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By R. A. Deju, R. B. Bhappu

The basic structural unit of all silicate minerals is a tetrahedron with a silicon atom at the center and four oxygen atoms at the corners. The oxygen-silicon distance is about 1.6 & and the oxygen-oxygen distance about 2.6 &. The different types of oxygen-silicon frameworks in the various silicates are based entirely on the combinations of the tetra-hedral oxygen-silicon groups through sharing of oxygen atoms. In recent years, infrared spectroscopy has permitted estimation of the ratio of the ionic character of the oxygen-silicon bond to be a few times that of the oxygen-carbon bond and the ratio of electro-negativity of the two bonds has also substantiated this finding. On this basis, it is generally accepted that the oxygen-silicon bond is the strongest one occurring in silicate minerals. As the oxygen-silicon ratio increases from quartz to the olivines, a greater percentage of the oxygen bonding power is available for bonding to cations other than silicon. Hence, with an increasing oxygen-silicon ratio, there is increasing oxygen-to-metal bonding. Upon the fracturing of a silicate mineral crystal, the oxygen-metal bond, which is almost entirely ionic in character, should break more easily than the stronger oxygen-silicon bond, resulting in a greater number of unsatisfied negative forces on the surface. If, then the mineral is immersed in a liquid containing hydrogen ions, these negative forces should tend to be neutralized by hydrogen ions from solution, resulting in a change of the pH of the solution. An increase in the degree of adsorption of hydrogen ions is to be expected as the oxygen-silicon ratio in the crystal structure increases. This study attempted to correlate the oxygen-silicon ratio for various representative silicate minerals to the adsorption of hydrogen ions. Experiments to determine the effect of surface area on this adsorption and to investigate the effect of surface iron were also conducted. It is believed that such studies of the surface properties of silicate minerals will supply pertinent information about their behavior in froth flotation systems. EXPERIMENTAL PROCEDURE Ion Exchange: Carefully selected, hand-picked samples of the minerals investigated were dry-crushed in a ceramic ball mill and sieved to obtain a minus 100 plus 200-mesh sample. The sized samples were then run through the electro-magnetic separator to remove any iron-bearing particles. A 10-g sample of each mineral was placed in 100 ml of freshly deionized water previously adjusted to a pH of 3.50 with HCl. The beaker containing the sample and the water was placed under a bell jar from which the air was displaced at once by nitrogen gas from a tank. All experiments were carried out in a nitrogen atmosphere. The sample and solution were stirred gently but continuously during the entire experiment, the stirring speed being kept about the same for all runs. Changes in pH were followed with a Beckman Zeromatic pH meter and recorded on a

Jan 1, 1967

By Michael Perch, Charles C. Russell

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated1 recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be conducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests. Several attempts have been made to derive formulas for such predictions. The relations of both ultimate and proximate analyses to coke physical properties and byproduct yields have been studied. Lowry and co-workers1 correlated statistically the U. S. Bureau of Mines-American Gas Association assay test results with coal analyses, using 90 coals and coal blends. Parry,² Spooner,3 and Gabinskii and Krym4 made similar correlations. Lowry concluded that there were definite relationships between the proximate analyses of the coals and the yields and properties of the products. Although this statistical study was made on test results from carbonizing coal in a cylindrical steel retort, the conclusions are important and provided one of the first steps in the simplification of this complex subject. Studies should be made of other references on this subject just cited. Studies of the coking process reported in the literature frequently were confined to a small number of coals, and very few have included coals from various ranks. It would seem logical, however, that a program for studying factors involved in the formation of coke should be based on a number of coals selected from each of the various classes or types of coking coal. The possible use of the scheme of classifi-

