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By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

By F. Weinberg, E. H. McLaren

Dilute binary alloys have been solidified under controlled thermal conditions, and solute distributions, temperatures during freezing and melting, and the position and morphology of the solid-liquid interfaces have been examined. Binary Zn, Sn, and Pb based alloys were investigated with solute additions of AgU°, AU°, Sb'24, TlZo4, snH3, and Zns5. Approximately 150 cc of metal was used in each ingot. Appreciable solute segregation occurred in most of the ingots, depending on the solute concentrations, distribution coefficients. and freezing conditions of the alloys. Measurements were made of the general solute distribution by sectioning layers of material from the ingot circumference and counting the activity of each layer. Local segregation was detected by autoradiographic techniques. Freezing and melting curves for the same alloys were obtained by precision resistance thermometry. These curves are related to the corresponding measured solute distribution curves and those calculated from theoretical expressions. The position and morphology of solid-liquid interfaces during freezing were determined by both decanting and quenching techniques. The results indicate the manner in which freezing and remelting occurred under the conditions investigated. If an isomorphous dilute binary alloy is solidified or melted under equilibrium conditions, the concentration of solute in both solid and liquid would be uniform at all stages in the freezing process. The solute concentrations during freezing could be determined from the phase diagram of the alloy, and the freezing curves would have an alloy slope defined by the solidus and liquidus points. In practice, however, solidification under equilibrium conditions rarely, if ever, occurs, primarily because of low rates of diffusion in the solid and incomplete mixing in the liquid. As a result, the solute distribution and the shape of the freezing and melting curves obtained in a given system depends on a number of factors. These include, in addition to the extent of diffusion and mixing, the initial solute distribution and concentration, the distribution coefficient, the rate of freezing or melting, supercooling of the liquid, the morphology of the solid-liquid interface, and the effect of annealing. The purpose of the present investigation was to determine, experimentally, actual solute distributions and thermal curves for a series of dilute binary alloys, using tracer techniques to determine the solute distributions and precision resistance thermometry for the temperature measurements. In addition, observations were made of the positions and morphologies of the solid-liquid interfaces during freezing and remelting. The distribution of solute in a dilute alloy, assuming complete mixing in the liquid, and negligible diffusion in the solid, is given by1 where Co is the mean solute concentration of the alloy, C, is the solute concentration in the solidg is the fraction of the ingot solidified, and ko is the equilibrium solute distribution coefficient (assumed to be independent of concentration for dilute alloys). For the case of partial mixing, ko can be replaced by an effective distribution coefficient k. If solute transport in the liquid is assumed to be entirely due to diffusion, with negligible diffusion in the solid, then the solute distribution in the solid is given by Tiller et a1.' as where R is the rate of advance of the solid-liquid interface, D is the solute diffusion coefficient in the liquid, and x is the position of the interface from the start of freezing. The temperature at the interface TI is related to the solute concentration of the solid at the interface C, by the expression where Tm is the freezing temperature of the pure solvent and ml is the slope of the liquidus for the binary alloy being considered. Accordingly, by relating TL to the actual temperatures measured in the present experiments, solute distributions can be deduced from the temperature measurements. Using the above expressions, the measured solute distribution of a given alloy may be compared to the theoretical distributions, as well as to the distribution calculated from the observed freezing curve. EXPERIMENTAL The solvent materials used in making up the binary alloys were C. P. New Jersey zinc (99.999 pct), Vulcan Extra Pure Tin (99.999 pet), and Tadanac lead (99.998 pct). The solute elements were of 99.99 pct purity or better, and were activated in the

Jan 1, 1963

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,&apos; in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young&apos;s modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B&apos;) where B and B&apos; are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By I. A. Goddard

