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By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.' Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By K. C. Gilbart, Edgar Stansfield

One of the most striking features of the coal series passing from peat through brown coal, lignite, etc., up to anthracite is the gradual reduction of moisture content with the increased coalification of the original plant material. Thus drained peat from a bog may contain 90 per cent water, brown coal contain 50 per cent, lignite 30 per cent, while a bituminous coal may contain only 1 per cent moisture. Moisture, therefore, is one of the important factors to be considered in coal classification, especially with the lower rank coals. With bituminous and higher rank coals the moisture content is less satisfactory for classification; it may even pass a minimum value and then increase with increasing rank to anthracite and superanthracite. Coal in an undisturbed seam contains moisture which is an integral part of the coal, but it may also be wet with free, underground water percolating through the seam. Only the former must be considered in evaluating the moisture content of the coal for classification purposes; this will be called the "true moisture" of the coal. When the seam is mined and sampled the sample taken may show the true moisture; on the contrary, it may contain in addition free mine water or, especially in dry, well ventilated mines, it may contain less than the true moisture. Coal contains unstable organic compounds which may decompose, with the production of moisture, when the coal is exposed to air at ordinary temperatures, or is heated with or without exposure to air. The potential moisture of a coal therefore is higher than its actual moisture. The lower the rank of the coal, the greater its instability, as a rule, and the greater the care necessary to avoid oxidation or decomposition in any investigation of moisture content. The majority of coal workers have preferred, on account of the difficulty in evaluating the true moisture of a coal, and for other reasons, to classify coals by analyses calculated to the dry-coal basis. A number of workers familiar with lower rank coals have recently insisted that the classification of such coals can be satisfactory only if analyses on the moist-coal basis are employed. The moisture-holding capacity of coal is therefore intimately connected with coal classification, and in this paper a procedure is outlined for determining the true moisture of a coal,

Jan 1, 1932

By J. B. Macelwane

Historically whenever application of scientific results to a new problem required the special experimental background, the economic outlook and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering based on the professional requirement grew up in the engineering colleges. This is precisely what is happening now in geophysical engineering. THE Mineral Industry Education Division of AIME has long been interested in geophysical education. Organized in 1938, a Committee on Geophysical Education presented a number of reports in succeeding years. The AIME is an engineering society; hence it might be expected that the interest of the Mineral Industry Education Division would have centered about the relation of courses in geophysics to engineering education. However, this was not the case. The burden of the discussion held under the auspices of the Committee on Geophysical Education bore on geophysics in general and particularly on its relation to geology. In the decade that has passed since those meetings much water has flowed under the bridge. Not only have the geophysical sciences developed at an extraordinarily rapid rate but the practical importance and the range of their applications have spread in ever widening circles and have even assumed a very prominent place in research programs of the military, the Army, the Navy and, particularly, the Geophysical Research Directorate of the Air Force at Cambridge, Mass. So enormously have the geophysical sciences as such grown in scope and in degree of specialization that no one man in a lifetime of study can hope to master the theoretical and experimental complexities or even to follow intelligently in the published literature all the varied accomplishments of basic research in these fields. As in the other sciences, most of the results of geophysical research have potential economic value and are being applied to a wider and wider range of human needs. Here we see a parallel with the older sciences and their relation to engineering. Whenever the applications of scientific results required the special experimental background, the economic outlook, and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering grew up in the colleges and universities. In the words of the "Report of the Committee on Adequacy and Standards of Engineering Education" in the January 1952 number of the Journal of Engineering Education: "Engineering education in America was not developed after a preconceived plan. It evolved in parallel with the needs of a growing country, a country engaged in the development of a vast industrialization. From the first it filled a practical need, and its design emanated largely from an evaluation of the professional requirement." The advent of the railroad created a need for scientifically trained engineers and the response was the curriculum in civil engineering. The development of steam power created the demand for a curriculum in mechanical engineering. Neither of these types of engineers was trained to cope with the requirements of electrical power, and so there came to be a curriculum in electrical engineering. The advent of radio communication and of electronics during the first World War and in the years that followed resulted in the establishment of electronics engineering, sometimes within the curriculum in electrical engineering and sometimes independent of it. The complexities of industrial management have created an ever increasing demand for industrial engineers and the consequent building up of a curriculum in industrial engineering. The wide industrial application of chemical processes required a type of engineer whose background was training in chemistry but who was able to design processes and plants on an industrial scale; hence we have the curriculum in chemical engineering. The advent of the airplane created an entirely new set of problems which were solved by the training of aeronautical engineers. Many of these have called for more and more science and mathematics. Such was the history of the older engineer-

