Isothermal oxidation of TiAl alloy

Isothermal oxidation behavior of Ti-48.6 at. pct Al alloy was studied in pure dry oxygen over the temperature range 850 °C to 1000 °C. The oxidation was essentially parabolic at all temperatures with significant increase in the rate at 1000 °C. Effective activation energy of 404 kJ/mol was deduced. The oxidation products were a mixture of TiO₂ (rutile) and α-Al₂O₃ at all temperatures. An external protective layer of alumina was not observed on this alloy at any of the temperatures studied. A layered structure of oxides was formed on the alloy at 1000 °C.     

Effect of Yttrium Alloying on Intermediate to High-Temperature Oxidation Behavior of Mo-Si-B Alloys

The oxidation behavior of 0.2 Y-alloyed Mo-9Si-8B (at. pct) was investigated in a wide temperature range from 923 K to 1673 K (650 °C to 1400 °C). Formation of a thin yttrium-silicate scale at the outer layer along with the thick silica-rich inner layer containing Y-rich oxide inclusions was detected beyond 1573 K (1300 °C). A substantial improvement in the oxidation resistance of the alloy could be realized at 1073 K to 1273 K (800 °C to 1000 °C) with the addition of yttrium. The formation of a viscous silica-rich protective scale could prevent the permeation of MoO₃ at the initial stages of oxidation at this temperature regime. The growth of the internal oxidation zone followed a parabolic rate at 1273 K to 1673 K (1000 °C to 1400 °C), and the activation energy values calculated for both the outer oxide scale and internal oxidation zone formation indicated the inward diffusion of oxygen as the dominant rate controlling mechanism. The microstructural and kinetic data obtained for internal and external oxidation indicate that yttrium-silicate scale reduces the inward diffusion of oxygen, thereby improving the oxidation resistance of the alloy at high temperatures in any oxidizing environment.     

Oxidation Kinetics of a Pb-30 At. Pct In Alloy

The solid-state oxidation kinetics of a Pb-30 at. pct In alloy were studied from 22 °C to 175 °C using Auger electron spectroscopy (AES) combined with argon ion sputtering. At 22 °C, oxidation followed a direct logarithmic relationship. The data were interpreted in terms of a model presented previously. [2] The predicted value of the model parameter using the structural data of In₂O₃ is within a factor of 2 from the experimentally determined value. At temperatures higher than 100 °C, the oxidation kinetics changed to a different mechanism. Rapid oxidation occurred initially, followed by slower parabolic oxidation. The oxide formed was found to be In₂O₃ with possible existence of a metastable indium suboxide near the oxide/alloy interface. These data were described quantitatively by the model proposed by Smeltzeret al. [5] The model assumes the existence of short-circuit diffusion in addition to lattice diffusion. The degree of short-circuit diffusion decreases exponentially with time. The activation energy for the parabolic oxidation was found to be 30.8 ± 4 kJ/mol (0.32 eV). The rather low activation energy was rationalized by the fact that the diffusion of oxygen vacancies in In₂O₃ responsible for the parabolic oxidation occurred in the extrinsic region. This rationalization was made by analyzing the defect structure of In₂O₃ using oxygen diffusion data and the enthalpy of forming oxygen vacancies in In₂O₃ reported in the literature. [10,11,12]     

Features of high-temperature oxidation in air of silver and alloy Ag-Cu, and adsorption of oxygen on silver

Thermodynamic calculations are provided for equilibrium in the system Ag-O₂. Kinetics of high-temperature (up to 900 °C) oxidation in air of plates made from pure silver (99.99 mass% Ag) and jewellery alloy 84 at.% Ag-16 at.% Cu are studied by nonisothermal thermogravimetry, and differential and petrographic analyses of the reaction products. Mechanisms are established for the corresponding oxidation reactions confirming the absence of chemical reaction for pure silver with oxygen at T > 422 K. The Wagner theory for oxidation of alloys containing precious metals is confirmed by the results. The temperature ranges are determined for van de Waals adsorption and chemisorption of oxygen at the surface of very pure silver powder with a specific surface area S = 0.4 m²/g.     

