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The Vapor Pressure of Palladium at Temperatures up to 1973K

Understanding high-temperature processes is imperative for modeling the formation of the solar system. It is unfortunate that since the 1950 s little has been done in the area of thermodynamics to continue gaining information on metals such as iron (Fe), nickel (Ni), cobalt (Co), palladium (Pd) and many others. Although the vapor pressures of these metals can be extrapolated to higher temperatures, the data is often limited to temperature ranges too low to be applicable to processes that occur during the formation of the solar system (T approx. 2000K). Experimental techniques inhibited the data in the past by restricting the testing of metals to temperatures below their melting point. Today, higher temperature testing is possible by using a Thermo- Cahn Thermogravimetric system that is able to reach temperatures up to 1973K in vacuo and measure a 10 gram change in a sample with mass of up to 100 grams.

Gardner, K. G.

Effects of Palladium Content, Quaternary Alloying, and Thermomechanical Processing on the Behavior of Ni-Ti-Pd Shape Memory Alloys for Actuator Applications

The need for compact, solid-state actuation systems for use in the aerospace, automotive, and other transportation industries is currently driving research in high-temperature shape memory alloys (HTSMA) having transformation temperatures above 100 C. One of the basic high temperature systems under investigation to fill this need is NiTiPd. Prior work on this alloy system has focused on phase transformations and respective temperatures, no-load shape memory behavior (strain recovery), and tensile behavior for selected alloys. In addition, a few tests have been done to determine the effect of boron additions and thermomechanical treatment on the aforementioned properties. The main properties that affect the performance of a solid state actuator, namely work output, transformation strain, and permanent deformation during thermal cycling under load have mainly been neglected. There is also no consistent data representing the mechanical behavior of this alloy system over a broad range of compositions. For this thesis, ternary NiTiPd alloys containing 15 to 46 at.% palladium were processed and the transformation temperatures, basic tensile properties, and work characteristics determined. However, testing reveals that at higher levels of alloying addition, the benefit of increased transformation temperature begins to be offset by lowered work output and permanent deformation or "walking" of the alloy during thermal cycling under load. In response to this dilemma, NiTiPd alloys have been further alloyed with gold, platinum, and hafnium additions to solid solution strengthen the martensite and parent austenite phases in order to improve the thermomechanical behavior of these materials. The tensile properties, work behavior, and dimensional stability during repeated thermal cycling under load for the ternary and quaternary alloys were compared and discussed. In addition, the benefits of more advanced thermomechanical processing or training on the dimensional stability of these alloys during repeated actuation were investigated. Finally, the effect of quaternary alloying on the thermal stability of NiTiPdX alloys is determined via thermal cycling of the materials to increasing temperatures under load. It was found that solid solution additions of platinum and gold resulted in about a 30 C increase in upper use temperature compared to the baseline NiTiPd alloy, providing an added measure of over-temperature protection.

Bigelow, Glen

Permeation Rate Equations for Hydrogen and Deuterium in a Palladium-Silver Alloy

Mass transfer of a gas through a selective, solid membrane is an effective method for separation of desired species. This selective permeability is evident in the flow of hydrogen and the isotope deuterium through palladium-silver metal alloy media. In this study, based upon Sieverts’s law and the Arrhenius diffusion equation, an empirical correlation was developed to determine the steady-state permeation rate R, dependence on media temperature T, gas supply pressure p(sub S), and gas backpressure p(sub B) on the lower pressure side. Because of an extensive range of experimental conditions and complete reporting of raw data, the research by Ackerman and Koskinas was used as a source for data allowing empirical equation fitting. Unfortunately, those authors reported best-fit equations that poorly represented their own results. To improve the modeling of the original data and demonstrate the quality of the measurements, the current study develops improved hydrogen and deuterium permeation rate equations: P = 4.22×10(exp −6) A[exp(−704/T)](sq. root p(sub S) − sq. root p(sub B))/t for hydrogen P = 2.12×10(exp −6) A[exp(−468/T )](sq. root p(sub S) − sq. root p(sub B))/t for deuterium for values of cross-sectional area A (sq.cm), medium thickness t (cm), pressure p (psia), and temperature T (Kelvin), giving a permeation rate in mole/minute. These equations model permeation rate data more closely than do several other existing literature sources.

Smith, Phillip J.

Transmutations Observed from Pressure Cycling Palladium Silver Metals with Deuterium Gas

Hydrogen, deuterium, and helium gases were separately cycled through a Johnson-Mattheypurifier containing coiled palladium silver alloy tubing: Pd25Ag (75 wt% Pd and 25 wt% Ag).During the cycling of D2 gas, evidence of anomalous heat production was observed. However,during the cycling of H2 and He,very little (H2) or no (He) unusual heat events were observed.After cycling the D2 gas through the coiled tubing for several months, Pd25Ag samples showedan increase in Cu and Fe compared with the amounts in unexposed Pd25Ag. Chromium,manganese, and zinc were detected in gas-cycled Pd25Ag samples, whereas they were notdetected in unexposed Pd25Ag samples. In particular, Zn was present in the gas-cycled Pd25Agmaterial in larger quantities than either Cr or Mn. Although a small amount of Cu was present inthe Pd25Ag coil before the D2 gas cycling, 7 times more was present after the cycling. Multiplematerial characterization techniques were used to obtain both pre-test and post-test elementalcomposition. The results indicate that novel post-test elements, primarily on the surface, werecreated by unknown nuclear mechanisms at low energy.