Jan 1, 1950

By George R. Elliott

Methods are presented for measuring and comparing "degree" of water drive, and for observing the control that rate of withdrawal exerts over decline of reservoir pressure. Degree of water drive is studied from pressure-production curves of 10 reservoirs; the method used to present these comparatively is to convert cumulative oil production from barrels to percentage of ultimate. Degree of water drive is also represented by a "water-encroachment factor," representing barrels of water influx per pound-month per acre-foot of oil reservoir. Pressure-production curves for the water-drive reservoirs after a period of declining pressure show a diminishing angle of slope, in some cases to the point where pressure ceases to decline or where it even increases; the shapes of these curves are in marked contrast to the dissolved-gas type of curve, which shows a general trend toward zero pressure at ultimate oil recovery. Yearly rate of oil production in percentage of ultimate oil recovery is correlated with pressure decline. The correct rate of production of oil with its associated gas and water sustains pressure in reservoirs having a high water-encroachment factor. For reservoirs having a low water-encroachment factor, it is necessary to inject the produced water and even inject large volumes of water from an outside source. The discussion of the actual reservoirs is preceded by a general review and is followed by a substantial bibliography. It is now generally accepted that water drive is capable of yielding 60 to 80 per cent of the original oil in place in most reservoirs, as compared with 20 to 40 per cent for dissolved-gas drive. There is no need to question the importance of controlling a reservoir in order to take advantage of such an efficient mechanism. What is a water-drive reservoir? Oil reservoirs usually combine two or more of the four basic mechanisms: dissolved-gas drive, gas-cap drive, water drive, gravity drainage. A water-drive reservoir is one in which water advances to take the place of the oil and gas produced. When the oil withdrawal rate is sufficiently low, the water will tend to maintain pressure. The maximum effectiveness is attained when the water follows the oil withdrawal so closely that little or no decline in pressure occurs. Oil in its underground reservoir is associated with water. This water is significant in the production of the oil according to the source of supply and the permeability of the surrounding formation. As oil is produced and the pressure is lowered, water can move in to replace the oil. With adequate supply and sufficient permeability, actual movement takes place on an extensive scale. The first movement of water takes place by expansion of the water and its associated fluids. While this expansion is of little importance in some fields, in others it is sufficient to supply all of the energy required for the production of oil. When a pressure differential has been established

Jan 1, 1946

By E. C. Bohlen, H. l. Burghoff

The work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and G1ocker;l Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45' to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (II3)[II2], (ooi)[ioo], and a combination of (II0)[II5] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,' who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. Test Materials and Equipment For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, I31/2 in wide and I1/2 in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By E. J. Valyi

The purpose of the continuous casting processes is twofold: As the name implies, they aim at performing a heretofore intermittent operation continuously; in this respect, they tend to satisfy the appetite of the beast that modern extrusion plants and rolling mills have grown to be. The effort invested in the development of these methods bore rich dividends in economy and in the improvement of technical characteristics. The other purpose of many continuous casting methods is to reduce the number o-f operations mushrooming between the liquid alloy and the finished mill product, essentially by substituting adequate chill in comparatively small cross sections for one or more "breakdown" steps. It is this second tendency of continuous casting that justifies description of the Soro process within the frame of our symposium: although not continuous, the Soro method constitutes a means of converting molten metal into a nearly finished mill product. The Process The name, Soro, is a composition of initials and abbreviations, with no particular technical significance. The process originates in Switzerland; it was adopted by numerous European plants between 1937 and 1940 and is now being installed in this country. It is applicable to ferrous and nonferrous alloys of an exceptionally wide range of composition. It is capable of producing rod from 1/2 in. to approxi- mately 4 in. in diameter, or other simple solid shapes of corresponding cross-sectional area. , Fig. I shows schematically the succession of operations involved. A ring is cast in a two-part centrifugal-casting metal mold. The cross section of the ring may be round, hexagonal, rectangular or some other solid shape, with the exception of any contour that is undercut with reference to the mold parting line. As cast, the ring has a riser along its inner periphery, which is removed in the next operation, so as to leave the ring with a dean cross section. Following the removal of the riser, the ring is severed at one point and one end is bent outward, leaving a slight clearance between the two ends. The next step is straightening of the ring in a special device, forming a bar with a slight bend; this is followed by any one of the conventional finishing operations that are necessary to obtain forging rod, screw-machine stock or strip. The outstanding features of this procedure are: I. The cross section cast is the same or within a few per cent of the cross section of the finished product (except for fabricating into strip and wire). 2. All operations following casting of the ring are performed cold. Equipment The equipment required is simple and inexpensive. The casting machine is a conventional horizontal-shaft mold assembly, similar to those found in centrifugal-casting foundries. Fig. 2 shows a battery of three machines- with their protecting hoods .swung open. One of these machines,