Oxidation behavior of a fine-grained rapidly solidified 18-8 stainless steel

The cyclic oxidation behavior of a fine-grained, rapidly solidified 303 stainless steel was determined at 900 °C in pure oxygen. The rapidly solidified alloy exhibited superior resistance to oxidation compared with that of a wrought 304 stainless steel; its oxidation resistance was as good as that of a wrought 310 stainless steel, even though the latter alloy contained more Cr and Ni. The matrix of the rapidly solidified steel contained a uniform dispersion of fine MnS precipitates (0.2 to 0.5 μm), which were effective in inhibiting grain growth at elevated temperatures. The enhanced resistance to oxidation of the rapidly solidified alloy is attributed to two factors: (1) the formation and growth of protective Cr₂O₃ and SiO₂ scales were promoted by the fine alloy grain size (5 to 8 =gmm) and by the presence of the MnS dispersion, and (2) the adherence of the scale was increased by the formation of intrusions of SiO₂ from the external scale into the alloy, which formed around MnS precipitates and along closely-spaced alloy grain boundaries, and which acted to key the scale mechanically to the alloy.     

Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

Ni-49Ti and Ni-30Pt-50Ti (nominal at. pct) shape memory alloys (SMAs) were isothermally oxidized in air over the temperature range of 773?K to 1173?K (500?°C to 900?°C) for 100?hours. The oxidation kinetics, presented in detail in a companion study, show ~4 times reduction in oxidation rate due to Pt.[1] The microstructure, composition, and phase content of the scales and depletion zones were determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). A relatively pure TiO₂ rutile structure was identified as the predominant scale surface feature, typified by a distinct highly striated and faceted crystal morphology, with crystal size proportional to oxidation temperature. The complex layered structure beneath these crystals was characterized by semiquantitative XRD of serial/taper polished sections and SEM/EDS of cross sections for samples oxidized at 973?K (700?°C). In general, graded mixtures of TiO₂, NiTiO₃, NiO, Ni(Ti), or Pt(Ni) metallic dispersoids, and continuous Ni₃Ti or Pt-rich metal depletion zones, were observed from the gas surface to the substrate interior. Overall, substantial depletion of Ti occurred due to the formation of predominantly TiO₂ scales. It is proposed that the Ni-30Pt-50Ti alloy oxidized more slowly than the binary Ni-49Ti alloy by decreasing oxygen and titanium diffusion through the thin Pt-rich layer.     

Influence of aluminium addition on oxidation resistance of Ta-W alloy

ABSTRACT

Alloys with composition of Ta-10?wt.% W and Ta-10?wt.% W-6?wt.% Al, respectively, were prepared by the hot-press sintering process. The oxidation behaviour at 900°C and 1000°C was studied. The oxidation weight gain curves of the Ta–10%W alloy followed the linear law and the final oxidation product was Ta₂O₅ solid solution. Meanwhile, due to the addition of Al, the oxidation weight gain curves of the Ta–10%W–6%Al alloy followed the parabolic law. The final oxidation products at 900°C formed a dense outer layer Al₂O₃ and an inner layer. However, after being oxidised at 1000°C, the oxidation products included Al₂O₃, AlTaO₄ and Ta₂₂W₄O₆₇. Since the dense Al₂O₃ oxide film was consumed by the generation of AlTaO₄, the inward diffusion of oxygen cannot be prevented. The oxidation resistance degraded at 1000°C. The addition of Al significantly improved the oxidation resistance of the Ta-W-based alloy system.     

High Temperature Oxidation Behavior of Conventional and Nb-Modified MAR-M246 Ni-Based Superalloy

The present investigations focused on the thermal oxidation of two variants of MAR-M246 alloy having the same contents of Ta and Nb in at. pct, considering the effects of total replacement of Ta by Nb. The alloys were produced by investment casting using high purity elements in induction furnace under vacuum atmosphere. The alloys were oxidized pseudo-isothermally at 800 °C, 900 °C and 1000 °C up to 1000 hours under lab air. Protective oxidation products growing on the surface of the oxidized samples were mainly Al₂O₃, Cr₂O₃. Other less protective oxide such as spinels (NiCr₂O₄ and CoCr₂O₄) and TiO₂ were also detected as oxidation products. The conventional alloy exhibited slight internal oxidation at 800 °C and an enhanced resistance at 900 °C and 1000 °C. The Nb-modified alloy presented an exacerbated internal oxidation and nitridation at 900 °C and 1000 °C and an enhanced resistance at 800 °C. At 1000 °C, Nb-modified alloy was particularly affected by excessive spalling as the main damage mechanisms. From a kinetic point of view, both alloys exhibit the same behavior at 800 °C and 900 °C, with k_p values typical of alumina forming alloys (2 × 10⁻¹⁴ to 3.6 × 10⁻¹³ g² cm⁻⁴ s⁻¹). However, Ta modified alloys exhibited superior oxidation resistance at 1000 °C when compared to the Nb modified alloy due to better adherence of the protective oxide scale.

