick-plate specimens to the case of through-thickness crack growth in thin-sheet materials, and to account for non-uniform crack fronts. Finally, the hydride microstructure was characterized in the vicinity of the crack tip by

Local crystal/chemical structures at iron sites in amorphous, magnetic, and nanocrystalline materials

NASA Astrophysics Data System (ADS)

Clark, Ted Michael

Order-disorder phenomena have been examined by means of Mossbauer spectroscopy in a variety of materials, including (a) tektites and other silicate glasses, (b) magnetic materials such as natural and synthetic magnetoplumbite, M-type hexagonal ferrites and magnetite, and (c) nanocrystalline zinc ferrite. A methodology has been established for the analysis of the local crystal/chemical structures of iron in tektites and its application has reconfirmed a low ferric/ferrous ratio of approximately 0.10 for tektites. Additionally, a greater degree of submirocscopic heterogeneity has been established for Muong Nong tektites in comparison with splash form tektites. The dynamics of the 2b site in hexagonal ferrites has been studied above and below the Curie temperature for magnetoplumbite and its synthetic analogs, and also for polycrystalline and oriented single-crystals of MeFesb{12}Osb{19} (Me=Ba, Sr, Pb). Cation ordering on this site is shown to be dependent on the thermal history of the material, while the dynamic disorder of the 2b site for the end-member hexagonal ferrites is shown to be influenced by the divalent heavy metal species, Me. The influence of chemical composition on the morphology of magnetite has been shown to depend on the site preference of impurity cations: Substitutional impurities with tetrahedral site preferences are postulated to result in the seldom-observed cubic habit. Based on the cation distributions of bulk and nanocrystalline material it is held that the enhanced magnetic moments and susceptibilities of nanocrystalline zinc ferrite are shown to be consistent with surface phenomena, independent of synthesis methodology, and contrary to claims of special effects resulting from a particular synthesis methodology.

Nanocrystalline Aluminum Truss Cores for Lightweight Sandwich Structures

NASA Astrophysics Data System (ADS)

Schaedler, Tobias A.; Chan, Lisa J.; Clough, Eric C.; Stilke, Morgan A.; Hundley, Jacob M.; Masur, Lawrence J.

2017-12-01

Substitution of conventional honeycomb composite sandwich structures with lighter alternatives has the potential to reduce the mass of future vehicles. Here we demonstrate nanocrystalline aluminum-manganese truss cores that achieve 2-4 times higher strength than aluminum alloy 5056 honeycombs of the same density. The scalable fabrication approach starts with additive manufacturing of polymer templates, followed by electrodeposition of nanocrystalline Al-Mn alloy, removal of the polymer, and facesheet integration. This facilitates curved and net-shaped sandwich structures, as well as co-curing of the facesheets, which eliminates the need for extra adhesive. The nanocrystalline Al-Mn alloy thin-film material exhibits high strength and ductility and can be converted into a three-dimensional hollow truss structure with this approach. Ultra-lightweight sandwich structures are of interest for a range of applications in aerospace, such as fairings, wings, and flaps, as well as for the automotive and sports industries.

Three-dimensional analysis by electron diffraction methods of nanocrystalline materials.

PubMed

Gammer, Christoph; Mangler, Clemens; Karnthaler, Hans-Peter; Rentenberger, Christian

2011-12-01

To analyze nanocrystalline structures quantitatively in 3D, a novel method is presented based on electron diffraction. It allows determination of the average size and morphology of the coherently scattering domains (CSD) in a straightforward way without the need to prepare multiple sections. The method is applicable to all kinds of bulk nanocrystalline materials. As an example, the average size of the CSD in nanocrystalline FeAl made by severe plastic deformation is determined in 3D. Assuming ellipsoidal CSD, it is deduced that the CSD have a width of 19 ± 2 nm, a length of 18 ± 1 nm, and a height of 10 ± 1 nm.

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

PubMed Central

Proust, Gwénaëlle; Trimby, Patrick; Piazolo, Sandra; Retraint, Delphine

2017-01-01

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and nanocrystalline materials. The traditional techniques associated with scanning electron microscopy (SEM), such as electron backscatter diffraction (EBSD), do not possess the required spatial resolution due to the large interaction volume between the electrons from the beam and the atoms of the material. Transmission electron microscopy (TEM) has the required spatial resolution. However, due to a lack of automation in the analysis system, the rate of data acquisition is slow which limits the area of the specimen that can be characterized. This paper presents a new characterization technique, Transmission Kikuchi Diffraction (TKD), which enables the analysis of the microstructure of UFG and nanocrystalline materials using an SEM equipped with a standard EBSD system. The spatial resolution of this technique can reach 2 nm. This technique can be applied to a large range of materials that would be difficult to analyze using traditional EBSD. After presenting the experimental set up and describing the different steps necessary to realize a TKD analysis, examples of its use on metal alloys and minerals are shown to illustrate the resolution of the technique and its flexibility in term of material to be characterized. PMID:28447998

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction.

