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By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

University or College Society President Secretary Alabama, University of University. Ala Mining and Metallurgical Society Warren G. Payne Melbon J. Langley Alaska Agr. College and School of Mines, College, Alaska Alaska Mining Society Robert McCombe Robert Mize Arizona, University of, Tucson, Aria Miners' Society Frank Bacon Charles V.' Harris California University of, Berkeley, Cal...: Students Mining Association C. F. Bedford J. R. Hollcraft, Jr. Came is Inst. of Technology, Pittsburgh, Pa The Miners and Metallurgists Society Richard M. Barnhart Jack E. Morris Case School of Applied Science, Cleveland, Ohio Pick and Shovel Club R. H. Randolph W. B. Scott Colorado School of Mines, Golden, Colo Student Branch of A. I. M. E, Donald Peaker T. H. Evans Jones Harvard University, Cambridge, Mass Geological Club H. E. Quinn Lincoln Thiesmeyer Idaho, University of, Moscow, Idaho Associated Miners John T. Carpenter Robert D. Baily Illinois, University of Urbane, Ill Mining Society H. M. Adams R. M. Sherer' Kansas University of, Lawrence, Kane : Student Branch of the A.I.M.E. Henry Gould Everett Stidham Kentucky, University of, Lexington, Ky : Norwood Mining and Metallurgical John D. Lancaster James A. Purnell

Jan 1, 1929

Preamble At the present time many bodies are engaged in -the formulation of standards. There is no uniformity in the rules for such procedure in the different organizations; in some cases the committees engaged in the work are not fully representative, and in. a considerable proportion of cases they do not consult all of the allied interests. The present custom results in a considerable duplication of work, and in some fields several "standards" are proposed for the same thing, differing from one another only slightly and often in unimportant details. It is very much more difficult to obtain agreement between the proposers of overlapping standards after they have been published than it would be to get the proposers to agree before they had committed themselves publicly. The American Institute of Electrical Engineers, the American Institute of Mining Engineers, the American Society of Civil Engineers, the American Society of Mechanical Engineers, and the American Society for Testing Materials have appointed a committee to consider the advisability of cooperating in engineering standardization. This committee recommends that these societies form a permanent organization by appointing a committee as proposed in the following constitution and rules of procedure to carry on this very important work.

Jan 3, 1918

By John K. Hammes, Stanley D. Michaelson

Generally, the mining costs reported for the large open-pit operations in the United States and South America lie within the range of $0.20 to $0.30 per ton of material moved. (These operations have strip- ping ratios ranging from 1.5 to 4.0.) Productivities for the larger North American properties are in excess of 200 tons of material per man shift, while those for the South American operations are less than 200 tons per man shift. The most significant variations in cost are in the categories of haulage and general mine cost. Haulage costs vary, as expected, according to the mine elevation, pit profile, crusher location, and accessibility of a dump area, and general cost variations depend largely on the overhead cost items included in this category. Drilling and Blasting Practice The majority of open-pit copper mine production drilling is performed by rotary drills. Hole diameter varies from 6 in. to 12 in., with 9-in. holes being most common, and penetration rates vary from 35 ft to 60 ft per hour.

Jan 1, 1968

By R. Costantini

Long-distance transportation of solids by hydraulic pipelines holds promise of great economic benefits. In most mineral processing plants today, moving of solids in slurry-form by pipeline is commonplace. Yet in spite of this, the method is slow in being adopted on a broad scale for moving solids over distances of many miles. This is especially surprising in view of the successful realization of two daring ventures in long-distance solids pipelines in this nation within the last five years. One is the 72-mile long, 6-in. diam. pipeline of the American Gilsonite Co. which has been satisfactorily transporting 700 tpd of gilsonite from the mine at Bonanza, Utah, to the processing plant at Grand Junction, Colo., since April 1957. The other is the 108-mile long, 10-in. pipeline of the Pittsburgh Consolidation Coal Co., which has been transporting about 4000 tpd of finely crushed coal from the mine at Cadiz, Ohio, to the Eastlake Power Plant of the Cleveland Electric Illuminating Co. since January 1958.