Jan 1, 1945

By Jack White, Ralph B. Adair

The Mufulira mine in Northern Rhodesia is 13° south of the Equator and at an altitude of 4100 ft above sea level. The concentrator was planned in 1930 to treat about 10,000 tons of ore per day, but before construction work had gone very far the size of the plant was reduced to 1500 tons daily capacity. Then just as the construction was finished in December 1931, the price of copper did not warrant the commencement of operations and it was not until October 1933 that the mine re-opened. Extensions have been made to the plant in 1934, 1935, 1936, 1937, 1940 and finally in 1945. The capacity of the plant when the 1945 extension is completed will be 9500 short tons per day. The various extensions have been carried out with the minimum confusion and with great skill on the part of the designers and the erection engineers. In dealing with the plant in this paper it is proposed to give an outline of the present practice and only to refer to past practice when it is considered of particular interest. Ore Treated The ore consists of fine grained highly siliceous, felspathic and argillaceous quartz- ites, the latter containing graphitic carbon and locally termed graywacke. These rocks are considerably altered near the surface and on the fringes of the ore body. Despite extensive efforts at mixing, both underground and in the crushing plant, many sudden changes of ore take place in the mill feed. The minerals are chalcocite, bornite and chalcopyrite with relatively unimportant amounts of malachite, native copper, azurite, covellite and chrysocolla. Gold is present at about I oz to a thousand tons, and silver at about 2 dwt. per ton. With increasing depth the nonsulphide content or,, as commonly termed locally, the oxide content of the ore is decreasing and is now less than 0.25 pct against a high of 0.77 pct- Crushing Operations The first stage of crushing is done under. ground where the oversize from I2-in. grizzlies is fed to a 56 X 72-in. jaw crusher. At the Selkirk shaft two 10-ton skips deliver the run of mine ore at a rate of 450 tons per hour to the 400-ton capacity shaft bins. One 6 ft wide Ross chain feeder and one locally made air-operated finger feeder feed the two 30-in. McCully crushers. Ahead of each crusher is a 6 X 9-ft spring grizzley spaced at 5 in. on a 35O slope. Neither the Ross chain feeder nor the finger feeder is entirely satisfactory and for the wet, muddy and sticky ore that has to be handled it is planned to replace these with two 6-ft wide apron pan feeders. The McCully crushers deliver a minus 5-in. product, at a.rate of over 500 tons per

Jan 1, 1949

By K. E. Brown, F. W. Jessen

It is deemed feasible to store atomic reactor fuel wastes in salt dome cavities when the differential pressure acting on the cavity does not exceed 3,000 psi and the temperature is less than 400°F. Tests at pressure increments of 1,000 psi were conducted on a 2-in, cylindrical cavity contained in a 6-in. long X 6-in. diameter salt core. The cavity exhibited stability under pressures up to 3,000 psi and temperatures to 300°F. At temperature ranges of 100 to 400°F and with pressures of 5,000 psi and above continuous deformation of the cavity resulted. Initial movement of the salt was observed at all pressares. This was evidenced by vertical deformation and cavity size reduction. INTRODUCTION The development of storage techniques for safe disposal of atomic reactor fuel wastes is a goal of the Atomic Energy Commission. Salt domes have been used successfully for storage of liquefied petroleum gases and hence should prove to be suitable for liquid waste products of atomic reactors. The purpose of the following work is to evaluate the practicability of utilizing salt dome cavities for such wastes and to de-termine particularly the effect of pressure and temperature on a salt cavity. This work represents a part of a comprehensive study covering the over-all problem of storing re- actor fuel wastes in salt domes and/ or salt beds. The problem of accurately determining the stresses which exist in rocks in the earth's crust is indeed a complex one. Theoretical studies have differed widely in many of the basic assumptions about the physical properties of the rock itself. Some solutions of problems in underground stress analysis assume that rock is elastic, homogeneous and isotropic in character; others assume that rock possesses plastic, viscous, elasticovis-cous properties, or a combination thereof. Experimental evidence has shown that salt possesses plastic, viscous and elasticoviscous properties.' Recent work has shown that salt becomes more plastic with temperature.' APPARATUS AND PROCEDURE For experimental study a cylindrical cavity was chosen for analysis since it provided maximum volume per unit of depth with constant diameter. This particular cavity shape, allowing for irregularities, can be easily leached out of salt domes in field operations. For the purpose of approaching underground storage conditions as nearly as possible, the following factors were considered: (1) control of pressure and temperatures, (2) measurements of temperature gradients throughout salt mass, and (3) measurement of structural stability of salt cavities. In order to obtain triaxial pressure on the salt cavity without resorting to the application of fluid pressure directly on the salt mass, a system was designed whereby the same effect could be produced through axial loading only. By cutting a core to close dimensions to fit a steel test cylinder and applying axial pressure, a lateral pressure was obtained. This equipment is shown in Figs 1 and 2. A steel cylinder was made from