PubMed

Proust, Gwénaëlle; Trimby, Patrick; Piazolo, Sandra; Retraint, Delphine

2017-04-01

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and nanocrystalline materials. The traditional techniques associated with scanning electron microscopy (SEM), such as electron backscatter diffraction (EBSD), do not possess the required spatial resolution due to the large interaction volume between the electrons from the beam and the atoms of the material. Transmission electron microscopy (TEM) has the required spatial resolution. However, due to a lack of automation in the analysis system, the rate of data acquisition is slow which limits the area of the specimen that can be characterized. This paper presents a new characterization technique, Transmission Kikuchi Diffraction (TKD), which enables the analysis of the microstructure of UFG and nanocrystalline materials using an SEM equipped with a standard EBSD system. The spatial resolution of this technique can reach 2 nm. This technique can be applied to a large range of materials that would be difficult to analyze using traditional EBSD. After presenting the experimental set up and describing the different steps necessary to realize a TKD analysis, examples of its use on metal alloys and minerals are shown to illustrate the resolution of the technique and its flexibility in term of material to be characterized.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMillan, Paul F.; Gryko, Jan; Bull, Craig

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr{sub 2}) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300{sup o}C. Syntheses at higher temperatures gave rise tomore » microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.« less

Syntheses of nanocrystalline BaTiO3 and their optical properties

NASA Astrophysics Data System (ADS)

Yu, J.; Chu, J.; Zhang, M.

Stoichiometric and titanium-excess nanocrystalline barium titanates were synthesized using a hydrothermal process at various hydrothermal temperatures and with further heat treatment at 500 °C and 900 °C. Owing to the different process conditions, the excess titanium exists in different states and configurations within the nanocrystalline BaTiO3 matrix; this was demonstrated by X-ray diffraction, Raman scattering, and photoluminescence. In these nanocrystalline BaTiO3, the 590, 571, 543 and 694 nm light emission bands were observed; mechanisms leading to such emissions were also discussed.

A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures.

PubMed

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-24

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

NASA Astrophysics Data System (ADS)

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-01

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

Distinctive glial and neuronal interfacing on nanocrystalline diamond.

PubMed

Bendali, Amel; Agnès, Charles; Meffert, Simone; Forster, Valérie; Bongrain, Alexandre; Arnault, Jean-Charles; Sahel, José-Alain; Offenhäusser, Andreas; Bergonzo, Philippe; Picaud, Serge

2014-01-01

Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth.

Distinctive Glial and Neuronal Interfacing on Nanocrystalline Diamond

PubMed Central

Bendali, Amel; Agnès, Charles; Meffert, Simone; Forster, Valérie; Bongrain, Alexandre; Arnault, Jean-Charles; Sahel, José-Alain; Offenhäusser, Andreas; Bergonzo, Philippe; Picaud, Serge

2014-01-01

Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth. PMID:24664111

In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

DOE PAGES

Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; ...

2017-02-20

The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. Furthermore, these experimental resultsmore » can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.« less

Direct synthesis and characterization of optically transparent conformal zinc oxide nanocrystalline thin films by rapid thermal plasma CVD

NASA Astrophysics Data System (ADS)

Pedersen, Joachim D.; Esposito, Heather J.; Teh, Kwok Siong

2011-10-01

We report a rapid, self-catalyzed, solid precursor-based thermal plasma chemical vapor deposition process for depositing a conformal, nonporous, and optically transparent nanocrystalline ZnO thin film at 130 Torr (0.17 atm). Pure solid zinc is inductively heated and melted, followed by ionization by thermal induction argon/oxygen plasma to produce conformal, nonporous nanocrystalline ZnO films at a growth rate of up to 50 nm/min on amorphous and crystalline substrates including Si (100), fused quartz, glass, muscovite, c- and a-plane sapphire (Al2O3), gold, titanium, and polyimide. X-ray diffraction indicates the grains of as-deposited ZnO to be highly textured, with the fastest growth occurring along the c-axis. The individual grains are observed to be faceted by (103) planes which are the slowest growth planes. ZnO nanocrystalline films of nominal thicknesses of 200 nm are deposited at substrate temperatures of 330°C and 160°C on metal/ceramic substrates and polymer substrates, respectively. In addition, 20-nm- and 200-nm-thick films are also deposited on quartz substrates for optical characterization. At optical spectra above 375 nm, the measured optical transmittance of a 200-nm-thick ZnO film is greater than 80%, while that of a 20-nm-thick film is close to 100%. For a 200-nm-thick ZnO film with an average grain size of 100 nm, a four-point probe measurement shows electrical conductivity of up to 910 S/m. Annealing of 200-nm-thick ZnO films in 300 sccm pure argon at temperatures ranging from 750°C to 950°C (at homologous temperatures between 0.46 and 0.54) alters the textures and morphologies of the thin film. Based on scanning electron microscope images, higher annealing temperatures appear to restructure the ZnO nanocrystalline films to form nanorods of ZnO due to a combination of grain boundary diffusion and bulk diffusion. PACS: films and coatings, 81.15.-z; nanocrystalline materials, 81.07.Bc; II-VI semiconductors, 81.05.Dz.