     

High-Temperature Oxidation of Alloy 617 in Helium Containing Part-Per-Million Levels of CO and CO<Subscript>2</Subscript> as Impurities

The objective of this study was to determine the mechanisms of carburization and decarburization of alloy 617 in impure helium. To avoid the coupling of multiple gas/metal reactions that occurs in impure helium, oxidation studies were conducted in binary He + CO + CO₂ gas mixtures with CO/CO₂ ratios of 9 and 1272 in the temperature range 1123 K to 1273 K (850 °C to 1000 °C). The mechanisms were corroborated through measurements of oxidation kinetics, gas-phase analysis, and surface/bulk microstructure examination. A critical temperature corresponding to the equilibrium of the reaction 27Cr + 6CO ↔ 2Cr₂O₃ + Cr₂₃C₆ was identified to lie between 1173 K and 1223 K (900 °C and 950 °C) at CO/CO₂ ratio 9, above which decarburization of the alloy occurred via a kinetic competition between two simultaneous surface reactions: chromia formation and chromia reduction. The reduction rate exceeded the formation rate, preventing the growth of a stable chromia film until carbon in the sample was depleted. Surface and bulk carburization of the samples occurred for a CO/CO₂ ratio of 1272 at all temperatures. The surface carbide, Cr₇C₃, was metastable and nucleated due to preferential adsorption of carbon on the chromia surface. The Cr₇C₃ precipitates grew at the gas/scale interface via outward diffusion of Cr cations through the chromia scale until the activity of Cr at the reaction site fell below a critical value. The decrease in activity of chromium triggered a reaction between chromia and carbide: Cr₂O₃ + Cr₇C₃ → 9Cr+3CO, which resulted in a porous surface scale. The results show that the industrial application of the alloy 617 at T > 1173 K (900 °C) in impure helium will be limited by oxidation.     

Thermodynamic consideration and phase evolution during oxidation of tungsten–copper electrical contactor scraps

Present studies account the feasibility studies on isothermal oxidation of W–Cu hard metal electrical contractor scraps for recycling by roasting-leaching method. This was investigated as one of main processes to produce friable oxidized product amenable to subsequent leaching process. Oxidation is facilitated using scrap turnings instead of solid W–Cu contactor rods. The alloy oxidizes to Cu_xO, WO_x and CuWO₄ upon heating in the temperature range 400–1000°C under oxygen flow. Apart from oxidized W and Cu phases, significant amount of Cu nuggets formed initially at 450°C that rose gravimetrically up to 750°C, and then disappeared at higher temperature. The maximum weight gain was about 22% compared to initial weight when oxidation was carried out at 750°C. Oxidation beyond the temperature of 750°C corresponded to significant loss of tungsten by evaporation of WO₂ · (OH)₂ gaseous product. Thermal oxidation of W–Cu metal electrical contractor tip scraps produced porous and friable oxidized product of W and Cu.     

A Study on the Oxidation Behavior of Nb Alloy (Nb-1 pct Zr-0.1 pct C) and Silicide-Coated Nb Alloys

