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By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies', the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,' vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell' published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson' has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By F. X. Tartaron

This paper deals with basic physical phenomena, which when combined and interpreted, lead to the same mathematical equations that describe comminution phenomena. Thus, a physical model is described that corresponds to the mathematical model presented in the writer's previous papers. '12 In the mathematical model, the energy consumed in breakage is related to the volume or weight of material broken and the size of particles broken. The equation E=2.303 Ck-a log x1/x2 was derived by multiplying the volume or weight of each size in an ideal Gates-Gaudin-Schumann size distribution by an energy factor. The product of these two factors gives the energy distribution among the different sizes in a single size distribution. The energy of breakage of a specific constant weight of one size distribution to another size distribution is given by the equation E = constant/kn-1. In this case, where the volume or weight is constant, the energy is proportional to the size factor 1/kn-1. In what follows, a physical theory will be presented showing that the energy consumed in comminution is proportional to the volume or weight of the material broken and to the reciprocal of the size of this material raised to a constant exponent. THE VOLUME FACTOR The atomic theory of matter reveals that in solids, atoms or ions are arranged so as to be in equilibrium at specific distances from one another. Although the atoms or ions are oscillating, there is a definite determinable mean distance between them and this distance is a balance between repulsive and attractive electrical forces. It therefore requires force to separate the atoms or ions and when an outside force is applied, it first produces strain in increasing the distance between the atoms or ions. This strain increases to the breakage limit on application of sufficient force. In brittle materials, there is negligible plasticity and when an elastic limit is exceeded, breakage takes place. The work done is the force applied per unit area times the cross sectional area of the ideal particle multiplied by the maximum strain per unit length at right angles to the area times the length of the particle. Thus the work done is proportional to the area times the length, which is equivalent to the volume of the ideal particle. If more than one feed particle is considered broken, each particle must be subjected to sufficient strain so that the breakage limit of its contained atoms or ions is reached in order for the particle to be broken. Thus, the energy of breakage is proportional to the total volume of the particles broken. If the particles are of different sizes, the size factor must be included to get a correct determination of energy of breakage. In the preceding, it has been assumed that there is a constant binding force between the atoms throughout the volume being strained. This, of course, is not true. It is known that there are many irregularities in the structure of matter and the binding force differs markedly in different portions. But the differences are only discernible by examining extremely small subdivisions of matter. In one order of magnitude of volume, cracks can be discerned separately from non-cracked neighboring material. In a smaller subdivision of volume, lattice dislocations can be isolated. When these situations are brought into focus, mechanisms of their behavior can be learned, leading to a fuller understanding of phenomena that occur in larger scale subdivisions of matter. Very often, however, the mechanisms that operate in small scale subdivisions have negligible effect in those of large scale, and there still is a place for deriving a mechanism for large scale conditions. The quantum theory is extremely valuable for use with photons and electrons, but is of negligible use with ordinary atoms and molecules. This paper deals with relatively large scale subdivisions of volume present in comminution phenomena. Hence, the effects of cracks, lattice dislocations, misplaced atoms, etc., are smoothed out in an average, constant for each relatively large subdivision of volume. This attitude is supported by experience. If two 10 cc samples of the same ore were ground identically, the same product would be obtained. However, if two samples, each a cubic micron, were conceived to be broken, then one sample might contain a crack and the other not, hence a different product would be obtained. Experience shows that ordinary samples used in comminution, behave as though no irregularity existed

Jan 1, 1964

By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By L. A. Rapoport, W. J. Leas