Jan 1, 1953

By J. D. McClung

INTRODUCTION The ever increasing demand for coal sues that meet exacting specifications has made necessary the installation of thousands of dollars worth of crushing equipment by the coal industry. At one time the operator at- tempted to recover as much lump as possible but today he is confronted with the necessity of crushing to facilitate the mechanical cleaning process and to meet the demand for a variety of uniform sizes. As a matter of fact, about 65 percent of the coal mined in the United States today goes through preparation plants where it is crushed and cleaned. One becomes more aware of the importance of the art of comminution when it is realized that practically all of the operations in mining are involved in comminution in one way or another. Whether the coal is mined conventionally or by continuous miners it is separated from the solid by a breaking, ripping or milling action which essentially amounts to a comminution operation. Even degradation resulting from material handling from the mine working face to the preparation plant might in a broad sense be so classified, Then of course crushing is usually necessary in the plant before the coal is ready to be marketed. THEORY Despite the various comminution operations there is a lack of satisfac- tory information concerning the fundamentals of crushing and their relation to the variable factors associated with the operation. There are certain laws and theories on mechanical reduction, such as those of Rittinger, Kick and Bond that are helpful and useful. The difficulty in developing exact mathematical relationships for specific crusher applications is due to the many variable physical characteristics found in coal. Hardness, as measured by the Hardgrove grindability index, is one parameter that has been used for years to determine the resistance of coal to comminution. While the coal properties as measured by grindability are complex, recent work has shown that a high correlation exists between the grindability of some coals and their petrographic analysis. Early research on the hardness of petrographic entities from an Illinois coal2 demonstrated that durain was the hardest constituent followed by clarain, vitrain and very soft fusain. Other research demonstrated that, for different size fractions of the same coal, a wide variation in hardness commonly exists. For example, the fines in about half of 39 coals studied were softer than their corresponding coarse sues while most of the remaining coals were uniformly hard in all sizes. A few coals contained fines which were harder than their coarser constituents. These variations in hardness give insight into the heterogeneous nature of coal.

Jan 1, 1968

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10'" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,' equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,' and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970

By T. J. Bosworth

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author's knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi' made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber's4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.

Jan 1, 1959

By S. L. Couling, D. J-P. Adenis

i2) twinning in poly crystalline magnesium does not usually occur homogeneously but is concentrated in localized regions or bands inclined at about 45 deg to the stress axis. These bands of twinning are in many ways similar to the Luders bands seen in mild steel alzd Al-Mg alloys. Within a hand the percentage of the volume twinned may approach 100 with no twinning outside the band. Bands are not produced in specimens of grain size a3 x 10-= in. or in samples deformed at temperatures 300°F. Annealing of heavily twinned regions leads to re crystallization textures markedly different from those found in the starting material. The exact preferred orientation appears to depend on the starting grain size, the amount of compres-sive strain and the manner in which it is introduced. MAGNESIUM, with its hexagonal crystal structure, deforms plastically at room temperature by a variety of deformation mechanisms, one of the most important of which is (1012) twinning. In single crystals such twinning occurs on compression parallel to the basal plane or tension perpendicular to it. In wrought polycrystalline magnesium, such as rolled sheet, the preferred orientation is such that almost all the grains have their basal planes nearly parallel to the sheet surface. Therefore, if sheet material is deformed by cold rolling or by tension in the plane of the sheet, deformation of the grains by (1012) twinning is not favored. On the other hand, twins form readily on compression parallel to the plane of the sheet as in a compression test, on the compression side of a bent sample, or at the outer rim of a drawn cup. The first part of this paper deals with the morphology of (1012) twinning in polycrystalline magnesium. Some aspects of this subject were covered by Barrett and ~aller.' Of direct bearing on the work to be reported here are the comments of Jetter' in discussion to Ref. 1. He shows that Mg + 1.5 pct Mn alloy sheet when bent about a transverse axis develops a pattern of transverse bands on the surface of compression. A longitudinal section through the sheet shows that the bands are wedge-shaped and inclined to the rolling direction. The bands were identified as "outcrops of regions in which deformation is localized as the result of the reorientation brought about by (1012) twinning". The second part of the paper treats the recrys-tallization texture of the specimens twinned by compression. Magnesium deformed and then annealed generally recrystallizes with no change in orientation.1'3'4 This statement is true provided that the amount of (1012) twinning occurring during deformation is small. In an isolated observation, Anse15 has shown that, when deformation produces much (1072) twinning, annealing causes new maxima to appear in the pole figure. The second part of the paper elaborates on this point. I) MATERIALS AND PROCEDURES All of the experimental work to be reported was done using the commercial sheet and plate alloy AZ31B (nominal composition: 3 pct Al, 1 pct Zn, 0.4 pct Mn, balance magnesium). This alloy is available commercially in two tempers, -0 (fully annealed) and -H24 (partially annealed), and specimens of both tempers were used in various experiments. The average grain. diameter (AGD) for -0 temper 0.125-in. sheet is about 0.5 x 10- in.; where material of larger grain size was desired, anneals at elevated temperature were used to grow the grains. compression tests were made on a screw-driven "hard" machine. The specimens were clamped in a