In the current work, silicide coatings were produced on the Nb alloy (Nb-1 pct Zr-0.1 pct C) using the halide activated pack cementation (HAPC) technique. Coating parameters (temperature and time) were optimized to produce a two-layer (Nb₅Si₃ and NbSi₂) coating on the Nb alloy. Subsequently, the oxidation behavior of the Nb alloy (Nb-1 pct Zr-0.1 pct C) and silicide-coated Nb alloy was studied using thermogravimetric analysis (TGA) and isothermal weight gain oxidation experiments. Phase identification and morphological examinations were carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. TGA showed that the Nb alloy started undergoing accelerated oxidation at and above 773 K (500 °C). Isothermal weight gain experiments carried out on the Nb alloy under air environment at 873 K (600 °C) up to a time period of 16 hours exhibited a linear growth rate law of oxidation. In the case of silicide-based coatings, TGA showed that oxidation resistance of silicide coatings was retained up to 1473 K (1200 °C). Isothermal weight gain experiments on the silicide coatings carried out at 1273 K (1000 °C) in air showed that initially up to 8 hours, the weight of the sample increased, and beyond 8 hours the weight of the sample remained constant. The oxide phases formed on the bare samples and on the coated samples during oxidation were found to be Nb₂O₅ and a mixture of SiO₂ and Nb₂O₅ phases, respectively. SEM showed the formation of nonprotective oxide layer on the bare Nb alloy and a protective (adherent, nonporous) oxide layer on silicide-coated samples. The formation of protective SiO₂ layer on the silicide-coated samples greatly improved the oxidation resistance at higher temperatures.     

Air-Oxidation Behavior of a [(Co50Cr15Mo14C15B6)97.5Er2.5]93Fe7 Bulk-Metallic Glass at 873?K to 973?K (600?°C to 700?°C)

The oxidation behavior of a [(Co₅₀Cr₁₅Mo₁₄C₁₅B₆)_97.5Er_2.5]₉₃Fe₇ bulk-metallic glass (Co7-BMG) was studied over the temperature range of 873?K to 973?K (600?°C to 700?°C) in dry air. The oxidation kinetics of the Co7-BMG generally followed the parabolic-rate law, as its oxidation rates increased with temperature. The scaling rate of the Co7-BMG was significantly lower than that of pure Co, which indicates a better oxidation resistance for the amorphous alloy. The scales formed on the Co7-BMG consisted mostly of CoMoO₄ and Co₃O₄, as well as minor amounts of CoO, Cr₂O₃, and uncorroded Co₃B. The formation of CoMoO₄ and Cr₂O₃ is responsible for the lower oxidation rates of the glassy alloy with respect to those of pure Co. In addition, the presence of Co₃B further indicated that the crystallization of the amorphous substrate during the oxidation was taken place.     

Development and elemental powder metallurgy of a Y-containing two-phase TiAl alloy

The Y modification of a two-phase (γ+α ₂) TiAl-(Mn,Mo,C) alloy was studied with an aim to improve, mainly, the oxidation resistance and the mechanical properties in a high-temperature air environment. The experimental alloy was prepared by the elemental powder metallurgy (EPM) method. The addition of up to 0.6 at. pct Y resulted in a significant improvement in tensile properties and compressive yield strength and an anomalous yielding phenomenon withal. Two structural characteristics were identified: first, microstructural refinement in terms of the grain size as well as the interlamellar spacing, and second, precipitation of fine oxides that might scavenge harmful oxygen. Deformation was found to be mainly provided by 1/2<110] ordinary dislocations and a much lesser amount of <011] superdislocations as compared to what has been reported in other (γ+α ₂) TiAl alloys. The oxidation resistance of the experimental alloy was evaluated by air-exposure tests at 800 °C, from which the oxidation kinetics and the morphological and phase characteristics of the oxide scales were analyzed. With a Y addition, the constituents of the oxide scale changed from those of the Y-free alloy. In the case of the Y-free alloy, the oxide scale which formed upon extended air exposure (350 hours) at 800 °C consisted of a mixture of TiO₂ and α-Al₂O₃. In the case of the alloy modified with Y (0.6 at. pct), however, the oxide scale formed in an identical environment was considerably different: it consisted of a complex mixture of TiO₂, α-Al₂O₃, Y₂O₃, and Al₅Y₃O₁₂. The formation of the multiphase (Y,Al)O-rich oxide scale impedes the oxygen transport and the thermal-expansion stress in the Al₂O₃ layer. It is also suggested that a Y addition reduces the oxygen solubility and concentration of oxygen vacancices in the TiO₂ layer. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

Effect of preoxidation and grain size on ductility of a boron-doped Ni3Al at elevated temperatures

