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By Lyden, Joseph P.

THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.- This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications.

Jan 1, 1950

By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By E. C. Rudolphy, M. E. Potter, J. R. Mitchell

The effects of 0.006 to 0.20 pet Sn ml the hot workability and the annealed mechanical properties were investigated for Types 302, 410, and 430 stainless steel. The hot workability of these steels was not significantly affected by their tin content within the range studied, although some effects on mechanical properties were noted. Apart from the effect of tin, optimum hot-working temperatures and V-notch Charpy impact transition temperatures for these grades were determined. HIGH tin residuals in some heats of stainless steel have been blamed for the poor hot workability, particularly during secondary mill rolling. However, very little quantitative information has been available. Previous work1"6 with carbon steels indicates that tin increases tensile strength and hardness but de- creases tensile and impact ductility. Halley,7 in reviewing the sources and effects of residual elements in carbon and alloy steels, concluded that much of the surface checking (hot shortness) encountered in rolling was caused by copper, and that tin, arsenic, and antimony combined with copper to form low-melting constituents which further increase the steel's sensitivity to hot shortness. These elements had little effect in the absence of copper. A more recent paper by Langenberg and Johnson8 concluded that tin reduces hot workability but that researchers disagree concerning the amounts which will cause trouble. They state that laboratory investigations with small ingots seem to indicate a higher tolerable level of tin than do statistical studies of mill data, and also that statistical analysis of mill data indicate that small amounts of residual tin are detrimental to the surface quality of stainless sheet. The accumulative increase in the general level of tin and other tramp elements in steelmaking materials will present greater problems to steelmakers in the future. The purpose of the present study was to obtain quantitative information on the specific effects of tin on the hot workability and mechanical properties of such common stainless steels as Types 302, 410, and 430.

Jan 1, 1962

Jan 1, 1970

By C. Chiou, M. E. Fine

While Gunier-Preston zones are growing in Al-4.2 pct Cu at room temperature, Young's modulus, measured dynamically, increases about 0.4 pct. From the change in modulus with time the exponent of time in the rate equation for growth of the zones was deduced to be %. From a comparison of the rates of increase of modulus at 1, 28, and 42°C an activation energy of 12 to 14 Kcal per mole is computed. These findings support the idea that copper atoms are supplied along dislocation channels to growing zones. In alloys the elastic constants will be functions of the distributions of the atoms. If the degree of ordering or clustering is changed, one expects a corresponding change in the elastic constants. During age-hardening of aluminum-copper alloys at room temperature, the copper atoms cluster on 100-type planes in the aluminum lattice forming

Jan 1, 1959

By Eric Jette

THE alloys of gold and iron were investigated in 1907 by Isaac and Tammann,1 who determined the thermal diagram for the entire system by thermal analysis and microscopic examination. They also reviewed the previous literature. Since that time the present authors have been able to find only two additional references. Guertler and Schulze2 examined the electrical resistance of iron alloys containing up to 40 per cent by weight of gold between 0° and 200° C.; the alloys were in the form of wires. The main result of this work was to confirm the solid solubility limit found by Isaac and Tammann; namely, about 20 per cent Au. More recently, Shih3 has examined the magnetic properties of gold alloys containing up to 10 weight per cent iron and particularly the range below 5 per cent. The alloys in the lower range were found to be paramagnetic; the 10 per cent alloy was ferromagnetic. The present investigation was undertaken to determine the solid solubility limits at various temperatures, particularly below the a-y transformation point of iron, since these solubilities are of some impor-tance in connection with the working of the alloys in the manufacture of certain "grey" and "blue" golds.

Jan 1, 1934

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strain-aging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that, wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 72o°C. The time of treatment is relatively short (about 3 hr, to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say aimost 30 per cent by volume. At this temperature. the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a verv low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,-ooo lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantiallv constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1944

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strain-aging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that, wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 72o°C. The time of treatment is relatively short (about 3 hr, to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say aimost 30 per cent by volume. At this temperature. the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a verv low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,-ooo lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantiallv constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1944

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By Wilbur I. Duvall, Thomas C. Atchison

