Kinetics of and preparation of nickel by Ni3S2−NiO reaction under reduced pressure

The reaction between Ni₃S₂ (liquid) and NiO (solid) resulting in the formation of Ni and SO₂ was investigated in the temperature range 800° to 1200°C under a reduced pressure of <0.1 mm Hg. From the kinetic studies in the temperature range 950° to 1150°C, the reaction was found to proceed in three stages: i) Up to about 25 pct reduction, the rate of reaction was high and followed approximately a cubic rate law. During this stage, the reaction is thought to be under mixed control. Activation energy for the first 10 pct reduction was found to be approximately 45 kcal per mole. ii) From about 25 to 90 pct reduction, it obeyed the parabolic rate law, with an activation energy of 86±6 kcal per mole. This value is in agreement with the activation energy reported in the literature for the diffusion of sulfur in nickel. iii) Beyond 90 pct reduction, the reaction was very sluggish owing to the poor availability of the reactants. Optimum conditions for preparing nickel sponge by the above reaction and its processing into thin strips have been standardized. Some of the properties of the metal thus produced have also been incorporated.     

Grain-boundary penetration of type 316 stainless steel exposed to cesium or cesium and tellurium

When 20 pct cold-worked Type 316 stainless steel is exposed to Cs at 700°C under controlled oxygen-chemical potential environment, Cs penetration into the stainless steel grain boundaries occurs at oxygen potentials ΔG_o2 ≥ -96 kcal per mole. At lower oxygen potentials (~ΔG_o2 ≤ —110 kcal per mole), no corrosion occurs. Under the same experimental conditions, when the stainless steel is exposed to Cs:Te (2:1, atomic), corrosion occurs and penetration morphology appears to depend strongly on the oxygen-potential environment. The stainless steel suffers intergranular corrosion by Te (in the presence of Cs-Te) under conditions where chromium oxidation is not expected to occur. The kinetics of grain-boundary penetration by Te have been studied at temperatures between 550 and 700°C. The depth of the penetrated zone varies as (time)^1/2, and the process has an activation energy of 34 kcal per mole. The results are discussed, and the effects of stainless steel microstructure and externally applied stress on corrosion reactions are also described.     

Copper diffusion in iron during high-temperature tensile creep

The diffusion of liquid copper in iron from a notched surface has been studied by metallographic, microanalysis, and sessile drop techniques. The diffusivity of copper was found to be 0.59×10^?6 sq cm per sec at 1100°C and 0.97×10^?6 sq cm per sec at 1130°C. The diffusion factor,D ₀ was 0.78×10^?3 sq cm per sec and the activation energy 19.0 kcal per mole. The predominant mode of copper penetration was along grain boundaries, but when larger volumes of copper at the iron surface were used, surface diffusion increased and grain boundary penetration remained constant. The most frequently occurring dihedral angle for liquid copper was 34 deg at 1100° and 1130°C. The liquid copper/austenite interfacial energy was found to be 444 ergs per sq cm between 1100 and 1130°C. From sessile drop measurements, the contact angle was determined as 35 deg at 1100°C and 28 deg at 1130°C, from which values the respective interfacial energies were calculated to be 387 ergs per sq cm and 301 ergs per sq cm.     

Grain-boundary penetration of type 316 stainless steel exposed to cesium or cesium and tellurium

When 20 pct cold-worked Type 316 stainless steel is exposed to Cs at 700°C under controlled oxygen-chemical potential environment, Cs penetration into the stainless steel grain boundaries occurs at oxygen potentials ΔG_o2 ≥ -96 kcal per mole. At lower oxygen potentials (~ΔG_o2 ≤ —110 kcal per mole), no corrosion occurs. Under the same experimental conditions, when the stainless steel is exposed to Cs:Te (2:1, atomic), corrosion occurs and penetration morphology appears to depend strongly on the oxygen-potential environment. The stainless steel suffers intergranular corrosion by Te (in the presence of Cs-Te) under conditions where chromium oxidation is not expected to occur. The kinetics of grain-boundary penetration by Te have been studied at temperatures between 550 and 700°C. The depth of the penetrated zone varies as (time)^1/2, and the process has an activation energy of 34 kcal per mole. The results are discussed, and the effects of stainless steel microstructure and externally applied stress on corrosion reactions are also described.     