By R. E. Zimmerman

The separation of fine sizes of coal from its impurities by means of various flotation methods has become of increasing importance in the coal industry. This, no doubt, will be even more so in the future as the quantity of high grade coal is depleted, particularly that used for metallurgical purposes. The purpose of this paper is to describe and report the results of research work done under the auspices of the Pittsburgh Coal Co. to determine the amenability of their bituminous fine sizes of coal to flotation, to investigate the value of various reagents and factors affecting their use, and compare the results between froth flotation and bulk oil flotation. Compared with the preferential flotation of complex minerals, or ores, the flotation of coal is comparatively easy. However, this statement should not lull one into the feeling that there are no special problems involved. For instance, the separation of coal from pyrite in high sulphur coals is still far from being 100 pet successful. Size consist has considerable effect on reagent consumption and recovery. Other factors will be described and finally it must be remembered that in the flotation of coal a low priced material is being treated and thus economic considerations govern more closely its application than is generally the case in treating other minerals. As a result of the research work done by the Pittsburgh Coal Co. on the flotation of coal, it was concluded that it was practical to clean the —48-mesh coal commercially by froth flotation and after several different types of flotation units and circuits were investigated by means of pilot plants, large scale units were installed at their Champion Nos. 1, 4 and 5 Preparation Plants for the cleaning of —48-mesh slurries. These large scale operations have been recently described by D. H. Davis.' C. P. Proctor and C. B. Carlson2 in their chapter on Froth Flotation of Coal in the AIME Seeley W. Mudd series book on Coal Preparation describe some of the practical applications of our Pittsburgh Coal Co. laboratory work in actual plant practice as well as summarizing part of the investiga-tional work. The author presents this paper, however, as a supplement to their reports, and records the basic research accomplished in the laboratory investiga-tional work as well as the results of experiments using bulk oil flotation. In presenting this work the author wishes to state much more work must be done in applying the principles of flotation to cleaning coal, especially in view of recent studies and practices in other mineral beneficiation fields. Methods of Conducting Laboratory Tests The bulk of the research work was conducted in the laboratory of the Champion No. I Preparation Plant. This plant has elaborate facilities for sampling and analyzing coal and proved to be an admirable location for the investigational work. Four types of laboratory flotation ma-

Jan 1, 1949

By Jack White, Ralph B. Adair

THE Mufulira mine in Northern Rhodesia is 13° south of the Equator and at an altitude of 4100 ft above sea level. The concentrator was planned in 1930 to treat about 10,000 tons of ore per day, but before construction work had gone very far the size of the plant was reduced to 1500 tons daily capacity. Then just as the construction was finished in December 1931, the price of copper did not warrant the commencement of operations and it was not until October 1933 that the mine re-opened. Extensions have been made to the plant in 1034, 1935, 1936 1937, 1940 and finally in 1945. The capacity of the plant when the 1945 extension is completed will be 9500 short tons per day. The various extensions have been carried out with the minimum confusion and with great skill on the part of the designers and the erection engineers. In dealing with the plant in this paper it is proposed to give an outline of the present practice and only to refer to past practice when it is considered of particular interest. ORE TREATED The ore consists of fine grained highly siliceous, felspathic and argillaceous quartzites, the latter containing graphitic carbon and locally termed graywacke. These rocks are considerably altered near the surface and on the fringes of the ore body. Despite extensive efforts at mixing, both underground and in the crushing plant, many sudden changes of ore take place in the mill feed. The minerals are chalcocite, bornite and chalcopyrite with relatively unimportant amounts of malachite, native copper, azurite, covellite and chrysocolla. Gold is present at about 1 oz to a thousand tons, and silver at about 2 dwt. per ton. With increasing depth the nonsulphide content or, as commonly termed locally, the oxide content of the ore is decreasing and is now less than 0.25 pct against a high of 0.77 pct. CRUSHING OPERATIONS The first stage of crushing is done underground where the oversize from 12-in. grizzleys is fed to a 56 X 72-in. jaw crusher. At the Selkirk shaft two 10-ton skips deliver the run of mine ore at a rate of 450 tons per hour to the 400-ton capacity shaft bins. One 6 ft wide Ross chain feeder and one locally made air-operated finger feeder feed the two 30-in. McCully crushers. Ahead of each crusher is a 6 X 9-ft spring grizzley spaced at 5 in. on a 35° slope. Neither the Ross chain feeder nor the finger feeder is entirely satisfactory and for the wet, muddy and sticky ore that has to be handled it is planned to replace these with two 6-ft wide apron pan feeders. The McCully crushers deliver a minus 5-in. product, at a rate of over 500 tons per

