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By Donald V. Fites

In the face of an increasing demand for minerals, the resulting technological developments, and rising overburden-to-ore ratios, many open-pit mines now incorporate totally different concepts for the removal of ore and overburden. Moreover, under a growing number of these concepts, wheel tractor scrapers are being assigned a major role in material- handling systems for unconsolidated overburden removal. To say that scrapers move only unconsolidated overburden is incorrect. On the contrary, ripped phosphate rock, copper ore, iron ore, and moderately consolidated overburden are also being moved by scrapers in various areas of the world. According to the Minerals Yearbook, about one half of the material moved in metal and nonmetal mines is never drilled, blasted or broken by other means. Scrapers Find Wider Application The increased use of scrapers in open-pit mining today is due in part to improved design which has endowed these units with added versatility and in- creased their production capability. The modern scraper, which is designed as a loading and hauling vehicle, cannot be compared to the original tractor- drawn scrapers which were limited in capacity, maneuverability, and speed. Improved design of the scraper bowl ejection system has aided production. Gravity ejection has been replaced with positive, forced ejection of material by hydraulic or mechanical action. Bowl and cutting-edge design which allows for maximum load with minimum effort has also increased production. An example of this was the introduction some years ago of the low-silhouette scraper bowl which reduced the work required to lift the material.

Jan 5, 1969

By John M. Dale

As much as half of the world's known reserves of elemental sulfur occur at or near the earth's surface in natural or native sulfur deposits of volcanic or sedimentary origin. Yet these reserves constitute only a small percentage of the world's supply. Looked on as marginal materials, they remain relatively untouched despite the current demand and improved prices for sulfur. There are two main reasons for this. The first is the nature and occurrence of the deposits. They are generally small and widely scattered in remote and often arid locations, and the gangue constituents of the ore are apt to vary considerably-not only between deposits but also within deposits. The second reason is the lack of workable and economically feasible processes for recovering sulfur from the ores in such deposits. Historically, the older thermal processes in which the sulfur is vaporized away from the gangue were probably the most successful, but they were inefficient and created pollution problems. A few of the historical processes remain in operation today. Recently, however, an improved thermal process to handle all sulfur-containing surface ores has been designed under sponsorship of the Pan American Sulfur Co. A schematic diagram of this process is shown in Fig. 1. The process equipment consists of a paddle trough conveyor retort which is operated as a closed unit to prevent any air or oxygen from entering the system. Ground surface sulfur ore and heated pebbles are fed to this unit simultaneously. The ore and heated pebbles are slowly conveyed and continuously mixed down the conveyor retort. Heat from the pebbles and heat supplied to the outside walls of the trough conveyor retort raise the ore temperature above the boiling point of sulfur. Sulfur vapors and steam originating from moisture in the ore are ducted to a condenser, and the sulfur is recovered as a liquid. The gangue and the pebbles are discharged from the trough conveyor and separated-the gangue being discarded, and the pebbles being conveyed to a direct-fired rotary pebble heater where they are reheated before they are again charged into the rotary trough conveyor retort. The hot gases which pass countercurrent to the pebbles are ducted to the outside of the rotary trough conveyor where they pass countercurrent to the flow of the ore in order to maximize heat recovery and utilization.

Jan 4, 1969

By Robert R. French

Beneficiation of low-grade nonmetalliferous mineral deposits by electronic color sorting is currently undergoing a period of rapid development. For those deposits in which the specific gravity, strength, soundness, and electric and magnetic properties of the ore and gangue are similar, the possibility of separation by color, reflectivity, or fluorescence offers hope for the utilization of much poorer quality ore than previously thought possible. For those ores in which consistency of color is required or for which a dry process is preferred, the electronic color sorter is particularly adaptable. Tests performed late in 1966 and reported herein are the result of the continued interest in the dry beneficiation of gypsum and the development of higher capacity color sorting machines. The ore used was a discarded fraction that consisted of – 1 ¼ -in, to + 3/8 -in. ore containing 63.1 to 71.4% (average 67.7%) gypsum. This material was contaminated by various amounts of both carbonate rock and shale, but no pretreatment was performed other than screening to closer size limits before electronic color sorting.