The original Burkley-Leverett theory has been extended and a more detailed formulation of the waterflood behavior in linear horizontal systems is presented. Particular consideration has been given to the evaluation of capillary pressure effects and differential equations permitting an explicit evaluation of these effects have been derived. On the basis of the developed theory it is recognized that the flooding behavior is dependent upon the length of the system and the rate of injection. At the same time it has been determined that systems of different lengths yield the same flooding behavior if the injection rates and or the fluid viscosities are properly adjrrsted or "scaled." It has also been found that the sensitivity of the flooding behavior with respect to rate and length decreases as any one of these {actors increases in value and that for sufficiently long systems and high rate.; of water injection the flooding behavior becomes independent of rate and length. or "stabilized." To such stabilized conditions the theory formulated by Buckley and Leverett is applicable. A number of laboratory flooding tests have been made and good agreement Iraq been found between theory and experimental observations. The experimental results are discussed and it is shown that under field conditions the flooding behavior is usually stabilized. As a result of these finding; a procedure is indicated for evaluating field performances either on the basis of tests performed with commonly available core samples or by means of calculations using relative permeability data INTRODUCTION In recent years the development of methods for evaluating oil recovery by waterflooding has been the object of considerable research. A theoretical analysis of the mechanisms involved in the displacement of immiscible fluids was originally established by Buckle!- and Leverettl and experimental investipatio~~s have been made by numerons workers." Many of the experimental results are in mutual agreement and bear out several significant features of the flooding mechanism as predicted by theory. Thus it lias been generally recognized that a flood corresponds to the movement of a steep saturation hank or "front" (primary phase), followed by additional gradual oil displacement (subordinate phase). It has also been found that for any porous medium the flooding behavior is largely dependent upon the oil-water viscosity ratio and that for increasing values of this ratio the relative importance of the primary displacement phase decreases while that of the subordinate phase becomes more pronounced. Although the studies to date have clarified certain aspects of the flooding process. they have given rise to observations of a somewhat contradictory nature that cannot he explained in terms of the original theory. These observations pertain mainly to the effect of injection rate or pressure gradient upon recovery. Some investigators report laboratory tests that indicate incresing oil recoverieq with increasing rates of water injectill, others find the flooding behavior to be independent of and other. mention lower oil recoveries with increased injection rates.3 The conflicting evidence indicated above creates considerable uncertainty with respect to laboratory testing procedures and the utilization of the resulting data for field evaluations. The principal purpose of this paper, then, is to resolve these Uncertainties by means of a comprehensive theoretical and experimental investigation of the flooding meanism. THEORETICAL DEVELOPMENT Derivation of Flooding Equations The mathematical description of transient flow phenomena is based upon the consideration of the various processes occurring during an infinitesimal time interval in an infinitesimal volume element and upon the correlation of these processes with those occurring in the adjacent elements. The volume elements are defined as being infinitesimal in comparison to the overall dimensions of the porous system, yet each sufficiently large so aS to encompass the full range of pore openings encountered throughout the system. If a porous system can arbitrarily be subdivided into an infinite number of volume elements all possessing the same distribution of pore openings and if this distribution is unformly continuous. the system may be said to be homogeneous. Such a homogeneous porous medium is considered in the present studivs. It is furthermore postulatecl that only oil and water are present in the pornu wediu. that they act a- totally incompressible and immiscible fluids. and that gravity effects are negligible. In n linear flow system of unit cross sertional area. as treated here. the infinitesimal volume element.; to he considered are cylindrical ".slices" of thickness dx. oriented perpendicularly to the direction of flow. The equations applicable to any such volume element. at my time. describe the movement. of oil and water across the element:

Jan 1, 1953

By R. Schuhmann

Distribution of material in the fine sizes of a comminution product generally is well represented by the empirical equation' y = 100 (x/k)a [1] in which y — cumulative percent finer, x = particle size, a -= distribution modulus, and k = size modulus. Charles3 found that the energy consumption in comminution is usefully expressed by another empirical relation, E = Ak(1-D) [2] in which E = energy input per unit volume of material, A = a constant, k = size modulus based on Eq. 1, and n = a constant; (1-n) is the slope of a plot of log E vs log k. Holmes3 has presented energy equations similar to Eq. 2. The constants a and n in Eqs. 1 and 2 have been shown to depend both on the nature of the material and on the comminuting device. Moreover, Charles showed that within experimental error a and n are a — n+1 = 0 [3] Combining Eqs. 2 and 3, E = A k-a [4] In the first sections of this article it is shown that the energy equation, Eq. 4, can be derived directly from the size distribution equation for the fine sizes, Eq. 1. The derivations are made without assuming any of the specific relationships between energy and particle size which have been common in previous literature. For comminution processes in which Eqs. 1 and 4 adequately represent the experimental data, the constant A in Eq. 4 is found to be a simple and useful inverse measure of grindability. That is, A is the energy consumption per unit volume of comminution product finer than unit size as determined from the straight line portion of the log-log plot of the size distribution. These considerations all lead to a unifying hypothesis of comminution mechanism from which both Eq. 1 and Eq. 4 can be derived. Finally, it is pointed out that this hypothesis raises serious questions as to the significance of the Rittinger hypothesis, the Kick hypothesis, and other theories in which energy numbers are systematically assigned to various size fractions of comminution products in order to calculate theoretical energy consumptions. Derivation of the Energy Equation from the Size Distribution Equation: For simplicity, consider the comminution of 100 volumes of a feed material of relatively uniform particle size. The comminution process may be considered as the summation of many individual and independent comminution events. The extent of comminution is most easily expressed as the number of comminution events, z. In the first derivation, the key assumption is that the characteristics of the comminution events in a given crushing or grinding process are substantially constant and do not vary with the progress of the comminution process. Accordingly the characteristics of an average comminution event may be defined. In one such event, a quantity of energy $E is applied to a single particle of size f and volume $v. The crushing of this particle produces fine particles with a size distribution similar to that given by Eq. 1: yw=100(x/ka)a0 [51 In this equation yo, a0, and k0 are used to characterize the product of an individual comminution event rather than the product of the comminution process as a whole. In using Eq. 5, we will not be concerned with values of x close to the feed size f and will therefore assume only that the equation is applicable to the finest sizes of the material. In 100 volumes of total product, the actual volume of product finer than x from a single comminution event, or dy, is given by The total volume of material below size x, resulting from z events, is then given by y = z(dy) =z(dv) (x/ka)a0 =" Eq. 7 reduces to Eq. 1 when we let a, = a and [8a] z =100/dv (ka/k )1 or k = ka (zdv/100)-1/a [8b] Eq. 8a shows that the distribution modulus of the comminution product is the same as for the product of an individual comminution event. Eq. 8b shows how the size modulus of the comminution product k varies with the extent of comminution as measured by the number of events, z, or as measured by the fraction of the feed actually subjected to com- minution1 zdv/100. The energy input to 100 volumes of total feed, or 100E, is the sum of the energy inputs for all the comminution events: 100E =z (dE) [9]