Over the past ten years a series of investigations have been conducted to determine some of the physical processes involved in breaking rock with confined concentrated charges. Detailed discussions of many of these investigations have been published elsewhere.1-6 Laboratory experiments made by other investigators using Hopkinson pressure-bar techniques have shown that solid materials are fractured in tension by the reflection of an incident compressive stress pulse at a free surface.7-12 In these tests a small charge of explosive is placed in contact with one end of a bar. Detonation produces some plastic flow and crushing of the bar near the charge and generates a compressive stress pulse that travels along the length of the bar. At the free end of the bar the compressive stress pulse is reflected back into the bar as a tensile stress pulse. If the tensile strength of the bar is exceeded during this reflection process, a tensile fracture normal to the length of the bar is produced, and the broken end of the bar moves forward with a constant velocity equal to the average particle velocity trapped in the broken fragment. The new surface formed by the fracture becomes the new free end of the bar that reflects the remaining portion of the incident compressive stress pulse. This process is repeated any number of times until all of the incident stress pulse is reflected.

Jan 6, 1959

By J. W. Spretnak, H. R. Ogden, A. G. Imgram

The effect of working reduction, stress-relief annealing, and recrystallized grain size on the tensile and notch-tensile properties of molybdenum and Mo-0.5 Ti was studied. It was found that increasing the amount of working reduction increased the strength and reduced the tendencies toward brittle behavior. Stress -relief annealing did not alter the strength but lowered the transition temperature. Increasing the recrystallized grain size lowered the strength and raised the transition temperature. The notch -unnotch strength ratio began to decrease with decreasing temperature at temperatures below those at which the notched ductility fell to zero for all of the micro structural conditions investigated. BEING bcc metals, the refractory metals in Groups Va and VIa (V, Cb, Ta, and Cr, Mo, W) undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures. Previous research has shown that molybdenum and tungsten not only have higher transition temperatures than columbium and tantalum but show a marked sensitivity of transition temperature to structure as well.' Recrystallized materials become brittle at considerably higher temperatures than is the case with material having a worked or fibered micro-structure. Evidence of structure sensitivity has also been detected in columbium- and tantalum-base alloys containing appreciable amounts of molybdenum or tungsten such as F-48 (Cb-15W-5Mo-1Zr) and Ta-10w.2 This paper describes the results of research conducted to further evaluate the effects of metal. lurgical structure on the low-temperature tensile and notch-tensile properties of molybdenum and Mo-0.5Ti. The effects of rolling reduction, stress-relief annealing temperature, and recrystallized grain size were studied. Considerable progress has been made in explaining the fundamental mechanisms of the flow and fracture characteristics of bcc metals. Several of these concepts are helpful in interpreting the data obtained in this study. Brittle fractures occur when the highly temperature-sensitive yield strength equals, or exceeds, the temperature-insensitive brittle cleavage fracture stress.3 The rapid increase in yield strength with decreasing temperature, characteristic of all bcc metals, is therefore of primary concern. petch4 has described the yield strength, ay, (stress required to initiate plastic flow) of bcc metals by the expression where ai is the frictional resistance to slip, Ky is a constant numerically equal to the slope of a a vs curve, and 2d is the average grain diamefer. The oi term itself is thought to be composed of a temperature-insensitive component dependent on impurity content and second-phase particles and a temperature-sensitive component dependent on the Pierls-Nabarro force.5 This equation has also been demonstrated to hold for the flow stress (stress required to maintain continued plastic flow).' Brittle-crack nucleation is thought to occur by the coalescence of dislocations piled up in slip planes at sessile dislocations or twin and grain boundaries.7,8 These proposed mechanisms require that a large number of dislocations be released into the active slip planes so that sufficiently large stress concentrations are produced at the dislocation pile-ups to enable coalescence into a micro-crack. Therefore, at least a microscopic amount of slip must occur in some grains to facilitate initial crack formation. Cottrell 7 has predicted that brittle fracture, nucleated by slip, should occur when where ty is the shear yield strength, ß = 1 in un- notched xension, u is the shear modulus, and y is the effective surface energy. This equation incorporates the Griffith concept of fracture that a crack will propagate if the decrease in strain energy equals or exceeds the increase in surface energy.