Gustave C Fralick

Electrical resistivity of some palladium-silver alloys containing hydrogen at 4.2 K

The electrical resistivities of the alloys 90at.%Pd - 10at.%Ag, 80at.%Pd - 20at.%Ag, 70at.%Pd - 30at.%Ag, 60at.%Pd - 40at.%Ag, and 50at.%Pd - 50at.%Ag were measured as functions of absorbed hydrogen x at 4.2 K. These results show a minimum in the resistivity for all the alloys except 90Pd-10Ag; they show a maximum for all the alloys except for 50Pd-Ag. We associate the shapes of the plots with a modification of the Pd D-band because of the substitutional alloying of Ag and the interstitial absorption of hydrogen.

Smith, R. J.

Tensile properties of palladium-silver alloys with absorbed hydrogen

The alloys 90Pd-10Ag, 80Pd-20Ag, 70Pd-30Ag, 60Pd-40Ag, and 50Pd-50Ag containing absorbed hydrogen were tested in tension. The results show the tensile properties to be independent of the phase transition. Also, hydrogen in the lattice does not necessarily cause embrittlement or poor elongation. The changes in the tensile properties appear dependent on the electron to atom site ratio.

Smith, R. J.

Superconductivity in the palladium-hydrogen system

Band theory and phonon measurements are used to calculate the electron-phonon coupling constant wavelength for Pd and PdD. The results indicate that superconductivity is absent in Pd metal because of the large value of the Coulomb pseudopotential, and that superconductivity occurs in PdD primarily because of coupling with the optic phonons. These results are consistent with superconducting transition-temperature measurements for these systems.

Papaconstantopoulos, D. A.

The 55 K specific heat anomaly in palladium hydride

A specific heat anomaly in PdH and PdD has been observed by Aston et al. (1957) close to 55 K. Its position was found to be independent of hydrogen concentration and its magnitude to be linear in hydrogen concentration. Ferguson's (1965) and Brodowsky's (1972) explanations of the anomaly are shown to be unsatisfactory. This is true also for the detailed mechanical statistical model proposed by Staford and McLellan (1974) for interstitial solid solutions of hydrogen in transition metals. It is shown that Gopal's (1966) simple Schottky model of specific heat anomaly, which considers a system of several levels with Boltzmann statistics, provides much better agreement with experiment than the more elaborate models, both in magnitude and in predicting a linear dependence on hydrogen concentration.

Jacobi, N.

Sulfur poisoning of hydrocarbon oxidation by palladium

Using a differential bed recycle reactor the oxidation of ethane and diethyl ketone by a Pd catalyst was studied at the 0-30 ppm level in air. In both cases first order kinetics were observed. The ethane oxidation rate was characterized n the Arrhenius form by a pre-exponential of 1.0 x 10 to the 8th power cm/sec and an E sub a of 27 kcal/mole. The diethyl ketone oxidation rate was characterized by a pre-exponential of 5.7 x -1000 cm/sec and E sub a of 14 kcal/mole. Poisoning of ethan oxidation was also investigated by hydrogen sulfide and to a smaller extent by the refrigerants Freon 22 and Gentron 142-B. Poisoning by Gentron 142-B was much more severe than by hydrogen sulfide. Kinetic experiments indicated that only the pre-exponential was changing.

Baumgartner, A. J.

Electrical conductivity and phase diagram of binary alloys. 21: The system palladium-chromium

Pd-Cr alloys were investigated by thermal analysis, hardness measurements, X-ray analysis, microscopic examination of etched pieces, and temperature-resistance curves of the solid alloys. Only one compound, Pd2Cr3, m, 1389 deg, is formed. It possesses a cubic face centered lattice and forms with excess Pd a series of solid solutions with a minimum m.p. at 45 atoms% Pd. Hardness maximum appears at the Pd2Cr3 point. Pd2Cr3 forms no solid solutions with Cr but eutectic point appears at 25 atoms% Pd, m. 1320 deg. The sp. resistance of pure Cr in an atom of H, indicates no allotropic forms. Cr2O3 is solid in molten Cr. Pure Cr melts at 1890 plus or minus 10 deg but Cr contg. Cr2O3 starts to melt at 1770 to 1790 deg.

Grube, G.

An inert marker study for palladium silicide formation - Si moves in polycrystalline Pd2Si

A novel use of Ti marker is introduced to investigate the moving species during Pd2Si formation on 111 and 100 line-type Si substrates. Silicide formed from amorphous Si is also studied using a W marker. Although these markers are observed to alter the silicide formation in the initial stage, the moving species can be identified once a normal growth rate is resumed. It is found that Si is the dominant moving species for all three types of Si crystallinity. However, Pd will participate in mass transport when Si motion becomes obstructed.

Ho, K. T.

Palladium silicide formation under the influence of nitrogen and oxygen impurities

The effect of impurities on the growth of the Pd2Si layer upon thermal annealing of a Pd film on 100 line-type and amorphous Si substrates is investigated. Nitrogen and oxygen impurities are introduced into either Pd or Si which are subsequently annealed to form Pd2Si. The complementary techniques of Rutherford backscattering spectrometry, and N-15(p, alpha)C-12 or O-18(p, alpha)N-15 nuclear reaction, are used to investigate the behavior of nitrogen or oxygen and the alterations each creates during silicide formation. Both nitrogen and oxygen retard the silicide growth rate if initially present in Si. When they are initially in Pd, there is no significant retardation; instead, an interesting snow-plowing effect of N or O by the reaction interface of Pd2Si is observed. By using N implanted into Si as a marker, Pd and Si appear to trade roles as the moving species when the silicide front reaches the nitrogen-rich region.

Ho, K. T.