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By George A. Roberts, Robert F. Mehl

When austenite first forms from aggregates of cementite and ferrite, it is not homogeneous.' This inhomogeneity, consisting of both undissolved carbide and carbon concentration gradients, has a profound effect upon the characteristics of the austenite-pearlite reaction. The rate of formation of pearlite is increased by the presence of inhomogeneities2,3 and because of this (when the inhomogeneity is sufficiently pronounced) the hardenability of the steel is reduced.4,5 In addition to this kinetic effect, inhomogeneities will cause the direct formation of spheroidite from austenite at temperatures just below the Ael.6-11 The present report attempts quantitatively to evaluate the effect of inhomogeneity upon the rate of the austenite-pearlite reaction, presents a method of determining the austenitizing cycle necessary to obtain "practical homogenization," and considers the effect of inhomogeneity on hardenability. Effect of Inhomogeneities on Reactions Near Ae1 Few quantitative data are available representing the effect of undissolved carbide or of carbon concentration gradients upon the rate of the austenite-pearlite reaction. In procuring such data it is necessary to separate the effect of undissolved carbide from that of grain size, and this is not an easy task. The solution of carbide is always accompanied by an increase in the grain size, both effects contributing to the retardation of the reaction rate. It has been possible to make this separation and to obtain data that are independent of the grain size by the use of steels that differ only with respect to their tendency toward grain-coarsening. Steels C and D in Table I are such steels. These steels have been studied previously ;l,2,12 they differ only with respect to deoxidation practice; C was deoxidized with silicon while D, teemed from a portion of the same heat, was deoxidized with additional auantities of aluminum in the mold. C therefore is what is normally termed a "coarse-grained steel" and D is a, "fine-grained steel." These steels can be compared at the same grain size by heating c to a low temperature and heating D to an elevated temperature, producing a structure of austenite plus residual carbide in the former while forming homogeneous austenite in the latter; in such

Jan 1, 1943

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult's law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world's silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After American interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and declined in earlier centuries in that a substantial part of its total production was made after 1900. While the district's accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1952

