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By Stephen D. Antolovich

RECENTLY, much interest has been generated in materials that undergo martensitic phase transformations on straining.')' While it is undoubtedly true that a large amount of ductility can be obtained at rather high strength levels, the question of the general way in which the phase transformation affects the plane strai fracture toughness, as measured by the parameter KIC, has yet to be answered. Let us consider a material that contains a sharp crack as shown in Fig. 1, and is subjected to a tensile stress 00. It is known that the presence of a crack tends to multiply the stress in the area of the crack according to the following equations:3

Jan 1, 1969

By M. J. Marcinkowski, A. S. Sastri

A detailed compressive stress-strain analysis and transmission electron microscopy investigation has been made of the deformation behavior occurring in a 50 at. pct Ni-Ti (hypoeutectoid) alloy and a 54.5 at. pct Ni-Ti (hypereutectoid) alloy. In the case of the hypoeutectoid alloy, three stages of work hardening are observed. Stage I occurs at a very low stress and is associated with plastic deformation via martensite formation. Stage 11 is characterized by very rapid work hardening and is due to difficulties in causing further deformation in the fine martensite aggregate produced in Stage I. Stage III which occurs at very high stress levels is characterized by smaller work hardening rates and is due to the plastic deformation arising from alternate reconversions of the original martensites to martensites of varying orientation. Rapid quenching of the hypereutectoid alloy leads to very high yield strengths and is related to a fine precipitate dispersion that such treatment brings about. The present investigation represents the final phase of a three-part study directed toward an understanding of the solid-state transformations in near equi-atomic Ni-Ti alloys as well as the deformation mechanisms associated with these alloys. In the first part,"2 to be henceforth referred to as I, it was found that alternate simple shears on {112} planes and in (111) directions convert the parent B2 structure in the equiatomic NiTi alloy into two distinct close-packed monoclinic martensites. All of the marten-sites were of this type, whether they were formed by cooling or by plastic deformation, whether induced to form in bulk samples or in thin foils, or whether examined in the electron microscope at room temperature or below. On the other hand, in the second part of this investigation,3 to be reffered to as 11, it was shown that upon slow cooling to about 640°C. alloys in the neighborhood of NiTi which possess the B2 structure transform eutectoidally into their equilibrium phases Ti2Ni and TiNi3. However, preceding the formation of these equilibrium phases a series of metastable intermediate phases are formed. This paper will set as its goal the elucidation of the remarkable deformation behavior exhibited by NiTi. In particular, Buehler and Wiley4 have found equiatomic NiTi to be surprisingly soft, while Buehler et al.5 have shown this alloy to possess a memory effect: i.e., upon bending at room temperature it will revert to its original shape when heated to above about 50°C. In I it was shown that NiTi was soft in the sense that the yield stress was low; nevertheless, the alloy work-hardened at an extremely rapid rate to very high stress levels. On the other hand, the hypereutectoid alloys with somewhat higher nickel, say 54.5 at. pct (60 wt pct) have enormously increased yield strengths compared to those of the equiatomic alloys. In order to determine the atomistic processes giving rise to the above behavior, it was decided to examine samples that were wafered from bulk specimens deformed in compression to various strains using the techniques of transmission electron microscopy. EXPERIMENTAL TECHNIQUE All of the alloys used in the present investigation contained either 50 at. pct Ni (55.06 wt pct) or 54.5 at. pct Ni (60 wt pct) and were arc-melted in the form of a finger using the same techniques described in I and II. The finger was capsulated in a stainless-steel jacket and swaged at 850°C into rods. Compression specimens 0.300 in, long and 0.200 in. in diam were machined from these rods. In order to completely re-crystallize the samples and remove residual stresses, all of them were capsulated in evacuated quartz, annealed for 1/2 at 1050°C. and then furnace-cooled. Compression tests were carried out in an Instron tensile testing machine covering a range of temperatures from —196° to 200°C using procedures described previously.6'7 In all cases crosshead speed was 0.02 in. per min. Wafers 0.015 in. thick were spark-cut from the cylindrical samples at 45 deg to the compression axes after they had been deformed to the desired strain. These specimens were then spark-planed to about 0.005 in. and then electrochemically thinned for examination by transmission electron microscopy as described in I.

Jan 1, 1969

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5'6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.' We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

By L. C. George

The Bureau of Mines measured the vapor pressures of selected mixtures in the binary systems CdCl2 ?SnCl2, CdCl2 -ZnC12, PbCl2 ?SnCl2, and PbCl2 -ZnCl2 by the static pressure method. These data were evaluated by the second-law (sigma-plot) method. Equations expressing the vapor pressures and the heats and free energies of vaporization as functions of temperature are given.