Jan 1, 1964

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal effect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24S-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to intercrystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot be accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. REVIEW OF PREVIOUS WORK In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknall1 demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K. 10m/T (I) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-Q/RT (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver- rich copper alloy2 and of duralumin. 3

Jan 1, 1945

By S. K. Nowak

The lithium solubility limit in solid aluminum was determined by the use of micro-graphic techniques. The solubility limit thus established was shown to be a true equilibrium by checking the reversibility of AlLi phase precipitation and dissolution around the equilibrium temperature. The experimental results fit a straight line by plotting log N(LI) against 1/T. The metallurgical reasons explaining the lack of agreement among previous investigations are discussed. THE solubility limit of lithium in solid aluminum was determined by Shamray and Saldau1 by micrography and by Grube et al.' and also Voss-Kiihler- by measurement of electrical resistivity. Since the addition of lithium induces extremely small changes in the aluminum lattice, X-ray techniques could not be employed for this purpose; in fact, the addition of lithium does not cause an expansion of the lattice as might be expected from a consideration of atomic radii, but causes a small contraction from 4.040 to 4.037A3, 4 when the solvent aluminum is saturated with this element. An analysis of the results from previous investiga-tions'" shows that with improvement of investigation techniques the solubility limit tends toward a lower lithium content. Again, some of the author's own experimental results on the action of atomic hydrogen on A1-Li alloys seemed to indicate that the solubility of lithium should be much lower, i.e., about 0.3 pet at 300°C: instead of 1.15 pet, the lowest published value.4 For the foregoing reasons it was decided to investigate this problem. The aluminum and the lithium used for this purpose were of the highest purity. The lithium solubility limit was determined by metallographic techniques, in particular by the use of a reagent especially developed for the purpose of revealing the AlLi phase. The solubility limit thus determined was shown to be a true equilibrium by checking the reversibility of AlLi phase dissolution and precipitation around the equilibrium temperature. All of the experimental work was carried out in 1951 at the Centre d'Etudes de Chimie Metallur-gique at Vitry, France, under the direction of Georges Chaudron.

Jan 1, 1957

By L. H. Cadoff, L. M. Adelsberg

The layer growth method has been used to investigate the reaction kinetics of liquid titanium and hafnium with carbon and the [liq] - [liq + TiC] and [liq] - [liq + HfC] phase boundaries at temperatures above 1800°C. The equipment and experimental procedures used in this investigation are basically identical to those described in an earlier paper' on the Zr-C reaction. Temperature control, however, was improved significantly by connecting a Latronics Colo-Ratio automatic pyrometer and a controller to the power source. The subsequent temperature variations were ±10°C; previously ±20°C was obtained using manual controls. The absolute accuracy of the pyrometer, however, must be considered to be only ±40°C.* The spectrographic analyses of the materials used in this study are listed in Table I. The isothermal reactions of titanium (1800° to 2700°C) and hafnium (2300" to 3000°C) with carbon (graphite crucibles) resulted in the formation of carbon-saturated liquid metal and layers of Tic and HfC, respectively. The thicknesses of the carbide layers, determined from metallographic measurements at 100 times, as a function of carburization time and temperature are given in Figs. 1 and 2. At each temperature, parabolic growth behavior for these reactions was observed and could be expressed as x2 =Kpt, where X is scale thickness (corrected for heating and coolingL), Kp the parabolic growth constant, and t the isothermal carburization time. Values of Kp as a function of temperature for the carbides are shown in Fig. 3 and listed in Table 11. The growth constants are expressible as: kpTiC = 0.2 exp(-61,800/RT) sq cm per sec for Tic and Kp HfC = 2.62 exp(-95,300/RT) sq cm per sec for HfC. The liquidus phase boundaries were determined from metal samples treated in graphite crucibles for different times ranging from 4 to 100 min at each of the temperatures indicated in Table 11. Metallographic examination revealed that the carbide precipitates were distributed uniformly throughout the frozen metal matrices. This is attributed to the rapid cooling rates (800°C per min) and the small difference in density between the precipitated carbide and the liquid metal.