INTRODUCTION This paper deals with the development of the sublevel open stoping (SLOS) method in lead orebodies at the Isa Mine of Mount Isa Mines Limited, during the last ten years. Open stoping in different forms has been used at the Isa Mine for many years. Prior to the period under review, stopes were small, pillars were not always recovered, and scrapers extracted the ore. By the end of the sixties, the use of load-haul-dump units was becoming more widespread. Wagner ST5&apos;s were the mucking units for the lead cut and fill stopes. Some of the open stopes in 5 orebody above 13 level had 100 kW slushers, but the more southerly stopes were the sites for the introduction of diesel front-end loaders for extraction. In the early seventies, new methods were used in the block of six stopes in 2 and 5 orebodies between 8 level and 13 level and a trial stoping project was undertaken in 7 orebody between 11 level and 13 level to determine possible stope dimensions for the extraction of the Racecourse orebodies below 13 level. By the mid-19701s, stoping was well underway in 5, 7 and 8 orebodies between 13 level and 15 level, using the &apos;triplet&apos; system, incorporating cemented hydraulic fill to allow greater pillar recovery. As the eighties were entered, development of the Racecourse orebodies below 15 level commenced, as did preparations for 1 orebody in the upper levels of the north end of the mine. In both cases, the pillar recovery method has been changed to reduce the amount of cemented fill required for pillar recovery. GEOLOGY Most of the lead orebodies at Isa Mine lie chiefly to the north of the central shaft complex. They are bedded sulphide deposits in a host rock called Urquhart Shale, which dips at roughly 650 to the west. The main minerals are galena and sphalerite, with the silver mineral, freibergite, being contained in the galena. To the hangingwall of the sequence are the Black Star orebodies (1, 2 and 5) which are relatively wide, pyritic and with low to above average grade lead. The Racecourse orebodies (6 to 16) lie to the footwall, and have a large variation in width, low to high grade lead, and gradation in the lead to zinc ratio from north to south. Stope outlines are often determined by economic or engineering considerations rather than geological. The published extraction reserves are 56 million tonnes of primary ore, containing 150 grams of silver per tonne, 6.4% lead and 6.5% zinc. Traditionally, it has been regarded as lead ore, although the dominant revenue earner varies from time to time. In the Black Star orebodies, the ore and hangingwalls are more competent and open stoping has long been used. The major Racecourse orebodies which have been open stoped are 7 and 8 orebodies. This has been where the orebodies are wider (to the south) and where hangingwall conditions allow. This latter aspect has been greatly influenced by the presence of &apos;silica dolomite1. This tough, relatively homogeneous, non-bedded rock is, in fact, the host rock for the copper mineralisation at Mount Isa, and provides a competent hangingwall for some of the lead stopes. While the shale&apos;s bedding and jointing has a major influence on the ground conditions, there is a major fault system which causes local problems. The principal virgin stress direction is perpendicular to the bedding, but the local stress situation is complicated because of shielding by filled stopes in the hangingwall copper orebodies and because of the interaction between orebodies being extracted to the footwall. Most development on strike is mined with a &apos;shanty-back’, with the back being as close to normal to the bedding as possible. This is near parallel to most jointing and the principal stress direction. Figure 1 is a plan view of 14 level north, which provides a representative horizontal section through the orebodies. A typical cross section is shown in Figure 2. The narrow, parallel footwall orebodies can be seen to differ from the wider hangingwall orebodies.

Jan 1, 1981

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.&apos; The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös&apos; law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By W. L. Phillips