Jan 1, 1961

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

THE following letter from the Rector of Louvain University, addressed to Mr. Adams and the other delegates of the Founder Societies, will be of interest to members of the Institute. It is my duty, in the name of the University of Louvain and in my own personal name, to thank you and the representatives of the Founder Societies of the "United Engineering Society" for the very kind letter of congratulations which you sent to me from Brussels on the 5th of July.

Jan 1, 1928

By J. Robert Van Peli

IT was a strange but highly fruitful marriage-that union of hardy explorers, seeking the rich treasures of copper in the Lake Superior wilderness, with Boston's aristocracy of brains, capital, and enterprise. This historic wedlock, which has continued happily to the present day, was the means by which the wealth of Lake Superior's copper was won for the use and benefit of an expanding America. One branch of this family tree, the western branch, begins with prehistoric Indian miners, embraces the early French explorers of the Upper Lakes, and finally includes the British and American pioneers who reduced the vague rumors of copper to known fact and actually began the mining of copper in the wilderness. The other branch, the New England line, begins

Jan 1, 1948

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick's second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. 'The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick's second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank' have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank's suggestions to diffusion in alloys has been discussed by Wagner.' Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By R. L. Perrine

The rise of drain holes drilled from a well to improve productivity is becoming increasingly common. This paper presents data on the productivity increase that may he expected. The data were obtained by use of an electrolytic tank mode1 of a reservoir. Parameter varied in the study to show their effect on productivity include the length, number, and arrangement of drain holes, formation thickness, and damage near the well-hore. The most important results are that very large increases in productivity can be expected only ill damaged wells. The distance, to which drain holes penetrate is of primary importance. Additional length is more effective than increasing the number of drain holes. INTRODUCTI O N In planning the use of drain holes to improve productivity, it is important to he able to estimate the increase in production that can be obtained for a given expenditure. It is also important to know what combination of parameters related to the use of drain holes can he chosen to give the largest production increase. This paper presents data on the productivity increase that may be expected, as obtained by use of an electrolytic tank model of the reservoir. In this study, :! number of parameters were varied to show their effect on productivity. These included the length, number, and arrangement of the drain holes. The presence or absence of a damaged zone of low permeability around the well-bore and the thickness of the producing formation were also considered. The productivity increase that might be expected due to drain holes is presented as the ratio: productivity of a well after drain holes are drilled and completed to the productivity of the same well in an undamaged state without drain holes. The symbol Q/Qo is used to represent this productivity ratio. Thus, the comparison in each case is with a formation of uniform and undamaged permeability. Additional notation includes I;, for the radial extent of the damaged zone, which is assumed to be cylindrical and concentric with the wellbore. Thus the effect of an actual block is approximated by a discontinuous varia-tion in permeability. For purposes of this paper, the permeability within the damaged zone, denoted by kb, is assumed to be 1/25 that in the remainder of the formation, or k. A necessary assumption in making comparative tests using an electrolytic model is that reservoir flow behavior can be approximated by single-phase, steady-\tate flow according to Darey's Law. In addition, the formation must be assumed to be homogeneous with equal horizontal and vertical permeability. The well-hore diameter in this study is assumed to be 11¾ in. and the drainage radius of the well equal to 500 ft. The drain holes are considered to have been completed without damage. THE ELECTROLYTlC MODEL 'She producing formation was modeled by forming a sheet of phosphor-bronze into a cylinder 40% in, in diameter to represent the boundary of the drainage area. This was enclosed in a waterproofed plywood box, and the box filled to an appropriate level with a dilute sodium chloride solution. Solution concentration was adjusted to give a total resistance from