Jan 1, 1964

By M. W. Legatski, D. L. Katz

The best currently available description of the longitudinal mixing properties of a porous medium is an equation of the form which relates the effective longitudinal dispersion coefficient Dp to the molecular diffusion coefficient Do, the electrical resistivity factor F, the porosity <f> and a Peclet number. If the parameters dpa and m are determined for a porous medium of known porosity and electrical resistivity factor, then a dispersion coefficient may be estimated for a given flow rate and a given gas pair. A new method, featuring on-line gas analysis by thermal conductivity and on-line data reduction by analog computation, was developed and used to determine these mixing parameters for eight naturally occurring sandstones and two dolomite samples. The exponent m of the above equation was found to vary between 1.0 and 1.5. The characteristic length dpa in the above equation was found to vary between 0.25 and 1.9 cm, with an average value of 0.4 cm for sandstones. Measurements were made on two cores in which paraffin wax had been deposited by evaporation from a pentane solution. They indicated that the presence of an immobile phase such as connate water could increase the dispersion coefficients significantly. INTRODUCTION While the petroleum and chemical industries have studied the mixing of miscible liquids flowing in consolidated porous media and of miscible gases flowing in unconsolidated porous media, relatively little data have been presented to describe the mixing of gases flowing through consolidated porous media. Such data are of particular interest to the gas storage industry. For instance, the U. S. Bureau of Mines is storing large quantities of a rich helium-nitrogen gas in contact with a natural gas in a dolomite reservoir. Since the rich gas occupies only 15 percent of the total reservoir volume, it is essential that the extent of rich gas-natural gas mixing be predicted and understood as a function of rock properties, pressure and rate of movement. This investigation was concerned only with the determination of longitudinal dispersion coefficients. It is understood that a transverse dispersion coefficient, which characterizes mixing perpendicular to the direction of flow, may be an order of magnitude less than the coefficient characterizing mixing in the direction of bulk flow.5719 It should also be recognized that the use of any dispersion coefficient is in itself a simplification. It is necessary to assume that mixing in a porous medium may be characterized by the equation for flow in a single direction. A number of authors1 l8,19 have pursued the mixing problem, not in terms of the so-called "dispersion model" described by Eq. 1, but in terms of a "mixing cell model". This model supposes that a porous medium is constructed of a large number of small mixing chambers and that the concentration of the diffusing component within each mixing chamber is uniform. Fick&apos;s law (Eq. 1) assumes that there is no gross by-passing of one fluid by another, and that there are not stagnant pockets of gas in the system under consideration as discussed by Coats and Smith.8 These assumptions are not always valid for flow through porous media and it is important to recognize the limitations upon Eq. 1. The most serious limitation upon the assumption of Fick&apos;s law mixing in a porous medium is

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.&apos;-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton&apos; argued in favor of silicification of erosion

Jan 1, 1951

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.&apos;" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-&apos; although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.&apos; This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].&apos; The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,&apos; was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,&apos; on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.&apos;-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton&apos; argued in favor of silicification of erosion