Jan 1, 1969

By E. N. Pugh, J. V. Craig

WhILE it has been established that well-defined microhardness impressions can be produced in germanium by room-temperature indentation,1-3 the role of dislocations in the process is the subject of continuing discussion.4-7 Recently, Carroll and ~anaka'

Jan 1, 1969

The authors describe two stratiform intrusions within a two miles thick ophiolite belt, one of the many ophiolite (serpentine) belts of the eugeosynclinal sequences of the Kalgoorlie System (metamorphic age c.2700 million years). Unusually good evidence of gravitational differentiation involving cumulates for an Alpine type peridotite-gabbro intrusion has been obtained, in spite of modifications of the original igneous rocks imposed by regional metamorphism. Unmetamorphosed relics of cumulate rocks are a surprising feature of this occurIfence.'fhe differentiation process reflected in the layered sequences is compared to that of the Stillwater Intrusion, Montana. Phase, cryptic and rhythmic layering are recognized. The economic significance of this study lies not only in the possibility of nickel mineralization in this ophiolite belt, but also in that much detailed information on the nature of these belts, which is difficult to obtain in the case of the more altered and sheared rocks of the belts carrying gold and nickel ore deposits nearby, is gathered from the Yilmia occurrences.

Jan 1, 1969

By Foster Fraas

This Bureau of Mines report describes a method for separating minerals at magnetic susceptibilities within the diamagnetic susceptibility range. The maximum feed rate varies directly with the square root of the lower limit of permissible susceptibility, while the lower limit of permissible susceptibility varies inversely as the square of the magnetic field strength. Minerals may be separated at particle sizes smaller than possible on conventional dry-type magnetic separators.

Jan 1, 1969

By J. A. R. Faucher

"Autogenous grinding may be an efficient and economical solution to your ore comminution problem.An important potential economic advantage of autogenous mills results from the availability of very large capacity units.Autogenous grinding could be more economical in terms of both capital and operating costs.Satisfactory pilot plant testing and thorough economic evaluation are required for a sound decision in comminution plant selection.INTRODUCTIONMankind's first weapon was probably the wooden club, but men soon learned to shape, smooth and polish stone for tools and weapons by pounding and rubbing them with sand and water. It was only about four thousand years ago that rocks were first broken to concentrate, smelt and return the metals they contained. In spite of our recent great technological advances we still break rock in essentially the same manner that was used thousands of years ago - by pounding, rubbing and squeezing - and we still waste much energy and metal in the process"

Jan 1, 1969

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By Donald M. Hausen

Microscopic evaluation of trace quantities of metalliferous phases in flotation products requires counting large numbers of particles. Particle counts of many thousands may be required for precision, but not obtained practically by conventional microscopic techniques. A less tedious microscopic method for evaluating trace sulfides in mill tailings was developed for the O'okiep Mining Company in South Africa. Hundreds of thousands of particles were evaluated by this method called "gross-counting." Gross-counting consists of counting microscopic fields rather than point-counting individual particles. Total counts are calculated by multiplying the average number of particles per field by the total number of fields examined over the entire mount. Total gross-counts range from about 20,000 particles for +200 to 100,000 or more for -400 mesh size material in lucite mounts. Sulfides and metallic particles in each field are identified and tallied along with field counts. Totals for each type of metallic particle are divided by the total gross-count to give volume percent which is corrected to weight percent by specific gravity factors.

Jan 1, 1969

By James M. Krese

The West Kentucky Division of Island Creek Coal Company, which is a wholly owned subsidiary of Occidental Petroleum Corporation, operates the new Hamilton Mine. It is located six miles West of Morganfield, Kentucky, in the Northwest section of Union County, adjacent to the Ohio River in Lock 50. On July 15, 1968, a unique new coal conveying system was put in operation. This system consists of eight conveyor units carrying coal from the bottom of the mine slope ultimately to barges on the Ohio River. It is over two miles in length and has a total of 3175 connected horsepower. The river loading conveyor is the longest 72" wide conveyor in operation in this country.