Jan 1, 1947

By B. H. Caudle, A. B. Dyes

In a recent publication' it was shown that wells with a free surface in a homogeneous gravity-drainage reservoir have a hyperbolic decline with index n '. This paper reports efforts to extend this theory to practical field cases. As a first step in making the extension, a large number of lease production curves from gravity-drainage fields in the stripper stage were fitted with the general hyperbolic decline equation, q/q, = 1/(1 + y) y and n in each case being determined by statistical methods. It was found that this equation is reliable for decline curve extrapolation for periods up to at least 25 years. The resrilts obtained were disturbing in the sense that values for the index, n, were often smaller than one, which fact leads to the prediction that a well would produce all infinite amount of oil in infinite time. A theoretical investigation based on the results of the previous paper provides a suitable explanation for these low values of n. It suggests that these are obtained if production occurs from two or more layers of diflerent permeabilitv and thicktress or two lnyers having different skin effects. It is predicted that as the more permeable layers are exhausted, the index of decline, n, will rise from a value smaller than 2, to n = 2. A practical method is given for fitting the general hyperbolic decline Eq. 6 to production decline data. When this method is used, the index of decline observed in gravity-drainage reservoirs in the stripper stage when wing only data over early years 01 decline usually agrees quite closely with that determined using data over 25 years or more. This indicates that the hyperbolic decline equation is reliable for predicting behavior of such reservoirs. A method is also suggested for taking into account any changes in the value of the index INTRODUCTION As a result of both experimental work with models and theoretical deductions, it was recently concluded' that wells having a free surface in a homogeneous reservoir producing by pure gravity drainage should have a hyperbolic decline with n = 2. The present report details efforts to extend this work on ideal homogeneous reservoirs to actual field cases. It should be remembered that both the previous work and the present extension are based on the assumption that the reservoir is at very low pressure, and hence, nearly all the potential available for driving fluid to the well is the gravity head. Attempts to apply conclusions of this study to reservoirs which have considerable pressures supplementing the gravity drive may lead to difficulty. WELLS WITH NO FREE SURFACE In a dipping gravity-drainage reservoir such as that shown in Fig. 1, some of the down-dip wells have no free surface. The previous study' showed that the up-dip wells, which have a free surface, should follow Eq. 1. The following approximate analysis, of a type which was justified experimentally for up-dip wells in the work just mentioned, leads to results for the down-dip wells.

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By C. F. Clausen

"Cement" means binding agent or glue. It is derived from the Latin word "Caementum," the name of a limestone, chips of which were used in mortar more than 2,000 years ago in Italy. During the middle ages "cement" or "cement" generally denoted mortar. Today it means any binding material. The Thomas Register lists nearly 200 classifications for "cement" including automobile cement, household cement, rubber cement, etc. The material most commonly associated with this word, however, is portland cement which, when mixed with water and allowed to hydrate, is a ceramic binding material used to cement aggregates (crushed stone, gravel and sand) together in "concrete," the most universally used building material of today. It is estimated that more tons of concrete are used annually than all other building materials put together including steel, lumber, gypsum, bricks, tiles, aluminum and glass. Its use in foundations, building construction, sanitary work, dams, railroads, and highways, makes it difficult to conceive of modem civilization without concrete. A survey made in October 1955 showed the following uses of portland cement: [Percent Highways20 Nonresidential buildings20 Residential buildings15 Military construction10 Sewer and water works8 Public utilities10 Other (conservation, farm, and maintenance and repair)17 100] As of today, the percentage for highways is probably even higher. Ceramic binding materials have unquestionably been used in construction work for thousands of years. The mortar between the blocks of the great pyramids was calcined gypsum (plaster of paris). The use of calcined and slaked limestone goes back earlier than the Roman Empire. Gypsum, however, is relatively soft, and common lime mortar is not "hydraulic," i.e., it does not harden under water. The Greeks and Romans discovered later that an addition of a finely divided active siliceous material (Santorin earth or Pozzolana) would react with slaked lime to form a stronger, and hydraulic, cement. The Appian Way in Italy, Colosseum, and the great Aqueducts built by the Romans were made with this type cement, and some of these structures are still in existence today. However, not until 1756 did some serious research result in the development of better cements. In that year the English engineer, John Smeaton produced a stronger cement by burning a limestone containing considerable proportions of clayey impurities. Other investigations and improvements were made by Bryan Higgins, Bergmann, Joseph Parker, L. J. Vicat, J. F. John, James Frost, and I. C. Johnson.2 Traditionally, but perhaps unfairly to others, the invention of the prototype of today's portland cement is credited to the English mason Joseph Aspdin who in 1824 obtained a patent and gave the product its name, because in color the mortar produced from it resembled a natural building stone obtained from the British Isle of Portland. The contributions of Johnson and Aspdin were primarily the important step of preparing a synthetic mixture of lime and clay without depending on raw materials found in nature which might contain such elements in desirable proportions. However, even these early