Thermal transformations in mechanically alloyed Fe-Zn-Si materials

The ball milling of elemental powders corresponding to Γ (Fe₃Zn₁₀)+0.12 wt pct Si; Γ₁ (Fe₅Zn₂₁) + 0.12 wt pct Si; δ (FeZn₇)+0.12 wt pct Si; and ζ (FeZn₁₃)+0.12 wt pct Si composition ratios yields crystalline, mechanically alloyed phases. Differential scanning calorimetry (DSC) measurements of these materials show that they evolve differently, with well-defined characteristic stages. The activation energies for processes corresponding to these stages, based on kinetic analyses, are determined and correlated to microstructural evolvements. The processes occurring during the first stage below 250 °C, for all of the materials studied using X-ray diffraction (XRD) analysis, are associated with release of strain, recovery, and limited atomic diffusion. The activation energies for recovery processes are 120 kJ/mole for the Γ+0.12 wt pct Si, 131 kJ/mole for δ+0.12 wt pct Si, and 96 kJ/mole for ζ+0.12 wt pct Si alloys. At higher temperatures, recrystallization and other structural transformations occur with activation energies of 130 and 278 kJ/mole for Γ+0.12 wt % Si; of 161 kJ/mole for Γ₁+0.12 wt pct Si; of 167 and 244 kJ/mole for δ+0.12 wt pct Si; and of 641 kJ/mole for the ζ+0.12 wt pct Si. In addition, a eutectic reaction at 420 °C±3 °C, corresponding to the Zn-Si system, and a melting of Zn in Fe-Zn systems are observed for the ζ+0.12 wt pct Si material. The relation of FeSi formation in the Sandelin process is discussed.     

Diffusion of cobalt,chromium, and titanium in Ni3Al

Diffusion studies of cobalt, chromium, and titanium in Ni₃Al (γ′) at temperatures between 1298 and 1573 K have been performed using diffusion couples of (Ni-24.2 at. pct Al/Ni-24.4 at. pct Al-2.91 at. pct Co), (Ni-24.2 at. pct Al/Ni-23.1 at. pct Al-2.84 at. pct Cr), and (Ni-24.2 at. pct Al/Ni-20.9 at. pct Al-3.17 at. pct Ti). The diffusion profiles were measured by an electron probe microanalyzer, and the diffusion coefficients of cobalt, chromium, and tita-nium in γ′ containing 24.2 at. pct Al were determined from those diffusion profiles by Hall’s method. The temperature dependencies of their diffusion coefficients (m[su2]/s) are as follows: ~D_(Co) = (4.2 ± 1.2) × 1O^-3exp {-325 ± 4 (kJ/mol)/RT} ~D_(Cr) = (1.1 ± 0.3) × 10^-1 exp {-366 ± 3 (kJ/mol)/RT} and D_(Ti) = (5.6 ± 3.1) × 10¹ exp {-468 ± 6 (kJ/mol)/RT} The values of activation energy increase in this order: cobalt, chromium, and titanium. These activation energies are closely related to the substitution behavior of cobalt, chromium, and titanium atoms in the Ll₂ lattice sites of γ′; the cobalt atoms occupying the face-centered sites in the Ll₂ structure diffuse with the normal activation energy, whereas the titanium atoms oc-cupying the cubic corner sites diffuse with a larger activation energy that includes the energy due to local disordering caused by the atomic jumps. The chromium atoms which can occupy both sites diffuse with an activation energy similar to that of cobalt atoms.     

Thermodynamic properties and electrical conductivity of Ta3N5 and TaON

TaON and Ta₃N₅ powders and thin films were prepared from Ta₂O₅ powders and tantalum thin films by equilibrating specimens with ammonia-bearing gas mixtures at 1100°K. TaON was found to be nonstoichiometric and to have semiconducting properties. The free energy of formation of TaO1.05N0.95, which is the composition in equilibrium with Ta₂O₅, is -94.1± 5 kcal per mole. The range of electrical conductivity observed at room temperature was 10^-3 to 5 (ohm-cm)^-1. Ta₃N₅ has a free energy of formation of -65 ± 10 kcal per mole, and its electrical conductivity is 1.3 x 10^-4 (ohm-cm)^-1. Formerly with Bell Telephone Laboratories, Murray Hill, N. J.     

The creep behavior of W-5 re

Polycrystalline W-5 wt pct Re was creep-tested in tension from 1500° to 1900°C at stresses from 2500 to 10,000 psi in a vacuum of 10^?8 torr. The steady-state strain rate was directly proportional to stress to the 5.5 power, and the apparent activation energy for creep was 104 kcal per mole. Dislocation substructure that developed during high-temperature deformation was studied by transmission electron microscopy. The total dislocation density was dependent on stress to the 2.1 power and was insensitive to temperature and strain. No subgrains were found in creep tested specimens. The rate-controlling deformation mechanism was ascribed to dislocation climb where the governing diffusion process was dislocation core diffusion. Comparison of creep data for tungsten, W-5 wt pct Re, and W-25 wt pct Re showed that W-5 wt pct Re alloy has significantly better creep properties than the other two materials.     