Jan 1, 1956

In the 100' years since AIME was founded in 1871, the Institute has issued a great many publications in a variety of forms: periodicals, Transactions volumes, and special volumes or books. The following is a brief history of AIME publishing with some suggestions for proper referencing. TRANSACTIONS AIME Transactions volumes have been numbered consecutively since No. 1 was issued in 1873, including papers for the period 1871-1873. One or more volumes have been issued each year and may be divided into three general time periods: General Volumes (1873-1927), Volumes classified by subject matter (1928-1949), and the present practice, begun in 1949, of issuing three volumes per year, one each in the fields of mining engineering, metallurgy, and petroleum technology. The broad divisions of subject matter in each of these volumes correspond to the technical areas of the three constituent societies of AIME. AIME's Technical Publications, usually designated by TP number's (until the change in numbering system by the Society of Mining Engineers in 1958), may, with some exceptions, be referenced to an AIME Transactions volume. Reference to a specific volume, rather than paper number, is the preferred reference, since the volumes are the form of publication most commonly available in libraries. In many cases, over the years, the Technical Publications may also have been available in some other form, either as separates or in a periodical. General. Volumes (Vols. 1-78, 1873-1927): Until 1927 all papers eligible for Transactions were published in general volumes with no systematic attempt made to segregate the material on the basis of the technological fields to which the papers related.. One volume per year was issued from 1873 until 1912; from 1912 until 1927 from two to four volumes were issued annually. In addition to the Transactions papers, these volumes carried some of the proceedings of the business meetings of AIMS. Subject Volumes. (Vols. 79-183; 1928-1949): The material for these volumes was segregated according to subject matter, and up. to seven volumes were issued a year. In the latter part of the period, from 1934 on, there was one volume each' year for the Petroleum, Institute of Metals, and Iron and Steel Divisions and-the remaining papers were grouped in various ways and is sued whenever sufficient numbers of papers had accumulated: The subject volumes containing mining engineering papers are listed in Table 1. The volumes for the period, 1936-1949 are included in this Cumulative Index. Each of the Transactions volumes carries on the binding the year of publication; this date does not give an indication of when the papers included were originally presented at meetings. The contents of the volumes usually list the meetings at which. the papers were presented. Not all papers from a given meeting necessarily are in one Transactions volume. Some of the earlier volumes do not have a number on the binding or within the volume. In 1934 numbers" were assigned to all Transactions volumes, commencing with the 1871-1873 volume as No. 1. Many of the papers published [ ]

Jan 1, 1972

By E. E. Donath

THE coal hydrogenation process is well known as a means for the production of liquid fuels -from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below, e.g., 325°C-can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.1 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydro¬gen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catch-pot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1952

By K. H. Adams, T. Vreeland

The basal stress-strain behavior, dislocation density, and strain vale sensitivity of the flow stress uqere measured at room temperature on single crystals oj-zone-refined zinc , 99.999 pct Zn, and zinc containing 0.0025 and 0.02 wt pct Al. No significant change in the stvain rate sensitivity of the flow stress occurs with the addition of aluminum. Changes in dislocation substructure and nonbasal dislocation density were obserrled with the addition of aluminum. The effect of aluminum on the basal slress-strain behavior is explained in terms of changes in nonbasal dislocation density which determines the separation distance of junctions between basal and nonbasal dislocations. The onset of basal slip is associated with the breaking of attractive junctions. The chunge in basal dislocation density was found to be proportional to the one-third power of the plastic shear strain, indepedent of purity. THE effect of impurities in solid solution on the stress-strain behavior of single crystals has been the subject of many theoretical studies. These studies have generally concentrated on the interactions between impurities and dislocations to explain the hardening effeet of impurity additions. The theories that have been proposed include those of yott and Nabarro,&apos;l&apos; Cott-re11; Suzuki; and Fisher. In practice, it is generally difficult to predict the relative importance of the vari- ous effects due to impurities. In addition, secondary effects of impurity additions such as induced changes in dislocation density and substructure in the as-grown crystals have received little attention. Many experimental investigations have been conducted on the effect of impurities on the stress-strain behavior of fcc crystals. Hcp crystals have not received much attention except for the extensive work of Levine et a1.= on magnesium alloy crystals. Stuwe~&apos;&apos; has studied the effect of copper impurity on the critical shear stress of zinc crystals and has interpreted the results in terms of the impurity atmosphere model of Cottrell and Jaswon. This report presents the results of an experimental study of the effect of aluminum additions to zinc on the basal stress-strain curve and the strain rate sensitivity of the flow stress. Etch pit techniques were used to measure and characterize the dislocation density and substructure in the zinc alloy crystals. EXPERIMENTAL PROCEDURE Specimen Preparation. Compression test specimens of four different purities of zinc were prepared from CP grade zinc of 99.999 pct purity obtained from the New Jersey Zinc Co. An analysis of this material furnished by the supplier indicated the following impurities in wt ~ct: Pb = 0.0002; Fe = 0.0002; Cd = 0.00005; other <0.60011. A quantity of material of this grade was further purified by zone refining. Zone refining was carried out under a helium atmosphere by passing a double &apos;One furnace Over a 6-ft-10ng charge at the rate of 2 in. Per hr. * total of ten double zone passes were made before the charge was removed from the furnace. The first one third of each charge was used to grow single crystals. Quantities of two