The ductility of a preoxidized Ni₃Al (Ni-23Al-0.5Hf-0.2B. at.%) alloy with various grain sizes (17–193 μm) was evaluated by means of tensile tests at 600 and 760°C in vacuum. The preoxidation does not affect the ductility of the finest-grained material at either temperature, whereas it causes severe embrittiement in the largest-grained material, especially at 760°C. Auger studies revealed very little oxygen penetration along grain boundaries in the finest-grained material but substantial oxygen penetration in the largest-grained one. A continuous, thin Al-rich oxide layer which forms on the fine-grained samples protects the underlying alloy from oxygen penetration, preventing any loss of ductility, whereas the nickel-rich oxide which forms on the large-grained samples allows oxygen to penetrate along grain boundaries, causing severe embrittiement. The grain boundaries act as short-circuit paths for rapid diffusion of aluminum atoms from the bulk to the surfaces, and this is responsible for the change in oxidation product from Ni-rich to Al-rich oxide with decreasing grain size.     

Oxidation Behavior of Nb-20Mo-15Si-25Cr and Nb-20Mo-15Si-25Cr-5B Alloys

Nb-20Mo-15Si-25Cr (25Cr alloy) and Nb-20Mo-15Si-25Cr-5B (25Cr/5B alloy) alloys have been subjected to oxidation in air for 24 hours from 973 K to 1673 K (700 °C to 1400 °C). Even though B additions do not improve oxidation resistance at temperatures higher than 1473 K (1200 °C), the lower temperature oxidation resistance is superior with B by influencing the microstructure. Porous oxide scale development at lower temperatures has been attributed to the dominant growth of Nb₂O₅ and the vaporization of MoO₃. An intermediate oxidation layer is developed between the scale and the metal for the 25Cr/5B alloy at temperatures above 1173 K (900 °C). Scale densification at elevated temperatures results in higher stress development as a result of the mismatch of coefficients of thermal expansion, ultimately resulting in oxide spallation.     

Superplasticity in a thermomechanically processed High-Mg,Al-Mg alloy

Superplastic elongations in excess of 400 pct have been observed in tension testing at 573 K (300 °C) and strain rate έ= 2 × 10^-3 s^-1 for a thermomechanically processed Al-10.2 pct Mg-0.52 pct Mn alloy. The thermomechanical processing consists of solution treatment and hot working, followed by extensive warm rolling at 573 K (300 °C), a temperature below the solvus for Mg in the alloy. This processing results in a fine subgrain structure in conjunction with refined and homogeneously distributed β(Al₈Mg₅) and MnAl₆ precipitates. This structure does not statically recrystallize when annealed at 573 K (300 °C) but appears to recrystallize continuously during deformation at such a temperature and the resulting fine grain structure deforms with minimal cavitation. At temperatures above the Mg-solvus,e.g., 673 K (400 °C), recrystallization and growth occur readily resulting in rela tively coarser structures which deform superplastically but with extensive grain boundary sliding and cavitation. Formerly in Materials Group, Mechanical Engineering, Naval Postgraduate School Formerly Graduate Student in Mechanical Engineering, Naval Postgraduate School     

Diffusion of oxygen in the Al2O3 oxidation product of TiAl3

The oxidation behavior of TiAl₃ was investigated. The studies were carried out using thermogravimetric analysis (TGA) in the temperature range from 1123 to 1273 K in a 1 atm pure oxygen environment. Samples were analyzed using the X-ray diffraction (XRD), scanning electron microscope (SEM), and energy dispersion X-ray analysis techniques. The oxidation product was determined to be Al₂O₃ over the temperature range of the investigation. The parabolic-rate constant for TiAl₃ was deduced and compared with those for Ti, TiAl, and Ti₃Al. The electronprobe microanalysis technique was used to obtain concentration profiles for O, Al, and Ti in the oxide layer and the matrix alloy. The parabolic-rate data were used to calculate the diffusivities of oxygen at various temperatures. The activation energy for diffusion was determined to be 337.66 kJ/mol, while the frequency factor (D ₀) was 167.2 × 10⁻⁴ m²/s.     