Preaging effects in Al-Mg-Si alloys

The aging characteristics of aluminum alloy extrusions containing 0.60 to 0.90 wt pct Mg₂Si were determined. At low Mg₂Si levels, preaging treatments at room temperature and at elevated temperatures refined the G.P. zone dispersion and increased the alloy’s hardness after final aging. Preaging had little effect on hardness at the high end of the Mg₂Si range. These results are explained on the basis of current aging theories which invoke the concept of a critical temperature, above which homogeneous nucleation does not take place. This temperature varies from ≃150°C at 0.6 pct Mg2Si to ≃220°C at 1.5 pct Mg₂Si. The apparent activation energy for final aging was estimated to be 21 kcal/mole, a value which is intermediate between the activation energies for vacancy motion and solute (silicon and magnesium) diffusion in aluminum.     

Viscosity of PbO-SiO2 melts

Viscosities (η) of PbO-SiO₂ melts that contained 25.0 to 48.8 mole pct SiO₂ were measured at temperatures 928 to 1273 K by a rotating cylinder method. The data were analyzed in terms of the conventional polymer theory. The results followed Arrhenius behavior in the different temperature ranges despite the general belief of non-Arrhenius behavior of viscosity in slag melts. The calculated activation energies were a function of temperature and composition of the melts. The activation energies for viscous flow, in general, at above approximately 850 °C were lower than those below 850 °C and varied between 25 and 150 kJ per mole. Formerly with National Research Council of Canada, Atlantic Research Laboratory, Halifax, NS, Canada     

Cation self-diffusion in chalcopyrite and pyrite

The self-diffusion coefficient of Fe⁵⁹ was measured in pyrite (FeS₂) and chalcopyrite (CuFeS₂) and found to exhibit an activation energy of 10.0 and 6.4 kcal/mole, respectively, in the temperature range of 100 to 300°C. The self-diffusion of Cu⁶⁴ and Ag^110m in chalcopyrite yielded activation energies of 12.1 and 17.5 kcal/mole in the same temperature range. The technique of nondestructive measurements is described, and diffusion mechanisms and implications for chemical leaching are discussed.     

Oxygen Permeation of Partly Molten Slags

The conductivities, oxygen ion transference numbers, and oxygen permeation fluxes of NiO-30, 36, 42, and 48 wt pct Bi₂O₃, In₂O₃-30, 36, 42, and 48 wt pct Bi₂O₃, ZnO-15, 20, 25, and 30 wt pct Bi₂O₃, ZrV₂O₇-16, 20, 24, and 28 wt pct V₂O₅, and BiVO₄-5, 7, 10, and 12 wt pct V₂O₅ partly molten slags have been measured by using the four-probe DC, volumetric measurements of the faradaic efficiency, and gas flow techniques, respectively, under various temperatures and oxygen partial pressure gradients. Results indicate that in the ranges of slag layer thicknesses 1 to 5 mm and temperatures 923 K to 1173 K (650 °C to 900 °C), used in the present study, the overall oxygen permeation kinetics is controlled by both chemical diffusion and surface exchange reactions. The oxygen permeation fluxes (3 × 10^?9 to 9 × 10^?8 mol/cm² s) were found to increase with volume fraction of liquid. The oxygen ion transference number was found to be in the range 0.2 to 0.8. The ambipolar conductivity, characteristic thickness, and surface exchange coefficient were estimated to be in the ranges 1.1 × 10^?3 to 2.3 × 10^?1 S/cm, 2 × 10^?2 to 7 × 10^?2 cm, and 1.3 × 10^?6 to 2.1 × 10^?6 cm/s, respectively.     

Electrotransport and diffusion of Co,Fe, and Ag in γ-Cerium

Electrotransport mobilities and diffusion coefficients were obtained for radiotracer impurities of Fe, Co, and Ag in Ce. The iron and cobalt moved toward the anode with mobilities of ～10^?3 cm²/v-s in the range of 550° to 650°C. The silver moved to the cathode with mobilities of ～10^?5 cm²/v-s in the range of 600° to 700°C. The, diffusion coefficients obtained fit an Arrhenius equationD=D _o e ^?ΔH/RT with the following parameters: Fe:D _o=3.3×10^?4, ΔH=4.6 kcal/mole Co:D _o=10^?2, ΔH=11 kcal/mole Ag:D _o=1.4, ΔH=28 kcal/mole The results are compared with other rare-earth diffusion data, and the possibility of a substitutional-interstitial diffusion mechanism, is considered.     