Jan 1, 1960

By E. A. Gulbransen, J. W. Hickman

DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may Occur to such a degree that oxides may form in the body Of the film and On the outer surface which are different from those that would normally form if the additional elements were not present. The use Of transmisson electron diffraction may aid us in jnterpreting these phenomena. UP to the Present time all Of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physica1 state of the "alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the remova1 of carbon by Oxygen in a decar-burization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with lifetime tests carried

Jan 1, 1949

By James C. Word, R. M. McLouski

This paper will describe the development and application of large-scale integration techniques employed in the fabrication of a germanium multielement array. The array consists of 100 by 228 PNP bipolar transistors fabricated on 5 mi1 centers. Back-biased p-n junction techniques are used for electrical isolation of the individual elements. The end use of the array is a high resolution, large area IR sensor. The monolithic array is fabricated in 1 ohm-cm p-type germanium epitaxially deposited on 6 ohm-cm n-type substrate. Epitaxy was accomplished through the hydrogen reduction of germanium te trachloride. Di-borane was used as the dopant. Base regions are achieved by the diffusion of arsenic from doped oxide or arsine sources. Oxide-masking of the arsenic im-pzlvity was achieved by the chemical deposition of a boron doped glass. The emitter is formed by an aluminum alloy diffusion technique. Vacuum deposited aluminum is used for the emitter, interconnections, and for the contact and bonding pads. ALTHOUGH a great volume of literature pertaining to the development of large scale integration techniques (LSI) has been published for silicon and in particular silicon imaging applications,' to date only a small number of similar devices have been constructed using germanium technology.' Since the physical and chemical properties of germanium are vastly different from those of silicon, the fabrication technology for integrated structures in germanium is also different from that of silicon. In particular germanium does not possess a stable oxide as can be grown on silicon by heating in an oxidizing ambient for masking of dopants and passivation. This paper describes the application of germanium LSI techniques employed in the fabrication of a multielement infrared sensor array. The array is used in a high resolution, large area infrared sensor for operation in the 0.8- to 1.5-u spectral range. Back biased p-n junction techniques are used for electrical isolation of individual elements. Discrete germanium devices have been fabricated routinely for some time. However, mainly due to the lack of a suitable mask for selective doping and the high current leakages inherent in germanium p-n isolation, few monolithic germanium structures have been constructed. THE INFRARED MOSAIC A cross-sectional view of the array is shown in Fig. 1. The monolithic structure consists of 12,800 PNP transistor elements in a 100 by 128 matrix fab- ricated on 5 mil centers. The emitters of each line of transistors are connected together using aluminum interconnects while the strip collectors are connected together in series at right angles to the emitter lines. The selection of this structure is dictated by the readout technique involved. Access to each element transistor is obtained by applying a bias voltage to a particular collector strip and separately interrogating each emitter row. A charge storage, i.e., an integration mode is used for reading out this particular array Construction techniques available for use with germanium do not include a selective p-type diffusion capability for surface concentrations greater than 10" per cu cm and junction depths greater than about 10 u. This fact limits the type of structure that may be used. Therefore, an array of PNP transistors that did not employ p-type diffusions was chosen. The structure was fabricated by growing a 1 ohm-cm p-type epitaxial layer on a carefully prepared 6 ohm-cm n-type substrate. N-type dopants were used for the isolation and base diffusions and alloyed aluminum was used to form the emitter junctions. The array was then completed by evaporation of aluminum interconnections and contact pads. SUBSTRATE AND SUBSTRATE PREPARATION Germanium substrates of (111) orientation grown by both Czochralski and zone leveling techniques were utilized for mosaic fabrication. Czochralski substrates were preferred because of the lower dislocation densities available in this type of material. Dislocation densities for the Czochralski material were typically less than 3000 per sq cm, while those for the zone leveled material were typically less than 5000 per sq cm. All substrates were uncompensated to minimize thermal conversion problems in subsequent epitaxial and diffusion processing. Both in-house and vendor polished wafers were used. The in-house polishing technique employed consisted of an initial gross chemical etch in CP4 to remove saw damage from both surfaces. This was followed by a chemical-mechanical polishing operation of one side of the wafer. The chemical-mechanical polishing solution used was Lustrox 1000 (Tizon Chemical Co.), and consists of zirconium dioxide, sodium hypochlorite, water and a surfactant. The wafer thickness before and after polishing was typically 0.020 and 0.010 in, respectively. THERMAL CONVERSION The problem of thermal conversion of both the substrate and epitaxial layer was particularly acute because of the relatively low carrier concentrations employed in both regions. This problem has been encountered by other workers in the past.3 Without special treatment before epitaxial growth substrate conversion (n-type to p-type) and changes in the re-