Jan 1, 1968

By Alfred E. Hunt

Professor EGGERTZ first published a method based upon the fact that, when steel is dissolved in dilute nitric acid, and heated until the separated flocculent carbonaceous matter goes into the solution, the liquid assomed a brown color proportionate in intensity to the amount of the combined carbon in the steel. This method has been so variously modified that at present but few chemists use exactly the same procedure. It is the object of this paper to present

Jan 1, 1884

By Stephen Taber

A vein may be defined as an aggregation of mineral matter, more or less tabular or lenticular in form, which was deposited from solution and is of later origin than the inclosing rock. This definition differs from the one found in many text-books in that no assumption is made as to the origin of the space occupied by the vein or the manner in which the mineral matter was deposited. In the present paper the writer purposes to discuss the mechanics of vein formation, and does not wish to begin by begging the question. The origin of ore deposits has been diligently investigated in recent years, but, while much has been written concerning the chemistry of the process, the physical side of the question has received less attention. The source of the ore minerals; the chemical composition of ore-bearing solutions; the relative importance of magmatic and meteoric waters as agents of concentration; and the causes of mineral precipitation have all been discussed at length. On the other hand, little has been written concerning the mechanics of vein formation, and the theories given in text-books today are essentially the same as those developed by the early Cornish and Saxon miners. Early investigators often regarded both veins and dikes as igneous in origin, but today the theory that vein minerals have been deposited from solutions, either liquid or gaseous, is firmly established. The latter view is supported by the fact that many vein-forming minerals are not found in unaltered igneous rocks; by evidence obtained in the laboratory regarding the solubility of minerals; by the presence of many ore minerals in hot-spring waters; by the occurrence of some veins in regions consisting exclusively of unaltered sedimentary rocks; by evidence as to the temperature at which some minerals are formed; and by the absence of mineral segregation due to difference in specific gravity. There is still, however, much difference of opinion as to whether certain tabular-shaped masses should be classed as veins or as dikes. Some of the earlier investigators have also advocated the theory that veins are contemporaneous in origin with the inclosing rock, while others have believed the vein minerals to represent a recrystallization or transforma-

Jan 1, 1920

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,' a pure metal and its vapor,' and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By Louis A. Carapella, Ralph Hultgren

WHEN F. Heusler1 found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.3 All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys" the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intelligently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. PREVIOUS WORK In the original work of F. Heusler1 and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for Cu2MnA1 of I = 443 was early measured. Ross and Grays found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 then reinvestigated the system, confirmed their results,

Jan 1, 1941

By Frank H. Riddle, Wilfrid R. Foster

GENERAL treatment of the various minerals of importance in refractories appears in the chapter entitled "Refractories" elsewhere in this volume. The present chapter is restricted to a discussion of minerals of the sillimanite group and brings up to date the excellent information contributed by Prof. Paul F. Kerr to the first edition (1937). Since the appearance of that edition, the status of the group has changed some- what. Kyanite remains the preferred source material for mullite refractories but total consumption of kyanite has increased considerably.85 The exigencies of World War II forced an increased dependence on domestic sources and led to an intensification of the search for higher-grade deposits of kyanite and allied minerals. The first discovery of massive kyanite similar to that of India has been reported from Georgia.37 British East Africa has joined India as a substantial supplier of our imported kyanite, but that from India continues to hold preference.85 During World War II, prices of both domestic and foreign grades reached peaks unparalleled since the earliest years of the use of kyanite and as yet have shown no tendency to return to prewar levels. Topaz, by virtue of the deposit outlined in South Carolina, merits inclusion in the group.20,36,95 Large andalusite deposits, which threaten to rival our one large domestic occurrence, have been found in Russia.69,88 Sillimanite has not yet attained an important position among these useful minerals because of the lack of accessible deposits of high-quality material in adequate supply.37,50,58 Tests by the Bureau of Mines have indicated the possibilities of economically beneficiating low-grade sillimanite and kyanite.105.106,140 Government, university, and industrial

Jan 1, 1949

By Charles Barrett

THE orientation of metal crystals and grains, both large and small,. can be determined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satis-factory in the laboratory the reflection of light from crystallographic etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographic projection is used to facilitate handling the data, this note may be considered as an appendix to an earlier review of the metallurgical uses of the stereographic projection.1 Various methods involving etch pits have been used by other investi-gators, Bridgman's method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4), holding it at arm's length, and marking a spot on it when it has been turned so that the etch pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2° and is extremely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czoehralski, 5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers"' developed a method for estimating the number of grains in a polycrystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and recrystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereo-

Jan 1, 1940