Stress-train curves were obtained for single crystals of silver, Ag-5 pct Zn, Ag-10 pct Zn, and Ag-20 pct Zn tested in tension and shear at 78°, 195°, and 297°K. At room temperature the critical resolced shear stress gC increased, the length of&apos; the easy-glide region increased, and the rate of&apos; work hardening dwving easy glide decreased with increasixg zinc concentration. The change in the ratio of uc at room temperature to that at lower temperatures was significantly greater for the alloys than for pure silver. It was found that an increment in stress was necessary to continue slip when the slip direction was rotated 60 deg. The magnitude of this increment increased with strain for all alloys, increased with zinc concentration for a given strain, and for a given strain increased with decreasing -temperature. DESPITE its practical importance in improving the mechanical properties, alloying is not fully understood. Except for copper alloys few sets of systematic data are available. Von Goler and Sachs&apos; studied the deformation of Cu-Zn alloys of increasing zinc content and found that, for dilute alloys, the critical resolved shear stress increases linearly with concentration. The range of easy glide was found to increase with increasing zinc content. Schmid and seliger,2 Sachs and Weerts,3 and Osswald4 have shown that with Mg-A1, Au-Ag, and Cu-Ni crystals, respectively, the critical resolved shear stress also varies linearly with concentration. More recently, Linde and his coworkers have investigated the variation of the critical shear stress of copper alloyed with tin , antimony, indium, germanium, silicon, nickel, and gold. They found that the slope of the critical resolved shear stress is related to the change of lattice parameter with composition, and also to the difference in Goldschmidt&apos;s atomic diameter between solvent and solute atoms. Garstone, Honey-combe, and creetham6 have shown that similar relationships can be found for small additions of silver, gold, and germanium to pure copper. They found that, with increasing silver or gold concentration, the critical shear stress for glide is increased by alloying, and so is the range of easy glide, which reaches as much as 60 pct for 0.50 pct Ag alloy and 0.62 pct Au alloy, as compared to 6 pct for pure copper of similar initial orientation. They also found that the alloying additions had little effect on the rate of hardening during easy glide, the slope scarcely changing with increasing alloy content. General secondary slip was detected only when the crystals began to harden rapidly. Although the slip appeared to be very fine in the early stages of deformation, coarser slip bands were formed towards the end of the extensive easy-glide range. The present investigation describes the deformation characteristics of single crystals of Ag-Zn containing different concentrations of zinc. Tension and shear testing were used for this study. EXPERIMENTAL PROCEDURE The method of growing the single crystals, sample preparation, and method of testing have been described in detail previously.&apos; EXPERIMENTAL RESULTS A) Tension-Room Temperature. The initial orientations and stress-strain curves of single crystals of silver, Ag-10.0 pct Zn, and Ag-20.0 pct Zn are shown in Fig. 1. It is evident that there is considerable change in the stress-strain characteristics as a function of zinc concentration. The effects of zinc concentration on the critical resolved shear stress for both CU-zn8 and Ag-Zn alloys are summarized in Fig. 2. At all concentrations the resolved shear stress of the Cu-Zn alloys is higher than that of the Ag-Zn alloys. The resolved shear stress increases parabolically as a function of composition for both alloy systems. The length of easy-glide region increased with increasing zinc concentration, Fig. 3b). As the length increased the slope (do/de) decreased slightly, Fig. 3(b). Metallographic investigations demonstrated two significant effects of increasing zinc concentration. First, the amount of clustering increased, compare Figs. 4(a) and (b). The slip lines changed from uniform in pure silver to clustered in the Ag-20 pct Zn and Ag-30 pct Zn alloys. Second, the amount of cross slip decreased as the amount of clustering decreased.

Jan 1, 1968

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.&apos; In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.&apos; APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.&apos; This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By O. D. Sherby, J. E. Dorn