Extraordinary snoek damping in an Fe−Mn−N alloy

Extraordinary Snoek damping was examined in an Fe-2 pct Mn-0.01 pct N alloy over a temperature range of ?50° to 290°C. The complex damping spectrum is composed of a relatively small nitrogen Snoek peak and a series of at least four extraordinary Snoek peaks that lie between 7° and 135°C at 1 Hz. The low temperature peak (at 7°C for 1 Hz) was investigated in some detail by varying the frequency between 0.19 and 2.5 Hz and by analyses of the peak shape. The peak-shift analyses give, an activation energy of 17.1 kcal per mole, which is 2 to 3 kcal per mole more than that given by the peak-shape analyses. Therefore, the lowtemperature peak is not characterized by a single relaxation time. Furthermore, analyses of a series of synthetic curves indicated that the low-temperature peak can be characterized by two relaxation times with the strength of one relaxation being about 15 pct of the other. The activation energy of 17.1 kcal per mole is in excellent agreement with the previously proposed proportionality between peak temperature and activation energy of relaxation peaks. The present findings are in general consistent with the model for the low-temperature peak that envisions a nitrogen atom jumping about a pair of manganese atoms.     

Cellular precipitation in Ni-51Cr lamellar eutectic and cast Ni-44Cr alloys

The phases present in directionally solidified Ni-51Cr lamellar eutectic and cast Ni-44Cr alloys are identified. These are the nickel-and chromium-rich lamellae, a Widmanstätten precipitation of nickel in the chromium-rich lamellae, grain boundary precipitation of chromium, and scattered discrete particles of chromium oxide. Upon annealing, the amount of the nickel precipitates increases drastically and a well defined cellular precipitation appears in the nickel-rich lamellae. The cellular precipitation conforms in almost every way to typical cellular reaction such as in the Pb-Sn system. Cellular (linear) growth rate, G, and interlamellar spacing, S, were measured on specimens annealed for times ranging from 1/2 to 100 hr at 625°, 700°, 760°, and 850°C. G increased from (average for both Ni-Cr alloys) 2.3 × 10^?8 cm per sec at 625°C to 7.7 × 10^?7 cm per sec at 760°C and decreased again at 850°C. S varied from 2 to 10 × 10^?5 cm as the annealing temperature was increased. The calculated grain boundary diffusivity, D^B, representing the diffusion of chromium in fcc Ni-Cr solid solution, increased from 6.7 × 10^?11 sq cm per sec at 625°C to 8.6 × 10^?8 sq cm per sec at 850°C. The activation energy 64 kcal per mole, is of the order of that obtained for self-diffusion.     

Diffusion of titanium in copper

Interdiffusion coefficients in copper-titanium alloys have been determined by Matano's method in the temperature range between 973 and 1283 K on (pure Cu)-(Cu-1.98 at. pct Ti alloy) and (pure Cu)-(Cu-2.91 at. pct Ti alloy) couples. Temperature dependence of the impurity diffusion coefficient of titanium in copper, determined by extrapolation of the concentration dependence of the interdiffusion coefficient to zero mole fraction of titanium, is expressed by the following Arrhenius equation along with the probable errors:D _Ti/Cu=(0.693 _−0.135 ^+0.169 )×10⁻⁴exp[−(196±2)kJ mol⁻¹/RT] m²/s. The difference in the activation energies for the impurity diffusion of the 3d-transition metals and self-diffusion in copper has been calculated by applying LeClaire's model with the oscillating potential of the impurity atom in copper. The calculated values agree well with the experimental values including the present one. Kazutomo Hoshino, formerly Graduate Student, Tohoku University     