Jan 8, 1961

By C. H. Curtis

The Esperanza mine of the Copper Division of Duval Sulphur & Potash Co. is located in the Twin Buttes District, 32 miles southwest of Tucson, Ariz. Records of mining activity in this vicinity date back to the 1850's. The New Year's Eve mine, which was last active briefly during the years of World War II, made the first actual penetration into what is now Duval's Esperanza property. Duval's exploration department became interested in the Esperanza in the fall of 1954. The first test hole was started on May 8, 1955. Two years of intensive exploration work together with metallurgical studies developed the basis for the decision to establish an operation.

Jan 11, 1961

By F. H. Willcox

THE CHAIRMAN (HENRY D. HIBBARD, Plainfield, N. J.).-This paper is timely because of the changed conditions due to the great war, but apparently its scope is limited to oxidation process steels. Referring to the four numbered observations on page 199: No. 1 seems to ignore Johnson's discoveries about oxygen in cast iron. No. 2 ignores crucible steel. No. 3 ignores red short steel containing enough gas solvents to make it solid, while No. 4 assumes that a deoxidizer is necessarily a gas decomposer or solvent and vice versa, which it not always is. From these observations it is deduced. that the only hole-forming gas in steel is an oxide of carbon (CO presumably is meant), which is not true.

Jan 4, 1917

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By R. L. Tobie, E. K. Staley

Because of high production demands at San Manuel mine (approximately 40,000 tpd) and the relatively narrow grade range of the orebody, no attempt is made by the company to mine selectively. The caving sequence is laid out to meet the production demands, and proceeds in a manner to induce the least amount of weight on extraction openings. Once an area is undercut, draw control procedures are applied uniformly until the area has been mined to depletion. The orebody, located 50 miles northeast of Tucsoil, Ariz., is a low-grade deposit of chalcopyrite disseminated throughout a structurally weak, highly fractured, strongly altered granitic host rock over- lain by several hundred feet of relatively competent andesitic conglomerate. When undercut, the granite ore caves readily into fragments which usually pass through the grizzly without either excessive breaking or an undue amount of secondary blasting.

Jan 6, 1967

[ PRESIDENTS DAVID THOMAS 1871 'R. W. RAYMOND 1872-1874 'A L. HOLLEY 1875 'ABRAM S. HEWITT 1876 'T. STERRY HUNT 1877 'ECKLEY B. COXE 1878-1879 'WILLIAM P. SHINNY 1880 'WILLIAM METCALF 1881 'RICHARD P. ROTHWELL 1882 'ROBERT W. HUNT 1883 'JAMES C. BAYLES 1884-1885 ROBERT H. RICHARDS 1886 'THOMAS EGLESTON 1887 'WILLIAM B. POTTER 1888 'RICHARD PEARCE 1889 'ABRAM S. HEWITT 1890 'JOHN BIRKINBINE 1891-1892 'H. M. Hows 1893 'JOHN FRITZ 1894 'J. D. WEEKS 1895 'E. G. SPILSBURY 1896 'THOMAS M. DROWN 1897 'CHARLES KIRCHHOFF 1898 'JAMES DOUGLAS 1899-1900 'E. E. OLCOTT 1901-1902 'ALBERT R. LEDOUX 1903 'JAMES GAYLEY 1904-1905 'ROBERT W. HUNT 1906 'JOHN HAYS HAMMOND 1907-1908 'D. W. BRUNTON 1909-1910 'CHARLES KIRCHHOFF 1911]

Jan 1, 1940

By John Tyssowski

IN 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temper-atures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several parti-cles had become one unit. From this dis-covery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the appli-cation of about 30c0 tons pressure on a 10-in. piston. Stout decided that cathode copper pro-duced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H, Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles.