For elevated temperature-constant load creep tests of a solid solution alloys, the creep strain is a function of a temperature-compensated time parameter 0 = je H/RT dt. The activation energy H is equal to o constant of about 36,000 cal per mol. The substructures resulting from a given creep stress condition are functions of the creep strain independent of temperature. Each new creep stress gives a new unique set of grain substructures; this is one of the factors responsible for the failure of the mechanical equation of state for creep. IN this report an attempt is made to correlate the creep properties of dilute a: solid solutions in aluminum with the subgrain structures that are developed during creep. The possibilities of such correlations have already been suggested by Wood et al. and others1-" who demonstrated that the subgrain structures are functions of the creep stress, creep strain, rate of creep, and temperature. Investigations by Sherby and Dorn&apos; have shown that the creep strain, E, at constant load for dilute a solid solutions of aluminum is given by the functional relationship: e = f(8,u,) [1] where: 0 equals te-AH/RT = temperature-compensated time; t, time; AH, activation energy, - 35,800 cal per mol; R, gas constant; T, absolute temperature, above 400°K; and u,, initial creep stress. Consequently, it was anticipated that the subgrain structure that develops during a constant load creep test should also correlate with any two of the three significant variables C, 8, and Another possible correlation between the subgrain structure and the creep variables is obtained by differentiating Eq. 1 with respect to time, whence the creep rate, 2, becomes: = (2L) (2) =f (, u,) e-AHRT [2] or: e = F (c e H/RT, 0) [3] For the minimum creep rate, ;,, 8 is solely a function of U, as revealed by Eq. 1. Consequently, at the minimum creep rate Eq. 3 reduces to: = F (eAH/RT) [41 Correlations between U, and i, eAH/RT were found valid for solid solution alloys of aluminum where AH was a constant of about 35,800 cal per mol. The parameter ;, eH/RT is identical to the Zener-Hollo-mon parameter8," used by them in evaluating the tensile properties of copper and other metals. Eq. 4 suggests that the subgrain structure developed during secondary creep might be correlatable with either of the two variables 2, e H/RT or u,. Some of the solid solution aluminum alloys which were discussed in an earlier report&apos; were also used in the present investigation. Sheets of these alloys were homogenized, cold rolled from 0.100 to 0.070 in. in thickness and then recrystallized to about the same grain size. Their chemical composition and grain size are recorded in Table I. Creep specimens were selected with their tensile axes in the rolling direction. The details for creep testing have been described10 and will not be repeated here. All creep tests were performed under constant load conditions. Experimental Results and Discussion Metallographic Structure of Creep Specimens: In order to obtain a preliminary concept of creep on the metallographic structure of high purity aluminum, the various ruptured specimens previously used to obtain the creep data for pure aluminum were polished and etched electrolytically in a dilute solution of fluoroboric acid. Oblique illumination was used to reveal the substructures which, for convenience, are shown in correlation with the vs. ;, eH/RT curve in Fig. 1. It is necessary to emphasize that the data for the curve refer to the various secondary stages of creep whereas the micrographs refer to the fractured creep specimens. Nevertheless a regular and systematic correlation is observed between E, eAH/RT (or the creep stress) and the micro-structure at fracture. For In (e, eAH/RT) = 42.3, which refers to creep at a high creep rate and a low creep temperature, the fractured aluminum specimen, as shown by the micrograph in the upper right-hand corner of Fig. 1, exhibited extensive deforma-

Jan 1, 1954

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß&apos;-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,&apos; alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0&apos; phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

Jan 1, 1968

By K. Tangri, M. Chaturvedi

On water-quenching from within the (a + ß) phase region Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys can undergo w transfirmation. This transformation has been attributed to the enrichment of ß Zr phase, at the solution-treatment temperature, by the solute atoms. The ß—w transformation is accompanied by a hardening 01 the alloys and in the optimum condition w-bearing specimens of the ternary alloy are about 14 pct harder than those bearing only a&apos; phase. On aging crl reverls thermally to more stable phases, which results in a considerable softening of the specirnens, as follows: w quenched -waged + ß Zr (enriched) waged - a + ß Nb The high-temperature bcc ß Zr in certain zirconium alloys can transform to a metastable w phase which has a primitive hexagonal structure. In the Zr-Nb alloy system w phase has been observed in the composition range of 7 to 15 wt pct Nb by a number of investigators.&apos;-&apos; In this composition range w can form by water-quenching ß Zr or by aging. known as athermal and thermal w, respectively. Hatt and Roberts&apos; have found that thermal w has a constant c/a ratio of 0.622 +0.002 regardless of the composition and tha: the lattice parameters are of the order of a = 5.02A and c = 3.0 ?. The actual lattice parameters depend upon composition and the temperature of aging. The lattice constants of athermal w. however, depend upon alloy composition.3 The presence of w phase in zirconium alloys can cause substantial strengthening which has been attributed as probably due to the coherency between w and parent ß Zr phase. Robinson et al.&apos; found that the presence of w can raise the strength of Zr-5.0 Nb-2.0 Sn and Zr-5.0 Mo-2.0 Sn alloys to about 170.000 psi: however. the ductility is considerably reduced. With the growing use of Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys in the nuclear reactors, and the significant effect of w transformation on the mechanical properties of zirconium alloys studies were undertaken to study the w transformation in Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys. This paper is concerned with the formation and reversion of w phase in these alloys. 1) MATERIALS AND EXPERIMENTAL TECHNIQUES The following two alloys were studied: 1) Zr-2.5 Nb-0.5 Cu (referred to as the ternary alloy): 2) Zr-2.5 Nb (referred to as the binary alloy). The chemical analysis of the alloys is given in Table I. The alloys, in the form of 3/8-in.-diam rods and 1/8-in.-thick sheets, were supplied by the Chalk River Nuclear Laboratories of the A.E.C.L. Initial fabrication for preparation of various specimens was carried out by cold rolling and swaging with intermediate anneals at 1000°C. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-% m of Hg. For optical metallography and hardness measurements disc specimens + in. diam by + in. thick were used. After the required heat treatments the specimens were mechanically and then chemically polished in a 45 pct HNO3, 45 pct H20. and 10 pct HF solution. The hardness measurements on the chemically polished specimens were carried out on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative hardness value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using copper K-a radiations in 114.6-mm-diam camera. Thin films for transmission electron microscopy were prepared by electropolishing heat-treated a by 7 by 0.005-in.-thick strips using a modified Bollmann-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol electropolishing bath was kepl at -5OCC and polishing was done at 5 to 10 v. The thinned specimens were washed in ethyl alcohol at -30" to -40°C and dried between filter papers. The thin films