By Milton R. Pickus, Earl R. Parker

THE modern theories of creep¹-4 in general have been based upon the concept of generation and migration of dislocations, with the generation process normally assumed to be rate controlling. The theories are generally deficient in that they fail to take into account many factors that are known to influence creep. The influence of the state of the surface of the test specimen has been almost completely overlooked; yet the present report shows that the nature of the surface may, in certain cases, govern the creep characteristics of a specimen. In the period since Taylor" applied the concept of dislocations to a study of metals, a school of thought has developed that closely relates the plastic deformation of metals to the generation and migration of dislocations through the crystal lattice. It might be expected that the thermal energy required for the generation of a dislocation would be different from that for migration of the dislocation through the lattice. Furthermore, the activation energy for generation would be expected to vary for different parts of the solid metal. It has been predicted that dislocations would be generated most easily at external surfaces, but could also be activated at certain internal surfaces such as grain or phase boundaries. Within the body of the metal a range of values for the activation energy might be expected because of different degrees of disorder at such regions as grain boundaries, impurities, and second-phase particles. The particular value of the activation energy that was rate determining could then depend on the specific conditions of a test. If, for example, the surface atoms were by some means constrained, the generation of dislocations in the body of the metal might become the important factor. On the other hand, other conditions may favor generation at the surface. It is possible then that the creep behavior may not be completely determined by the inherent properties of the metal. Even the environment in which a test is carried out could have a significant effect. In fact it is conceivable that in order to obtain the maximum creep resistance from a given alloy, the surface atoms must be so constrained that the activation energy for generating dislocations on the surface is at least equal to that required for generation in the body of the metal. On the basis of such considerations, and in view of the limited number of publications discussing this subject, it seemed that an investigation of the influence of the state of the surface on creep might yield information of both theoretical and engineering interest. Experiments on single crystals, demonstrating a variation in the mechanical properties due to alterations in the surface layer, have been reported by several investigators.6-13 he results of these experiments have been briefly summarized;14 consequently, the earlier work will not be reviewed here. As an example of these findings the observations of Cottrell and Gibbons may be cited. They reported the critical shear stress of a lightly oxidized cadmium single crystal is greater by a factor of 2½ than a specimen with a clean surface. Materials and Methods Single crystals M in. in diam and 8 in. long were prepared from Horse Head Special zinc, melted under an atmosphere of helium in a large pyrex test tube, and drawn up into a long ½ in. diam pyrex tube by means of a vacuum pump. The cast zinc rods thus produced were cut into convenient lengths and sealed in evacuated pyrex tubes. Single crystals were grown by gradual solidification of the remelted rods. Cleaving the ends of the single crystal specimens chilled by liquid nitrogen proved a simple method for determining orientations from the exposed basal plane from the markings left on the cleaved surface that gave the slip directions with sufficient accuracy for the experimental work. The specimens chosen for the experiments were those having the angle between the basal plane and the specimen axis within the range of 15" to 65". Since zinc single crystals are quite delicate, it was necessary to devise an appropriate method of gripping the specimens in order to suspend them in the furnace and apply the load. Stainless steel collars were prepared having an inside taper, the smaller end of the taper being of such a size that the specimen could just pass through freely. The tapered hole did not extend the full length of the collar; a sufficient thickness of metal remained so that a hook could be attached to provide a means of applying the load and suspending the specimen. One of the collars was slipped over the upper end of a specimen which was supported vertically in a steel jig. The collar was then heated electrically until the end of the crystal melted and filled the collar with molten zinc. At this point the application of heat was discontinued, whereupon the molten zinc quickly solidified, due to the chilling effect of the jig. The specimen was then inverted and the second collar applied in a similar manner. The jig served several purposes: limiting the length of specimen that was melted, providing excellent alignment of the collars with respect to the specimen axis, and protecting the specimen from mechanical damage. Once the specimen was suspended in the furnace and loaded, it was desired to accomplish the surface treatment with a minimum of disturbance of the specimen. Around the specimen was a long pyrex tube, the upper portion of which was approximately 1 in. in diam, and in it was a copper coil of such a diameter to fit snugly against the tube. A specimen, approximately ½ in. in diam and 4 in. long, was suspended by means of a stainless steel rod so that it hung within the copper coil. The lower portion of the glass tube was approximately ¼ in. in diarn, and passing through it was a 5/32 in. diam stainless steel rod which hung from the lower specimen collar. This portion of the glass tube and the stainless steel rod extended through the bottom of the furnace. A T-connector, with suitable packing, was attached to the lower end of the stainless rod to provide a water-