Jan 1, 1940

By Uros Bajzelj

To mine very weak carboniferous schists subjected to high ground pressures the underhand cut-and-fill stoping method was proposed using an artificial plate roof. An experimental stope was mined using three consecutive levels. Rock pressures, deformation of the reinforced concrete plate, and the quality of stowing were evaluated. It was found that roof deformations were minimized if the reinforced concrete plate and uncemented backfill were replaced with cemented backfill containing reinforcement near the bottom. The mining method prevented the occurrence of high rock pressures at the face. The method is suitable for mining subvertical ore bodies with large horizontal areas.

Jan 1, 1984

ALABAMA Altoona.-Cain, J. America.-Foreman, J. T. Anniston.-Cowie, L. K. Foster, R. N. Ashland.-Sturdevant, J C Bessemer.-Ball, E. M. McKenzie, W. C., Jr Birmingham.-Abbott, C. E. Aldrich, T. H. Aldrich, T. H, Jr. Ashton, J J. Ball, T. L. Blair, C. S. Brown, T S. Bush, M. W.

Jan 1, 1923

By O&apos, R. G. Meara, M. M. Fine

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By M. M. Fine, R. G. Meara, O&apos

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

Executive J V W. REYNDERS, Chairman WILLIAM H. BASSETT E DEGOLYER H C BELLINGER RICHARD PETERS. JR. Finance H. A. GUESS GEORGE OTIS SMITH, Chairman F. JULIUS FONS Admissions GEORGE D. BARRON, Chairman DAVID LEVINGER P. A MOSMAN El K MASTERS J. A. SINGMASTIIR Alternates F. G. BREYER C W HAMILTON F. E PIERCE

Jan 1, 1923

By M. N. Dunlap

Tries article summarizes the successful incorporation of a flash-flooding stream into the tailing-disposal system at the St. Joseph Lead Company's Federal Division mill, in St. Francois County, Missouri. The mill was built in 1906, by the Federal Lead Co., as its No. 3 mill for the concentration of southeastern Missouri lead ores, and damming Davis Creek was first considered in 1908. Plans were made also in 1925 and in 1937. Dam layouts varied from a reinforced concrete structure to a barrier built of tailings alone. All were abandoned because of liability that would be incurred by flashflood rupturing of an incompleted dam. By 1942 mill capacity had reached 12,000 tons daily and increasing tailing-disposal costs again focused attention on the Davis Creek basin. This time the problem of riskless dam building was solved. Moreover, most of the items that appeared in the answer were materials that normally required wasting and the major portion of labor involved performed functions that it would normally have done, without constructive benefit, elsewhere. The new layout also made possible advantageous changes in mill-water supply pumping; static head being reduced from 514 ft to 95 ft, friction head from 4900 ft to 2860 ft, and pumping can be done now at periods of low power demand. The following facts about the Davis Creek watershed explain the 36-year reluctance to reach these, and other, benefits. Size: 3600 acres. Outline: roughly pear-shaped, 2 1/2 by 3 miles at the largest dimensions. Topography: mostly hill land with steep valleys. Relief : 760 minimum to 1153 maximum. Maximum rainfall: 3.36 in. per hour. Permanent water: none natural. Now 2200 gpm discharged through 16-in. drill hole from mine pumps underground. Geology: the 17 acres near dam centerline is Bonne Terre dolomite covered with sand and gravel eroded from Pleistocene beds that cap some of the hills. The remainder of the pond basin is on Davis shale. Soil cover: mostly second-growth timber with some abandoned fields; all subject to careless burning, which reduces water-retaining ability. Flood history: flash-flooding that had taken at least one life. Downstream values: two railroad bridges before creek intersection with Flat River. Immediately below confluence, a highway bridge, a low-water crossing, a few business establishments and several blocks of residences. In July 1942 the following segments of an ingenious plan were put into operation. A ditch 270 ft long, 16 ft wide and 5 1/2 ft deep was excavated to bedrock in the gravelly soil along the proposed dam's centerline. This excavation, which exposed many gravel-filled channels, was run full of slimes drawn from a riser set in the top of an adjacent tailings-disposal