Jan 4, 1969

Rustenburg Platinum Mines, Ltd. is the largest producer of platinum metals in the western world. It is also the only major platinum producer this side of the Iron Curtain. One of its mines is situated at Rustenburg, 80 miles northwest of Johannesburg. It also has a smaller operation, the Union Section, 60 miles north of the Rustenburg property. Both mines exploit the Merensky Reef, which forms a part of the Transvaal's remarkable Bushveld Igneous Complex, an irregular oval area covering some 15,000 square miles. In order to cope with an increasing world demand for platinum and such platinum-group metals as palladium, rhodium, ruthenium, iridium and osmium, Rustenburg Platinum Mines embarked on a major expansion program some time ago. It is expected that production will reach an annual rate of 850,000 oz of platinum by the middle of 1969 and increase to 1 million oz by the middle of 1970. Capital expenditures at Rustenburg during the next few years will be about $60 million. It is believed that the ore at Rustenburg averages about 4.5 oz of precious metals per ton. About 70% of the metal is platinum, some 15% is palladium, and the rest is made up of the other metals in the platinum group.

Jan 4, 1969

By John V. Beall

There is an underlying surge to mining in the Philippines." So said A. R. "Ham" Reed, general manager Itogon-Suyoc Mines, Inc., to this reporter last November. Itogon-Suyoc is a small company with a struggling gold mine, a mixed sulfide mine and some prospects. In the Republic of Philippines (ROP), politics, which have an effect on mining, create some uncertainties. By July 1974, no mining company may have more than 40% foreign ownership. The ownership provision is a matter of concern to such important companies as Atlas and Benguet Consolidated and is generally considered a deterrent to new foreign investment. Under these circumstances, Reed's comments are of interest. On foreign prospectors: Don't come in cold; find a Philippine partner or buy into a company already here. Physical conditions of exploration are tough-terrain, communications -but the mineral potential is excellent.

Jan 4, 1969

By C. D. Michaelson

The memory of D. C. Jackling serves chiefly to remind us how much we owe to the pioneers of our industry. Jackling was one of the giants. Orphaned at the age of two, he made his way through sheer persistence and plain hard work. His brilliance gave rise to a vision, and his tenacity made his vision a reality. Foreseeing that economies of scale would make the handling of low-grade ore profitable, he introduced the revolutionary concept of open-pit copper mining. During World War I, the defense effort of the United States was immeasurably strengthened by the tremendous supplies of copper from the western mines that Jackling had made possible. Again in World War II, the demands for copper were supplied, and the nation once more had profound reason to be grateful to this rugged, stubborn man who had long ago ventured into the mountains and unlocked their wealth. We are now embarked upon another great era of change, and we must devise new concepts to meet it. The task is not only to create new techniques of mining, but to forge better ties between men and institutions which will let us work in harmony with the techniques we have. We might recall that while Jackling was a man of towering pride and formidable will, he was also adept at getting others to share his vision and join his purpose. Today our reach for cooperative endeavor must go far beyond our own shores as we seek to develop the buried riches of distant lands. And we would do well to remember that Jackling's remarkable insight would have come to nothing had not British investors been willing to provide much of the initial capital. As was true of so many early enterprises in America, European capital was absolutely essential.

Jan 4, 1969

By I. R. Taylor

Union Carbide has recently developed two open- pit vanadium mines in the Wilson Srpings area of central Arkansas about five miles southeast of Hot Springs. The ores from these mines, together with those from a larger vanadium deposit at nearby Magnet Cove, are processed at a new 1600- tpd plant built by the company in the immediate vicinity (Fig. 1). The Wilson Springs vanadium deposits are associated with the Potash Sulfur Springs intrusive, a circular igneous complex which is exposed over an area that is somewhat less than a mile in diameter.1 The complex has a crude ring structure similar to that of the larger Magnet Cove instrusive six miles to the east.2

Jan 4, 1969

By R. A. MacGregor

The Stanrock mine of Stanrock Uranium Mines Ltd. is located on Quirke Lake in the Elliot Lake area of northern Ontario, about 25 miles north of Lake Huron. The property was developed and brought into production at a rate of 3000 tons of ore per day during the uranium boom of the mid-1950's. The mine workings are from 1200 to 2100 ft below sea level. Mining was done by the room-and-pillar method with 65 to 80% extraction. The plant is located at an elevation of 1400 ft above sea level. The orebodies are conglomeratic beds, 6 to 40 ft in thickness and dipping 5º to 40º. The ore is a quartz pebble conglomerate with a pyritized sericitic matrix. The ore minerals are brannerite, frequently intergrown with anatase or rutile, uraninite, and some monazite and minor coffinite and thucolite. Sulfides constitute 5 to 10% of the ore as pyrite with minor amounts of pyrrhotite, chalcopyrite and galena.