Jan 1, 1969

By J. F. Gallie

From the standpoint of exploration and new discoveries, South Arkansas had a discouraging year in 1944. In January there were 73 untested drilling blocks, and 60 additions were made during the year. Of the total, 65 were condemned by dry holes on or adjacent to them, while 5 proved productive. The latter resulted in the discovery of the Salem Church, Calhoun Wilks, and Strong fields, and the extension of the Village field to the southeast. The year ended with 63 untested blocks, 41 of which were scheduled for tests to the Smackover lime, the state&apos;s deepest oil-producing formation. Geophysical activity in 1944 totaled 164 crew weeks, of which 110 were seismic, 43 gravity, and 11 radioactive (Fig. I), in contrast with 674 crew weeks reported for 1943, of, which 563 were seismic and in gravity, Five seismograph and two gravity crews were engaged in exploration in South Arkansas during January 1944. but only two seismograph crews were working there at the end of the year. In addition, exploratory core drills were used for a total of 38 weeks during the year. The year&apos;s few discoveries, none of which is considered as having added appreciably to state reserves, were the meager results obtained in the drilling of 62 wildcat wells 2000 ft. or deeper. Of this total (a detail of which appears in Table 2), 42 were drilled to the Smack-over lime or below, The average depth of the 62 wells was 5384 ft., as compared with 4992 ft. in the preceding year, while the average depth of the 42 wildcats in the lime was 5913 ft. in 1944. Fig. 2 has been prepared to show all , wells penetrating to the Reynolds oölitic lime. The 1944 dry holes are circled lightly, while discoveries are heavily circled and shown as producers. Smackover lime fields, producing from the Reynolds oolitic lime member, are indicated in black, and the locations of dry wildcat wells drilled prior to 1944 are also shown. Table 3 provides a listing of all Smackover lime wells drilled through the end of 1944. Production for the year was slightly more than in 1943, totaling 29,282,747 bbl., as compared with 27,521,943 bbl. for the preceding year. The increase was 1,760,804 bbl., or 6.4 per cent, bringing production to a peak exceeded only in the 1923 to 1928 period of flush production from the older shallow fields, principally Smackover. The increase was largely attributable to additional development in the Dorcheat-Macedonia, Atlanta, Fouke, Stephens-Smart, Haynesville, and Village fields, little production deriving from 1944 discoveries. These six fields accounted for loo of the 122 field wells drilled during the year. Annual and cumulative production for the producing life of the state are presented graphically in Fig. 3. Fig. 6 has been prepared by the author to show the producing ages and present known productive limits of all fields in South Arkansas. Production data, as usual, are assembled in Table 2, and provide a further breakdown of producing formations in the individual fields.

Jan 1, 1945

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By Francis M. Walters

IN spite of the war and the preoccupation of many physical metallurgists with work on secret or confidential problems, definite progress was made during 1944 in our understanding of the behavior of steel and of the effect of alloying elements. During the first two years of the war there was much concern over the possible unavailability of certain alloying elements; this period saw the development of the N.E. (National Emergency) steels. However, the measures taken eased the alloy situation and currently, highly practical problems under study are the graphitization of low-carbon steel and weld-cracking, while investigations of more theoretical interest have concerned hardenability, isothermal reactions, the effect of hydrogen and the interpretation of the notched-bar impact test.

Jan 1, 1945