Jan 1, 1947

By William M. Brewer

Until quite recently, in fact within the past two gears, but little attention has been given to the outcrops on the west coast of Vancouver Island, and their copper-contents. During the past few months the writer has been engaged in examining and developing some of these prospects. In many respects he has found characteristics associated with these prospects which, in his experience, are unique. In the first place, nearly all the outcroppings which overlie chalcopyrite-ore along the west coast of the island are composed of a high-grade magnetite. The magnetic qualities of some of these outcrops arc so pronounced that the magnetite possesses polarity. Although the writer hinlsclf had no analyses of this magnetite made, yet from its appearance he can readily believe that analyses made for other parties, which show a yield' of 62 or 63 per cent. of metallic iron, with only traces of phosphorus and silica, are correct. At a very shallow depth, masses of chalcopyrite, yielding in some instances as high as 32.6 per cent. of copper, occur associated with the magnetite; and in one instance, which recently came under the writer's observation, a solid body of high-grade chalcopyrite, fully 4 feet in thickness, occurs Within 6 feet of ; the surface. Usually this solid sulphide-ore carries low values in gold. Probably ail average of' $2 per toil would be fairly representative. But in some instances development has determined the occurrence of narrow stringers of pyritous quartz, associated with the sulphide-ores, which yield by assay more than $20 per ton in gold. In the districts examined by the writer, the country-rock is usually crystalline limestone, with dikes of igneous rock as intrusions. Sometimes the outcrops of magnetic iron-ore are

Jan 1, 1900

By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969

By Harry M. Mikami, Harold A. Heiligman

The term chromite is often used to cover all chrome ores and concentrates which are the designations actually employed by most industrial users and producers. Chromite is, of course, the predominant mineral in chrome ores which are aggregates of chromite and gangue minerals, most commonly magnesian silicates. Most chrome ores now used are petrographically chromitites which is a rock, rather than an individual mineral term. The title of this chapter, following past usage, is meant in the broad sense. Chromite is the only primary commercial source of chromium. This book is intended to deal only with nonmetallic minerals and rocks. Chromite uses are both metallic (ferroalloys) and nonmetallic (refractories and chemicals), but any discussion of mineralogy, geology, and mining is common for all types. A number of the major commercial ores are interchangeable, and their uses are determined by economic considerations. Mineralogy COMPOSITION [Chromite is a term embracing a wide range of chromium-bearing spinel*-group minerals the compositions of which can be expressed as (Mg,Fe2+)0.(Cr,AI,Fe3+ )203.t This can be further generalized to R2+O.R23+03 and the molecular RO: R,03 ratio is generally close to one. The exact composition may be arbitrarily expressed as a solid solution of six end-members, MgAI2O4, MgCr2O4, MgFe2O4 FeCr2O4, FeA12O4, and Fe2+.Fe23+04 with the proportions of each stated or plotted in the six-cornered prism of Johnston and Stevens61 or this scheme may be simplified to comprise only three endmembers making up a composition triangle, Fig 1. [ ] FIG 1-Triaxial composition diagram showing molecular compositions of chromites listed in Table 1. The RO.Fe2O3 corner includes Ti02 norms listed in the table. Note that the high-alumina chromites (1, 2, 3, 9), form a cluster well apart from the high-Cr2O3 chromites. There is a tendency for high-iron chromites to be higher in Fe2O3 + TiO2 but it is not a consistent or systematic relationship. The MgO/RO ratio must also be known to characterize the chromite chemically. Simplest and most convenient method is Thayer&apos;s&apos; in which a chromite such as (Mg.65Fe.352+)O.(Cr.40Al.50Fe.103+)203 would be written as (Mge,) Cr eAlo. The molecular pro- portions of ferrous and ferric oxides can be seen at a glance as the divalent and trivalent oxides]

Jan 1, 1960