Jan 1, 1952

By H. Margolin, E. Ence

Two versions of the Ti-Mn binary diagram have been published recently.' , -0th diagrams show two compounds in the region between 40 and 70 wt pct Mn, but disagree as to the reaction in which these compounds are involved. The investigation of the manganese-rich portion of the Ti-Mn binary diagram was undertaken at New York University as part of an investigation of ternary systems with titanium and manganese in order to determine which of the proposed diagrams is correct. A number of alloys between 31 and 70 pct Mn were prepared in a manner similar to that described by Cadoff and Nielsen; except that low currents (110 amp in argon atmosphere) and long melting times (up to 20 min) were used to prepare the alloys. Compositions were determined from weight-loss data, assuming all loss as due to manganese. Heat treatments were carried out with relatively large pieces, since there was a tendency for manganese to be lost during heat treatment. When X-ray diffraction data was to be obtained, the central parts of heat-treated specimens were used to make filings or powders which were not heat treated. Specimens were heat treated from the as-cast state. Heat-treatment times were as follows: 1150°C, 1 day; ll00°C, 2 days; 1000°C, 5 days; and 900°C, 15 days. It should be noted that equilibrium was not attained at 900°, 1000°, and in one case, at 1150°C. Metallographic specimens were electrolytically polished and strain etched by a technique described elsewhere.' At least four, and possibly six, phases were found in the region investigated. On the basis of information available at this time, a completely self-consistent diagram cannot be constructed, and therefore data are presented only for those phases which have been identified by both X-ray and microstruc-ture. Of the compounds detected, the one highest in manganese is the Laves phase, TiMn,, which is hexagonal with a MgZn, type of structure.V he diffraction data for TiMn2 from a 70 pct Mn alloy annealed at 1150°C are shown in Table I. The c/a ratio and parameters of TiMn2 agree well with those of Wall-baum hnd Rostoker et al. The values obtained here are c/a = 1.641, a = 4.825A. Another compound is the y-phase which is estimated to contain about 60 pct Mn. The y-phase has a structure which is identical to that of TiMn, with c/a = 1.639, a = 4.906Å. The fact that y has a Laves-type lattice would suggest that TiMn, has a range of solubility which extends from the composition of TiMn2 (69.6 Mn) to that of y (60 pct Mn). However, this could not account for microstructures which, in the 60 to 70 pct Mn region, show several phases in both the as-cast state and after annealing at 1150°C. Fig. 1 shows a two-phase structure of a 60 pct Mn alloy annealed at 1150°C. The phases present are y (white) and e (dark). If y were TiMn, then, according to Rostoker et al.,' the second phase of Fig. 1 should be P-Ti. The diffraction data for the 60 pct Mn alloy of Fig. 1 are shown in Table I. The starred d-values are from the e-phase and these lines do not correspond to those of &Ti. Comparison of as-cast and 1150°C microstructures of the 60 pct Mn alloy indicates that e precipitated from y. Since y has a

Jan 1, 1955

By E. C. Wright

THE bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth. edition of "The . Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after 1910 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blast-furnace capacity complementary to bessemer operations, combined with the availability of the necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the expense of bessemer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Rephosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 .to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complex discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full. oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By F. C. von der Weid

THE mining district of São Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineração de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis-the ore to be concentrated being mostly of a very high grade. MINERALIZATION AND ORES The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60° and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Macabú), the São Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and São Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in São Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydrothermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and

Jan 1, 1946

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1-4 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio,' in the 1920's to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably those from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu's in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920's were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1952

By J. W. Marx

A method is given for predicting the complete gravity drainage characteristics of arbitrarily long columns from centrifuge drainage measurements on reconstituted core samples. Oil residuals corresponding to hundreds of years of normal gravity depletion can be obtained in a few hours on the centrifuge. The gravity flow rate at any stage of the depletion process may be determined from the time correlation derived, and experimentally checked, in this study. INTRODUCTION Apart from the original observations of Muskat et al1, research publications2,3,4 on the subject of gravity drainage have been largely concerned with establishing in detail the saturation, S as a function of the height, z, in a draining column at any given time, t. Some form of numerical integration must be employed to obtain production rates and cumulative production even when S(z, t) is known. Furthermore, the relevant experimental work has been concentrated on drainage of a single wetting liquid from unconsolidated media. Since oil production usually concerns the drainage of a partially wetting liquid from consolidated media, in the presence of connate water, and since it is unlikely that sufficient information exists to establish S(z, t) in detail for any natural reservoir, the published research work appears to be, at best, only qualitatively applicable to production problems. With this in mind, the present study was undertaken by the writer. Experiments were planned whose results would have two advantages over existing measurements: 1. Observations were to be made on specific reservoir rock, reconstituted with formation water and formation oil. This would reduce their generality, from the research viewpoint, but increase their utility for production purposes. 2. The measurements were to be self-integrating, i.e., the phenomena were to be described and interpreted in terms of cumulative results. THEORETICAL DEVELOPMENT It was commonly known that centrifuging a liquid bearing porous medium increases the drainage rates and minimizes capillary end effects. The specific problem lay in selecting an acceleration, a, such that the mean residual saturation of a model cylinder was equal to the residual saturation of an arbitrarily long prototype column when the latter was drained by earth gravity alone. The physical conditions required to permit a valid scaling of model drainage time, tm with prototype drainage time, t, may be stated as follows: (a) At t = tm = O, So = Smo; (b) At t = tm? 8 Sr. = Smr.; (c) For all intermediate values of t and dS/dt=dsm/dtm whenever S = Sm; (d) S(z) = Sm(z) = a constant when t = tm = 0. 1 Here S = T I S(z)dz, where h is the length of the « Jo cylindrical column being drained and the subscripts S,Sm, and refer to model, initial, and residual systems, respectively. The first three conditions mean, simply, that an 3 vs t plot will be numerically identical with an S, vs t, plot,