The diffusion of hydrogen in liquid iron alloys

Rates of absorption of hydrogen in stagnant liquid iron and ten (Fe-X) binary iron alloy systems were studied by an unsteady-state gas-liquid metal diffusion cell technique. These rates were found to be controlled by diffusion of hydrogen in the liquid phase. Chemical diffusion coefficients (D _h) were measured in pure iron and Fe-X alloys in the following (at. pct) composition ranges: Mn (0 to 5), Cr (0 to 25), V (0 to 25), Nb (0 to 10), Mo (0 to 25), W (0 to 5), Ni (0 to 75), Co (0 to 75), Sn (0 to 10), and Cu (0 to 25). All measuredD _H values at 1600°C lie between 7 × 10^-4 and 16 × 10^-4 sq cm per sec. The diffusion coefficients found for pure iron can be represented by D_H ^Fe = 4.37 × 10⁻³ exp (−4134 ± 1012)/RT cm²/sec where the uncertainty in the activation energy, Q, in cal per mole, corresponds to the 90 pct confidence level. A linear relationship was found between the logarithm of the hydrogen diffusion coefficient D_H ^Fe-X and the interaction parameter ε_H ^X for low and medium concentrations of alloying elementX, when applied to a fixed concentration ofX(5 or 25 at. pct) and to individual periods in the periodic table. A useful linear correlation also appears to exist between logD_H ^Fe-X and hydrogen solubility for fixed concentration ofX and with respect to the period in whichX is found. Formerly Research Assistant, Department of Mineral Engineering, Stanford University, Stanford, Calif. This paper is based upon a thesis submitted by P. J. DEPUYDT in partial fulfillment of the requirements of the degree of Doctor of Philosophy at Stanford University and part of a presentation made at the 1970 Annual AIME Meeting.     

Liquidlike sintering behavior of nanometric Fe and Cu powders: Experimental approach

Nanometric Fe and Cu powders were sintered in vacuum, He, and H₂ atmospheres after uniaxial cold pressing. The shrinkage behavior of samples was studied using three different dilatometric techniques: constant heating rate, isothermal annealing, and the Dorn method. Density greater than 90 pct was obtained at sintering temperatures of 900 °C. In nanometric powders, densification and grain coarsening occurred in a narrow temperature interval. Despite the low oxide content in the starting powders (1.5 to 4 wt pct), the reducing atmosphere plays a relevant role in the sintering process. The self-diffusion activation energies obtained for nanometric Fe were 116 and 60 kJ/mole in vacuum and H₂, and those obtained for nanometric Cu were 70 and 43 kJ/mole in He and H₂. According to the present results, the activation energies obtained from both nanometric powders in H₂ could be associated with those for self-diffusion in liquid Fe (65 kJ/mole) and Cu (41 kJ/mole).     

The oxidation behavior of Ni-Cr-Al-2ThO2 alloys at 1093° and 1204°C

A pack diffusion process has been developed which permits the introduction of nearly 6 wt pct Al into solid solution in the near surface region of TDNiCr (Ni-20 wt pct Cr-2 vol pct ThO₂) and Ni-20Cr. Alumina scales, adherent under cyclic heating and cooling conditions, were produced on TDNiCr-5.86A1 upon exposure to an environment of 1.33 × 10³N/m² (10 torr) or 1.01 × 10⁵N/m² (760 torr) air at temperatures of 1093° and 1204°C. While the same oxidation kinetics were observed in isothermal tests for Ni-14.6Cr-5.86Al as were obtained for the TDNiCr-5.86A1, the dispersion strengthened alloy exhibited superior oxide scale adhesion during cyclic testing. At 1204°C continuous weight gains were observed under all test conditions for TDNiCr-5.86A1, in contrast to the weight loss with time which occurred several hours after exposure of TDNiCr to an oxidizing environment. TDNiCr with an initial aluminum surface concentration of 4.95 wt pct has nearly comparable oxidation resistance to the TDNiCr-5.86Al alloy. Specimens with 4.3 wt pct Al at the surface have inadequate aluminum to form Al₂O₃ scales, and weight losses are observed after 40 h upon exposure of these specimens to 1.01 × 10⁵N/m² (760 torr) air at 1204°C.     

The surface tension of liquid silver alloys: Part II. Ag−O alloys

The surface tensions of liquid Ag-O alloys have been determined by the sessile drop method. The surface activity of oxygen, as measured by ?(dσ/dX _O)X_O→0_j, where σ is the surface tension of the metal andX _O the mole fraction of oxygen, is quite large and equals 3.80×10⁵ dyne per cm at 980°C and 1.35×10⁵ dyne per cm at 1108°C. The heat of adsorption of oxygen is estimated to be of the order of 30 kcal per mole. Application of the monolayer approximation shows that liquid silver becomes saturated with oxygen when each adsorbed oxygen atom occupies an area of 33±5Ų. Small additions of platinum to silver do not change the characteristics of the adsorption of oxygen appreciably. An analysis of the data is consistent with the conclusion that saturation of the surface of liquid silver with oxygen results from the formation of an ionic two-dimensional compound at the surface. This hypothesis is tested in the case of several other systems and yields satisfactory results. The structure of these compounds is discussed. In the case of the Ag-O system, it appears to correspond to the stoichiometry Ag₃O.