Jan 1, 1970

By C. B. Manula, R. Venkataramani

Application of computers to present-day open-pit mining with bucket wheel excavators (BWE) is discussed. The development of the wheel excavators and their use in mining are discussed along with the necessity for building a computer model of the bucket wheel and the mathematical formulation of the problem. The simulation procedure, testing the model, and test results are summarized. Even though the mining industry in 1966 produced more ore than ever before, current extraction rates are only a fraction of what is expected in the later years of the 20th century. Nearly 90% of all metals and mineral products consumed last year was recovered by open-pit mining. This has placed great pressure on this segment of the industry which has, consequently, resulted in some spectacular developments. With increasing size of projects, the need for increased sophistication of engineering, planning, management, and administration of modern mining installations has never become more apparent. The design of complete systems for the mine and plant that fit the mold of today's business and social environments is undergoing an evolutionary process. Traditional concepts in mine development and operations are being sidestepped in favor of new ideas and principles. As the overburden thickness increases, materials handling presents a major problem to mining companies, especially those concerned with the mass production of ore and waste from low-grade deposits. The profit margin here is likely to be significantly less as to take chances with capital investment. Constant efforts are needed to improve upon productivity if the ore is to be economically mined. The development of vast low-grade deposits and thick overburden deposits calls for better tools to handle the enormous amount of materials. A natural solution to this problem is the use of bucket wheel excavators (BWE), which employ a continuous cutting head to feed the materials handling system. High productivity, versatility, economy of operation, and adaptability to most types of haulage systems combine to make BWE's attractive for large earth-moving operations. "Operating costs are being pushed down by the impact of giant haulage units, by high-speed conveyors, and computerized railroads. Matching all these with the continuous output of BWEs, one can visualize increased production at much lower costs." Historical Background The wheel excavator, which was patented in Germany in 1913, made its first appearance in an open-pit lignite mine in 1920. From this early beginning, however, BWEs were slow coming into practice. Initial developments were dampened by many design problems. From 1936 onward, major developments in design improved the wheel's ability, capacity, and versatility. A literature survey shows that wheel excavators are being used in Australia, Zambia, South Africa, the Congo, India, Indonesia, Czechoslovakia, Russia, Great Britain, Guyana, Yugoslavia, Morocco, Germany, Canada, and the U.S. for mining and loading chalk, lignite, clay, sandstone, phosphate, broken ore of iron, coal, shale, loose and semi-loose rock overburden.' A recent LMG* BWE at work in a German lignite mine weighs 6790 tons with an hourly capacity of 11,000 cu m. Although the BWE has wide applicability, its application to new mining areas poses a problem. Because of the large capital investment involved in BWE application and the narrow profit margins in mining low-grade ores or coal at depth, little margin of error can be tolerated in the selection, design, and operation of these machines. The questions that need to be answered prior to installation of a BWE for a mineable deposit are: 1.) What are the anticipated BWE performance characteristics? 2) Which method of BWE operation is most efficient? Attempts to answer these questions require a thorough knowledge of the mining system and the BWE operation. One approach is the building of a computer-ori-ented simulation model to determine how information and policy create the character of the BWE system under consideration. BWE Operation Modern BWEs generally excavate in blocks. Fig. la shows a BWE working in an established cut. The wheel is positioned to travel on the pit floor in line with the top edge of the old highwall. As it advances, a new highwall is exposed in the direction of excavation. Digging is done by rotating the wheel, swinging it from side to side in long parallel arcs, and "crowding" into the bank, by advancing the entire machine, or by the travel of the digging boom if an automatic crowd is available (Fig. lb). A second way by which the wheel can be advanced into the bank is by the falling cut method. A brief description of each of these methods follows. Cut with a Crowding Machine: At the end of every swing, the digging boom can be extended by the thickness of cut desired and the boom swung back in the reverse direction. Obviously, the thickness of bank excavated does not vary with the boom position; therefore, the slewing motion of the boom is fairly constant for uniform output. The thickness through which the digging boom can be advanced into the bank is theoretically calculated from the formula'