Jan 1, 1957

By C. C. Templeton, S. S. Rushing

Methods previously developed for the study of air-liquid displacements in microscopic capillaries (inner diameters of 3 to 40 microns) have been used to investigate oil-water displacements in capillaries initially filled with water. Displacement calculations assuming perfect displacement and no capillary pressure hysteresis yielded oil effective viscosities smaller than the macroscopic viscosities. For a given liquid pair, the oil effective viscosity decreased both with decreasing capillary size and with increasing oil-water viscosity ratio. This behavior can be explained by the existence of an annular water film (20 A to 260 A thick) on the capillary wall. When the capillary was first filled with oil, the ratio of the oil effective viscosity to the normal oil vircosity was highest for the first water displacement and decreased with subsequent displacements. Sometimes the oil effective viscosity ratio during the initial water displacement was greater than unity. INTRODUCTION In a previous paper1 a technique was described for studying air-liquid and liquid-liquid displacements in very small capillaries of uniform diameter, in the hope that such microscopic data would further the understanding of the nature of multiphase fluid flow through porous media. That paper contained comprehensive data for air-liquid displacements in Pyrex capillaries, with a few data for oil-water displacements in capillaries initially filled with water. The purpose of this paper is to present more complete results for oil-water displacements in capillaries initially filled with water, and to describe for the first time such observations in capillaries initially filled with oil. In this way the effect of the wetting history of the system upon the displacement process may be studied. METHODS The basic techniques employed were described in the previous paper.1 The measuring procedure and the working equations will be briefly summarized here and a few modilications will be pointed out. For the present study, temperature control within 0.l °C was obtained by placing the microscope and its immediate accessories in a thermostated air bath made of a steel frame covered with plexiglas. The water and oils used in this work were the same as in the previous paper,1 with the addition of "Medium Mineral Oil, U.S.P. supplied by the Harshaw Scientific Co. When the first liquid was introduced into the horizontal capillary, the air-liquid static capillary pressure Poc was measured along the observable length of the capillary. From the relation Poc = 4y cos 0/d, the capillary diameter d could be calculated from Poc if the "microscopic" air-liquid boundary tension, To = y cos On, was taken as equal to its known "macroscopic" value. This calculation involves assuming that cos 6 = 1 and that capillary size or the resulting high interfa-cial curvature has no effect on surface tension, or y cos 6, as was verified by our work, and also by that of Cohan and Meyers on air-liquid-solid systems. For several capillaries these calculated diameter values were compared with values measured visually with a filar micrometer eyepiece. For a given capillary the average values for the two methods agreed within 1 or 2 per cent, but the visual values were less reproducible than the calculated values. Further the calculated values were much less subject to personal bias and took into account any slight ellipticity that might be present. Hence diameters calculated from air-liquid Poc data were used throughout this paper. The second liquid was introduced in such a way that a single spherical interface separated the two liquids. Displacements were always made with a constant pressure, Pt, between the ends of the capillary. The times (t) at which the interface passed certain