Jan 1, 1969

By Frank E. Williams

Nuclear detonation data were accumulated, studied, and evaluated by the Bureau of Mines to visualize how nuclear explosives might be used in a shale?-oil industry, The evaluation shows that the Green River Formation at the semi-isolated locale of Piceance Creek Basin, in northwestern Colorado; is thick and widespread enough to warrant consideration of nuclear mining in lieu of conventional methods, Because cost data for nuclear explosions are limited; cost comparisons are made largely by assumptions. Also described are the history of the shale-oil industry, the geology and size of oil-shale resources; and conventional mining methods and processing technology.

Jan 1, 1969

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.'5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By Francis Cameron

Gloomy predictions that domestic mineral reserves are approaching exhaustion are unwarranted and may be harmful, this author contends. Specific mineral forecasting errors in the Paley Report are cited to support this contention, and steps that can be taken to insure a progressive mineral industry capable of keeping pace with the major raw material needs of the nation through advancing technology are suggested. Mining is both exciting and rewarding —although at times somewhat frustrating— and we all can have real pride in our industry, in its people, and in its accomplishments. It is, however, with concern that I have noted a deterioration in this Country in what might be called mining's stature and in the growth of a belief in many quarters that our mineral reserves are rapidly approaching exhaustion. In other words, there is a popular image that we are fast becoming a "have not" nation in many respects and that the domestic mining industry can no longer be considered, in the vernacular of Wall Street to offer much in the way of "growth potential." I do not subscribe to this hypothesis, nor do I be-li4ve that the record of the mining industry bears this out. However, let me add that we can, in time, talk ourselves into this frame of mind and we can hasten the day when this very well might come about by unnecessary and unwise legislation or regulation. My remarks today are basically designed to give my reasons for refuting this negative philosophy and to review our record. With your help, I know we can improve our image, and the public's recognition of our industry's peculiar problems. The progress of our civilization over the centuries has been fundamentally based upon proper use of raw materials, both agricultural and mineral, and upon energy, human or otherwise. As the standard of living has progressed century by century, the demands for mineral raw materials have increased in an irregular, but steadily rising progression. Fortunately, those minerals on which we depend most, i.e., iron, coal, petroleum, copper, aluminum, lead, and zinc have been neither too difficult to find nor to process into useful form. Iron, the most useful of all metals, is present in various amounts in most rock types and soils. Gold, seemingly the most generally desired (but certainly not the most useful of all metals), occurs in sea water in a far greater total tonnage than has been won from all of the world's known gold mines. If the latter is true, then why do we not see large installations treating sea water for the recovery of its gold content? The answer, of course, is that even the French, who seem, from their recent actions, to value gold above all else, have not devised a way of doing this at a profit. Theoretically, it is possible, but not with today's technology at a cost which would justify the effort. Man has exploited only those mineral concentrations which accidents of nature have placed within his so far limited means of finding and utilizing. What we geologists and engineers refer to as an orebody is nothing more than a concentration of minerals, exploitable with available knowledge, that will yield a value greater than the value attached to the energy and capital required to produce it. What is "ore" and what is not "ore" is, in the end, a matter of economics. The economic problem stems from the physical and chemical character of mineral deposits. The good Lord stacked the cards heavily in favor of rising costs by limiting the amount of the higher grade ores easily available. As the best and most accessible ores are depleted, it becomes necessary to work harder and with greater ingenuity to produce more from less accessible and lower grade resources. The quantity of mineral raw materials we can have in the future will be determined largely by what we can afford to pay for them in terms of human effort, capital outlay and production energies. We will always have the problem of cost with us and our only real means of keeping ahead of rising costs is by continually improving our technical abilities. We, in this country at least, no longer have open to us large and unexplored virgin wildernesses in which a pick-and-shovel prospector might uncover an untouched mineral bonanza. The rest of the world also has few conventional frontiers left in which the explorer-prospector is free to roam. We do, however, have enormous land areas unexplored, and untouched po-

Jan 1, 1969

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By N. G. W., Cook

When an excavation is made underground the original rock stresses are removed from the surfaces of the excavation. These surfaces converge to partially close the excavation and the superincumbent rock mass moves down towards the excavation. If the convergence of the surfaces of the excavation were controlled, energy generated by their motion against the controlling forces could be extracted. Since the total forces in the rock mass are not significantly affected by the excavation, stress concentrations arise around the excavation, which compensate exactly for those stresses no longer transmitted through the excavation. These phenomena give rise to two general principles which provide the basis for analyzing the effects of making any underground excavation. The first of these is that the total force resulting from the stresses across any plane in the rock, including any plane through the excavation, must be the same before and after the excavation is made. The second of these is that energy must necessarily be released as a result of making an underground excavation.

Jan 1, 1969

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969