Jan 1, 1970

By Howard Martens, Pol Duwez

XPERIMENTS were performed on a Cr-Fc alloy Econtaining 44.7 pet Cr in order to determine the heat evolved during the transformation of the a solid solution into the s phase, and the change in volume accompanying the transformation. Since previous measurements on the rate of formation of a from s indicated that the reaction was quite fast as soon as the equilibrium temperature of 820°C was exceeded by some 50°, standard thermal analysis experiments were performed on heating specimens of s at the rate of approximately 40°C per sec. A definite thermal arrest was observed at 870"C, Fig. 1. This result indicates that the reverse seaction of into a is exothermic. From the heating curve of Fig. 1, taking 15°C per sec as the heating rate in the neighborhood of the transformation, 2.4 sec as the time for transformation, and assuming that the specific heat of the alloy at 850°C is an average between iron and chromium, namely 9.5 cal per mol per "C, the latent heat of transformation is approximately 342 cal per mol. The order of magnitude of this latent heat was also obtained by comparing the heating curve of Fig. 1 with a similar curve obtained with pure iron under identical experimental conditions. It was found that the length of the thermal arrest for s was about 1.8 times as long as that for iron. Since the latent heat of the a to 7 iron transformation is 203 cal per mol1, 2 the latent heat of it to a would be 365 cal per mol, which is in relatively good agreement with the value determined from the heating curve. For the determination of volume change, thermal expansion curves were recorded using a specimen containing 44.7 pet Cr and completely transformed to cr by previous treatment. The curves were recorded at a rate of heating of about 4°C per min and at approximately 840°C a sharr, increase in length of about 0.08 pet took place. Fig. 2. It is therefore established that the specific volume of a near the transformation temperature is about 0.24 pet smaller than that of a, and consequently, when the s phase forms in an a matrix, it would tend to shrink away from the matrix. Since the s phase is known to be extremely brittle, these results offer an explanation for the microscopic cracks often observed in the a phase under the microscope. The results of this study are in qualitative agreement with previously published data on stainless steel 19-9DLa and on a Cr-Fe alloy containing 45 pet Cr.&apos; The increase in density due to the transformation from n to s given in ref. 4 is 0.90 pet. These measurements, however, were made at room temperature. whereas the presently reported 0.24 pet is the change at the temperature at which the transformation takes place during heating. In the graph of Fig. 2, the percentage change in length that would be observed at room temperature is given by the length X, which is about 0.27 pet. This would correspond to 0.81 pet in volume change. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-ORD-18 with the Army Ordnance Corps, Washington, D. C. The authors wish to thank this agency for permission to publish the results of this investigation. References I H. Klinkhardt: Measurements of True Specific Heats at High Temperatures. Annalen der Physik (1927) 84, pp. 167-200. - H. Esser and W. Runghardt: Influence of the Method, of Dctcrmination on the Measured Heat Content of Iron. Archtvo ffur Dct Eisenhiittenwesen 11934) 8, pp. 37-38. J. J. Gilman, P. K. Koh, and 0. Zmeskal. Delta Ferrite Formation and its influence on the Formation of Sigma in a Wrought Heat Resisting Steel. Trans. ASM 1 1949) 11, pp. 1371-1388. 1 J. M. Thomas: Discussion of ref. 3. Trans. ASM (1949) 41, pp. 3 390-1392.

Jan 1, 1957