Jan 1, 1957

By Alexander L. Field

This paper contains an account of experimental results obtained in an extensive investigation of steels containing zirconium. There recently appeared' an announcement by F. M. Becket, at whose suggestion and under whose general direction this investigation was made, a statement of the outstanding features of the work and a brief explanation of the factors that led to its inception. It is not possible, in a paper of this character, to record all of the operating and test data collected, which includes the production of more than 350 heats of steel. The difficulty of a complete presentation is increased by the fact that several lines of experimentation are too incomplete to warrant publication of the results at the present time. In addition to the methods of manufacture and test employed in the work, there is described experimental evidence on which are based certain definite conclusions regarding the remarkable effects brought about by the presence in steel of relatively small percentages of zirconium. When added to a molten steel bath, zirconium combines chemically with dissolved oxygen, nitrogen, and sulfur, in the order named, and is capable of neutralizing the embrittling effect of phosphorus in whole or in part; although in the case of phosphorus there is no evidence so far of actual chemical combination. These effects arc not in the nature of suppositions supported by theory, nor is their existence deduced merely on the basis of analytical evidence. In each phase of its relation to or reaction with the four impurities mentioned, zirconium affects beneficiauy the mechanical properties of the steel to which it is added, in a manner which it is one of the purposes of this paper to explain in terms of a tentative working theory.

Jan 1, 1923

By Alexander L. Field

This paper contains an account of experimental results obtained in an extensive investigation of steels containing zirconium. There recently appeared' an announcement by F. M. Becket, at whose suggestion and under whose general direction this investigation was made, a statement of the outstanding features of the work and a brief explanation of the factors that led to its inception. It is not possible, in a paper of this character, to record all of the operating and test data collected, which includes the production of more than 350 heats of steel. The difficulty of a complete presentation is increased by the fact that several lines of experimentation are too incomplete to warrant publication of the results at the present time. In addition to the methods of manufacture and test employed in the work, there is described experimental evidence on which are based certain definite conclusions regarding the remarkable effects brought about by the presence in steel of relatively small percentages of zirconium. When added to a molten steel bath, zirconium combines chemically with dissolved oxygen, nitrogen, and sulfur, in the order named, and is capable of neutralizing the embrittling effect of phosphorus in whole or in part; although in the case of phosphorus there is no evidence so far of actual chemical combination. These effects arc not in the nature of suppositions supported by theory, nor is their existence deduced merely on the basis of analytical evidence. In each phase of its relation to or reaction with the four impurities mentioned, zirconium affects beneficiauy the mechanical properties of the steel to which it is added, in a manner which it is one of the purposes of this paper to explain in terms of a tentative working theory.

Jan 1, 1923

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:' where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx's paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5'7'8'10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1'-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3'' of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6'8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By Tsuyoshi Kawahara

INTRODUCTION A medium sized mine like the Mamut is not considered a standard size porphyry copper mine. If the infrastructure such as roads, bridges, port facilities, power supply, etc. is inadequate, construction cost per ton of copper produced will be unavoidably high. At the Mamut mine, all efforts had been concentrated to minimize construction cost and overcome an adverse natural environment. Consequently, it was inevitable that the amount of equipment and other arrangements were far from ideal. Some of the construction work was carried out by Japanese contractors, but most was done by local contractors, especially the buildings, installation of machines, roads, and tailings disposal dam, etc. All construction works, including a test run of an 18 000 t/d capacity mill, were completed in September 1975. The total development cost was about 100 million including interest converted into principal during the construction period. HISTORY The Mamut copper mineralization was discovered in mid-1965 by the United Nations' Labuk Valley Project. Following this discovery, further exploratory works, including geochemical survey, pitting, and shallow diamond drilling, which were carried out by the Geological Survey of Malaysia, revealed the existence of a disseminated copper mineralization of porphyry type. In July 1968, I.P. survey and deep-hole diamond drilling were