Jan 3, 1969

By Gill Montgomery

The strong upward curve of fluorspar consumption continued through 1968, with domestic producers unable to furnish more than 30% of U.S. requirements. Stocks of all grades were quite short at all points during most of 1968. This resulted in price increases as both domestic and foreign producers sought to cover spiralling labor costs. Further increases are probable for 1969. All Illinois mines were closed by strikes in January and February. The strong trend in metallurgical imports reflects the increased use of fluorspar in steelmaking, as new oxygen process steel plants come into production. The growth of use of all fluorocarbon chemicals continues to require additional acid grade fluorspar, with military uses a major factor. Several new aluminum smelting facilities coming into production are adding to the aluminum fluoride needs, bringing further pressure upon the world supply of acid grade fluorspar. The world-wide consumption pressure on all grades of fluorspar is pushing prices up, and no end to the tight supply is in sight, even assuming that all the new projects cited here are finished on schedule.

Jan 3, 1969

By A. B. Fly

Borehole mining combines the principles of hydraulic mining, slurry mucking and rotary drilling. The borehole is drilled with conventional equipment and is cased down to the top of the mining zone. The borehole mining tool is comprised of the kelly-swivel assembly, multiple drill-pipe sections, and the jet-pump barrel assembly as shown in Fig. 1. The kelly swivel is fitted with a bail to support the mining tool. The kelly drive bushing engages the rotary table to allow the rotation of the mining tool while it is being operated. The jet-pump barrel assembly is comprised of the sidewall jet nozzles, the jet-pump assembly, the suction screen, and the tricone rock bit. Clean fluid is pumped at high pressure through the kelly hose to the high-pressure swivel on the mining tool. The high-pressure pipe conducts the fluid down to the sidewall jet nozzles, the pump jet nozzle, and the tricone rock bit. The sidewall jet streams cut the formation and wash the cuttings down to the rock bit. High-pressure fluid issues from the water courses to clean the bit and to agitate the cuttings. Rotation of the mining tool causes the rock bit to grind any oversize material enough to permit its passage through the suction screen. High- pressure fluid issues from the pump jet nozzle to provide the lift needed to pump the slurry to the surface. The slurry is discharged into the settling pits where the cuttings are deposited and the clean fluid is returned to the suction of the high-pressure pump.

Jan 3, 1969

By A. J. Fenn

Long experience with underground mining inspired the unusual idea of using an underground crusher-conveyor system as a substitute for surface haulage at the Cananea open-pit copper mine in Sonora, Mexico. Now implemented and working well, the system has born out the expectations of its originator, Cia. Minera de Cananea S.A. de C.V., that it would effect substantial cuts in the high cost of haulage. The Cananea deposit is a large, low-grade orebody above the mined-out Colorada pipe which was once one of the largest high-grade underground deposits in the district. Present facilities at the pit consist of: (1) A large open-pit mine capable of moving 80,000 tons of material per day with a shovel-truck, underground crusher and belt conveyor haulage system. (2) A 25,000-tpd concentrator equipped for four stages of crushing, rod mill-ball mill grinding with cyclone classification, and flotation in conventional machines. (3) A dump leaching process producing 1 million lb of copper per month in a tin-can scrap precipitation plant. (4) A two-reverberatory, six-converter smelter which can make 140 tons of blister copper per day. (5) A well-integrated contingent of supporting departments running the gauntlet from housing to power generation.

Jan 3, 1969

By R. Havens, K. C. Dean, H. Dolezal

Mine, mill, and smelter wastes aggregating billions of tons are scattered across the country as unattractive barren piles that mar the natural beauty of the land. As the population of the United States increases and the demand for land intensifies, populous centers are slowly encroaching on these formerly isolated wastes. Encroachment sharply intensifies the importance of controlling the air and water pollution derived from natural weathering of such wastes. Use or stabilization of these wastes comprises the only viable means for minimizing pollution. Utilization is preferable to stabilization, because full use would both eliminate the waste and broaden the mineral resource base. However, the wastes typically comprise immense tonnages of materials discarded by selective mining or after recovering the significant mineral values by milling and/or smelting. Only rarely can such low-grade material be reprocessed to extract additional minerals at a profit. Some mineral wastes are suitable for disposal as mine fill, railroad and highway road ballast, and land fill. Similarly, some mineral wastes can be utilized as raw materials for making brick, rock wool, concrete, and ceramic products. Several means exist for stabilization of relatively fine-sized wastes, which constitute the chief sources of air and water pollution. These include physical, chemical, and vegetative stabilization, and combinations thereof. Massive coverings of coarse slag, concrete, and soil may be used to prevent erosion of waste piles. A variety of chemicals can be used to bond the particles of fine-size waste into a relatively inert mass. However, the most promising method of producing an esthetically appealing storage site is vegetative stabilization. Numerous species of plants can germinate, grow, and reseed in waste materials which have been adequately prepared to support plant life.