The oxidation behavior of some Ni-Cr-Al alloys at high temperatures

Oxidation of ternary Ni-Cr-Al alloys containing different Cr/Al ratios has been studied in the temperature range 800° to 1300°C. Most of the studies were performed in 1 atm oxygen or air, but the oxygen pressure dependence for one of the alloys was also investigated. The experimental methods included thermogravimetric measurements of oxidation rates and studies on reacted specimens by means of X-ray diffraction, metallographic techniques, electron microprobe analysis, and electron microscopy. In general, the oxidation rates decrease faster with time than that for an ideal parabolic behavior. The major reaction products were NiO, Cr₂O₃,α-Al₂O₃, and Ni(Cr,Al)₂O₄. The relative amounts of these were a function of composition, temperature, oxygen pressure, and reaction time. The Ni-9Cr-6Al alloy has the best oxidation resistance due to the formation ofα-Al₂O₃ at all temperatures investigated. The oxidation mechanism of the alloy is discussed.     

Oxidation Behavior of a Pd<Subscript>43</Subscript>Cu<Subscript>27</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> Bulk Metallic Glass and Foam in Dry Air

The oxidation behavior of both Pd₄₃Cu₂₇Ni₁₀P₂₀ bulk metallic glass (Pd4-BMG) and its amorphous foam containing 45 pct porosity (Pd4-AF) was investigated over the temperature range of 343 K (70 °C) to 623 K (350 °C) in dry air. The results showed that virtually no oxidation occurred in the Pd4-BMG at T < 523 K (250 °C), revealing the alloy’s favorable oxidation resistance in this temperature range. In addition, the oxidation kinetics at T ≥ 523 K (250 °C) followed a parabolic-rate law, and the parabolic-rate constants (k _p values) generally increased with temperature. It was found that the oxidation k _p values of the Pd4-AF are slightly lower than those of the Pd4-BMG, indicating that the porous structure contributes to improving the overall oxidation resistance. The scale formed on the alloys was composed exclusively of CuO at T ≥ 548 K (275 °C), whose thickness gradually increased with increasing temperature. In addition, the amorphous structure remained unchanged at T ≤ 548 K (275 °C), while a triplex-phase structure developed after the oxidation at higher temperatures, consisting of Pd₂Ni₂P, Cu₃P, and Pd₃P.     

Phase relations and thermodynamics of the system Fe-Cr-0 in the temperature range of 1600 °C to 1825 °C (1873 to 2098 K) under strongly reducing conditions

Equilibrium relations involving alloy and oxide phases in the system Fe-Cr-O were determined in the temperature range from 1600 °C to 1825 °C (1873 to 2087 K). Compositions of coexisting alloy and spinel phases were established as a function of oxygen pressure by equilibrating liquid Fe-Cr alloys with iron chromite (Fe_3-xCr_xO₄) solid solutions at 1600 °C and 1700 °C. Combinations of these experimental data and thermodynamic calculations were used to construct composition-oxygen pressure diagrams for the system at 1600 °C and 1700 °C. Additional runs for selected mixtures were made at still higher temperatures (1700 °C to 1825 °C), and thermodynamic parameters were derived for spinel-containing phase assemblages at temperatures up to 1865 °C. The spinel phases occurring in the present system are typically in the high-chromium range of the solid-solution series Fe₃O₄-Cr₃O₄,i.e., in the range between stoichiometric iron chromite (FeCr₂O₄) and Cr₃O₄. The activities of the various oxide components of the spinel solid solution at 1600 °C were calculated from experimentally determined parameters for coexisting alloy and spinel phases, as well as by statistical-mechanical modeling of the same spinel solid solution based on crystal-chemical considerations. The agreement between the two sets of results was excellent. Temperature variation of parameters characterizing the univariant equilibria spinel + Cr₂O₃ + alloy and spinel + alloy + liquid oxide was established. The univariant curves were found to display temperature maxima of 1715 °C ± 5 °C and approximately 1865 °C, respectively. In analogy with relations in the Cr-O system, the increase in divalent chromium of the liquid oxide phase with decreasing oxygen potential was identified as the main cause of the sharp decrease in liquidus temperatures of chromites in contact with Fe-Cr alloys of high Cr contents. Formerly Graduate Research Assistant, Department of Metallurgy, The Pennsylvania State University L.S. DARKEN and ARNULF MUAN, formerly Professors of Geochemistry and Materials Science, The Pennsylvania State University, University Park, PA 16802, are deceased.