Jan 1, 1976

By Harwick Johnson, E. W. Schilling

THE separation of hematite by hysteretic repulsion was first brought to the attention of the public in 1922, by W. M. Mordey1. Three years later another paper2 was published and after another four years a third paper3 appeared in the South African publications. Certain data were lacking in these papers. In order to continue the work intelligently a knowledge of the shapes of the hysteresis curves for certain minerals was very necessary. This information was not available until the present year4. It was known that reduction of certain ores rendered them amenable to this process of separation but definite data in the form of curves showing exactly the effect of such treatment were lacking. Probably our best source of information on the separation of minerals by the use of alternating-current magnetic fields today is the reports from the U. S. Bureau of Mines5-7. It is not the purpose of this paper to tell the reader in detail how to make a commercial separator. Experimental models have recently been made7 and the results obtained have been so good that it is the opinion of the authors that the public will soon take an active interest in the subject and its development. The writers have constructed a separator that is considerably different in construction and operation from the two types described by Mr. Davis. This will be described, but the real purpose of this paper is to outline certain experiments and give curves showing data that have a fundamental bearing upon the practical construction of a separator of this type.

Jan 1, 1935

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By John S. Crandall

The mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sand-paper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where the Garnet Mines, Inc., and the Idaho Garnet Abrasive Co. with mills at Fernwood, Idaho, operate. This paper is confined to a discussion of production and marketing of garnet sand by Idaho Garnet Abrasive Co.

Jan 5, 1950

By Sherwin F. Kelly

PLAIN mining engineers usually avoid any gathering of geo¬physicists because of the incomprehensibility of their discussion to the uninitiated. This being so, gradients, gravity and gammas will be deferred to the end of this review, the first part of which will be devoted to what has been done in applying geophysics to the solution of real field problems. From the West, J. J. Jakosky reports that International Geophysics has had its activities fairly well 'divided between mining (both placer and lode), oil structural work, and clans-site and reservoir investigations. In oil exploration, electrical methods are used for depths down to 2500 ft., beyond which they utilize seismic methods. They find in their placer work that the many 'magnetic anomalies encountered in the bedrock of the Southwest render the electrical techniques more satisfactory, and with them they are obtaining thickness and tonnage of gravels, depth to and contour of the underlying bedrock as well as important structural features therein, and water-table elevations.

Jan 1, 1934

By Henry Howe

W. E. RUDER, Schenectady, N. Y.-In 1913 I presented a paper before this society on Grain Growth, and at that time it seemed to me that the only explanation for grain growth was that of critical strain. I do not think I published the photographs at the time, but I made some experiments on the effect of stretching sheets of metal. This allowed for fairly accurate determinations of the amount of cold deformation, At the time I worked-with silicon steel because one could see the change in grain growth with the naked eye. I stretched about 10-samples from 0.5 per cent. to 10 per cent., and, after heating to 1,050° C., I found that the maximum grain growth occurred at about 2 ½ per cent. cold deformation. This I designated "the critical strain" for maximum grain growth. About a year ago I talked with Prof. Jeffries, who explained to me his ideas of grain growth. It occurred to me that it would be a very easy thing to check the strain hypothesis against the strain and temperature hypothesis, if we took a certain number of these strips, strained exactly alike and heated to different temperatures; in that case the maximum grain growth ought to appear at a different percentage of deformation for each temperature. These experiments showed that there was, as Mr. Jeffries shows in his present paper, a decrease in germinative temperature with increased cold deformation. The samples were stretched from ½ to 8 per cent. and heated for 10 hr. in hydrogen. Samples were introduced into a furnace previously heated to temperature. A maximum grain growth was obtained at 5 per cent. deformation, when heated to 750° C.; at 2 ½ per cent. when heated to 800' C.; at 1 1/4 per cent., if heated at 950°C.; and at 5/8 per cent.. when heated at 1,100° C. This shows very clearly that the germinative temperature decreases with the increase in cold deformation. The growth was very much more marked, however, at the high temperature, i.e., the grain grew more rapidly and attained a much larger size than at lower temperature. In considering the photographs (Fig. A) those along the lateral edges should be ignored because.

Jan 4, 1917