Jan 1, 1971

By R. Ebeling, M. F. Ashby

The paper is in two parts. The first develops the formulae and method needed to calculate the size, nu)nber, spacing, and volume fraction of hard or inert particles in the interior of a specimen from measurernents made on an extraction replica; throughout, the spread of- particle sizes in a single specimen is taken into account, and the extraction efficiency of the replica is considered. A method for testing whether the particles are randotnly distributed in space is described, and the spacing of randomly distributed particles is discussed. The second Part describes the application of the method to copper containing spherical particles of silica; the description includes an estimate of the errors involved, and a comparison of this with alternative methods. All parameters except uolume fraction can be determined satisfactorily, and the method offers advantages over other electron-,rzicroscopic techniques when dealing with hard particles in a softer matrix, or inert particles in a chem-ically less inert matrix. 1 HE experimental measurement of sizes and numbers of discrete particles of a second phase embedded in a matrix material from opaque, plane sections has been considered by many authors, notably by Fullman.' It is assumed that, when the specimen is sectioned, the particles are also sectioned, so that the diameters of the circles of intersection of particles with the plane of the cross section ("surface diameters") are measured. It is difficult to derive the distribution of true particle diameters ("volume diameters") from measurements of the distribution of "surface diameters" on a plane section. The measurement of size and numbers of small second-phase particles by transmission electron microscopy through thin foils of matrix containing the particles has been described by Cahn and ~uttin~' and by ~illiard.~ Because of overlap and the fact that particles which intersect the foil surface may be sectioned whereas those in the bulk of the foil are not, it is again difficult to measure the true distribution of particle sizes. The use of replicas for this sort of measurement has not been analyzed in detail. A replica made from an opaque cross section, thus replicating the circles of intersection of particles with the plane of section, is analyzed by Fullman's method and suffers from the same difficulties. Under certain circumstances, however, extraction replicas can be used, and offer a special advantage in that they make the determination of the true distribution of particle diameters particularly simple. It is the purpose of this paper to describe this extraction replica method. Consider the example of an alloy consisting of SiOz particles, whose mean diameter is about 1000A, dispersed in a copper matrix. When the alloy is sectioned and mechanically polished, the particles are not sectioned, because they are much harder than the matrix, and so will be either left in the surface or pulled out whole, and because the particle size is smaller than the abrasive size of even the finest abrasive. The particles are chemically inert in solutions which chemically etch or electropolish the matrix, so that chemical treatments do not section the particles either. (Experimental measurements of particle shape in this alloy confirm this—truncated particles are never seen.) Small, hard or inert, particles are therefore not sectioned when the specimen is sectioned and polished. An extraction replica taken from this polished surface shows the true "volume" diameter of each extracted particle; the distribution of diameters seen on the replica is the surface distribution of true "volume" diameters, and the volume distribution of true "volume" diameters is easily derived from it. The extraction replica method is not subject to the difficulties associated with sectioning of particles, and avoids the problem of overlap from which the transmission method suffers. The method is well-suited for studying hard particles in a soft matrix. Examples are provided by internally oxidized alloys, oxide-dispersion strengthened metals like T.D. Nickel, and carbides, nitrides, and strong intermetallic compounds in metals. It should be possible to adapt polishing techniques in alloys containing softer but inert particles to avoid sectioning the particles (say by electropolishing or etching). The method is tested and illustrated in Sections 8 and 9 by applying it to a dispersion of spherical SiO2 particles in a copper matrix. I) SYMBOLS Symbols are defined where they first appear in the text. Volume fractions of particles are denoted by the symbol f, particle diameters by x, center-to-center particle spacings by D, and numbers of particles by N. Mean particle diameters and standard deviations about these means are denoted by x and a. Both arithmetic (subscript A) and geometric (subscript G) means are employed. In this paper we measure the distribution of true diameters of particles which touch or pass through a random-plane section of the specimen. We may want to know the distribution of particle diameters in the

Jan 1, 1967

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967