Jan 3, 1969

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Jan 2, 1969

By Robert L. Frantz

Progress and improvement continue to be the bywords of a dynamic coal industry. The industry continues to gain strength and expand its horizons in the face of competition from atomic energy and the problems of restrictive legislation. The direct contribution of coal mining and transportation to the national economy is about $3 billion a year ac- cording to a study made by the National Coal Policy conference. Coal remains the backbone of the power industry producing almost two-thirds of all the electrical energy generated by fossil fuels and one-quarter of all the energy consumed in the nation. Power supplied by electric utilities increased 6.9% last year. The chairman of the Federal Power Commission predicted a 7.5% growth rate until 1980 for the nation's electric output. Some 80,500 MW of fossil fired power plant capacity are on order or under construction before 1974, compared to a present capacity, all sources, of about 290,000 MW. The comparable new additions of nuclear power plants is expected to total about 51,000 MW.

Jan 2, 1969

By F. F. Aplan

Mineral processing engineers have recorded an- other year of active research and development work. Most gratifying was the broadly based attendance at the Mineral Processing Fundamental (formerly Basic Science) Committee sessions at the 1968 Annual Meeting of the AIME. Because of the availability of good papers, the active discussion and the growing attendance, sessions have grown from one to three at the annual meeting. Prof. M. C. Fuerstenau of the University of Utah will chair the Mineral Processing Fundamentals Committee for the next two years and we may thus be assured of continued active leadership. The name change from "Basic Science Committee" to the more descriptive "Mineral Processing Fundamentals Committee" approved by the MBD executive council is a welcome improvement. Our profession continues to attract the interest and cooperation of those in other professional groups. The 1968 Engineering Foundation Particulate Matter Conference, under the chairmanship of John Karpinski of Bethlehem Steel, was devoted exclusively to comminution this year. It attracted conferees from five continents and served as a particularly stimulating source of interchange of knowledge from many technical fields. Next year's conference will be under the chairmanship of Professor L,. G. Austin of The Pennsylvania State University. This conference plus the Symposium on Wettability and Flotation to be held at the annual American Chemical Society meeting in Minneapolis in April indicates the success achieved in the inter-disciplinary approach to problems. Other evidence of this spirit of professional cooperation is the forth- coming book on Size Reduction edited by D. W. Fuerstenau. This is the outgrowth of an AIChE symposium on size reduction held in 1965.

Jan 2, 1969

By O. T. Berge

Development and production from open cut mines continued its vigorous growth trend during the year 1968. Material handling and transportation were again exposed to the use of larger equipment with shovels, trucks and front end loaders leading the way. Highlights of World Mining Activities Africa: The Anglo American Corp. opened a new high-grade copper mine in Zambia during the year. In Angola, the Companhia Minera do Lobita planned a 3 million ton iron ore production for 1968 from new mines which will ultimately produce 5 million tons per year. A feasibility study of Bethlehem Steel Co., for the development of large high- grade iron ore reserves in Gabon, was in final stages of completion this year and Pickands Mather and Co. continued its investigation of iron ore deposits along the Ivory Coast.

Jan 2, 1969

By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By J. J. Fischer

COMPOSITES containing cold-drawn, high-strength steel wires have shown promise for normal and slightly elevated temperature applications, particularly where strength-to-weight ratios or corrosion resistance are important.'-3 Although tensile strengths up to 500,000 psi may be obtained by cold drawing these wires, processing the composite at elevated temperatures will result in a rapid decrease of the wires' strength. In wrought maraging steels, high-strength levels can be obtained by aging at 900' . Because these alloys do not rely on heavy cold working to achieve their strength, and because they do not overage readily, they are of potential interest for use in composites. In view of this, the tensile strengths of composites containing The total heat effect thus represents the heat of formation, AHf of the compound at 273' . Since the heat of solution of tin in the tin solvent bath is zero, AHz = 3( - H273)Sn and Hf is given by: For LaSn3, AH3 had a measured value of 11,285 i 380 cal per g-atom while for La2Sn, the corresponding value was 33,658 870 cal per g-atom. Using the measured data for the compounds and pure lanthanum, a value of -15,150 200 cal per g-atom was calculated for the heat of formation of LaSn, at 273°K, while Hf for La2Sn3 was found to be -28,090 400 cal per g-i&om. The authors would like to acknowledge the financial support of the Army Research Office, Durham, North Carolina. under contract No. DA-31-124-ARO-D-384.

Jan 1, 1969