Jan 1, 1951

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&apos;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&apos;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 W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors&apos; calculations. *** AUTHORS&apos; REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth&apos;s crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth&apos;s crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955

By H. H. Hausner, H. S. Kalish

M. Hansen—This paper certainly is an interesting study. Although I have not had too much experience in the powder metallurgical methods of studying phase equilibria, I would like to say the following concerning the interpretations of the results obtained: 1. The existence of a zirconium-rich eutectic having a melting point close to 950°C and containing approximately 5 pct beryllium is well established. 2. Undoubtedly sintering of the original compacts (i.e., without repressing and resintering at 1350°C) resulted in a condition being far from equilibrium, even in the low-melting point zircon-rich region where undissolved zirconium particles have been observed. This means that only partial reaction between the component powders has taken place. 3. In preparing and handling powder mixtures for pressing and sintering, we have found that with powders differing considerably in density, and also in particle size, separation in layers of different composition may occur. This means that a concentration gradient would exist within such samples. This phenomenon may, at least to some extent, account for the difference in microstructure of the top and bottom regions of some of the sintered samples. If this is the case, density figures for some of the nominal compositions would not represent actual densities of those mixtures. 4. Fig. 1 shows that the low densities of mixtures with 40 and 60 pct beryllium sintered at 1350°C are changed to much higher densities if the products sintered at 1100°C are repressed and resintered at 1350°C, whereby an approach toward equilibrium takes place. This would mean that the low density and growth in volume is due to nonequilibrium conditions. If this is true, would it be justified, then, to conclude that "the remarkable growth of the alloys in the vicinity of 40 to 60 pct Be indicates the formation of a high-melting point phase, probably accompanied by a considerable change in volume due to a large alteration of the crystal structure from that of the original compounds"? If some compound formation has taken place already during the first sintering at 950" to 1350°C, more compound would be formed by repressing and re-sintering of the 1100" samples. This treatment, however, results in higher, rather than lower, densities. In general, the density-composition curve of alloy systems containing one or more intermediate phases is characterized by a more or less defined contraction (decrease in specific volume, increase in density) over the "theoretical" density. Does not discrepancy exist between the two statements that "growth of the alloy indicates the formation of a high-melting phase . . ." and "even at 1350°C, no indications of sintering have been observed"? 5. I am not sure that the explanation given for the fact that fig. 4 did not reveal as much eutectic as the top portions of the mixture with 2 pct Be, is correct. The density of the melt containing only 5 pct Be or even perhaps less, is not too much different from that of the nominal composition. The reason might be also that there was already some separation of the components in the pressed compact. 6. I do not understand why the microstructure of the bottom regions of the compact with 5 pct Be (fig. 6) is so different from that of the top regions (fig. 5). The compact was melted on sintering at 1100°C. Its composition lies close to the eutectic point. There should be at least some lamellar structure in the bottom regions too; otherwise, the composition of top and bottom must have been very different after sintering, because the eutectic is said to extend as far as the composition ZrBe2. In case the white and gray areas of fig. 6 are both gamma, and the black areas undissolved zirconium, this composition would be close to the phase coexisting with zirconium, that is, ZrBe2, according to the hypothetical diagram, or a compound richer in zirconium. 7. Figs. 9 and 10 are not mentioned in the text. 8. The great difference in microstructure of the composition 20 pct Be of figs. 8 and 14 on one side and fig. 15 on the other side proves that sintering at 950" and 1100°C results only in partial reaction of the powers. 9. The mixture with 60 pct Be (fig. 19) seems to consist of two phases, rather than one phase, one interspersed in a matrix of another. 10. The statement that the eta phase "may be an intermetallic compound or the product of a peritectic or monotectic reaction" seems to be misleading, because the product of a peritectic or monotectic reaction in this region of the system must be an intermetallic compound. 11. If there is some solid solubility of Be in alpha and beta-Zr, it would be expected to be higher in beta-Zr (b.c.c.) than in alpha-Zr (h.c.p.). The temperature of the polymorphic transformation of zirconium then would be lowered, rather than increased. In accordance with this, Battelle has found that the transformation point of titanium is decreased by beryllium. 12. In case the phases present in alloys with 80, 90, and 95 pct Be are identical (which appears to be correct), it is striking that the relative amounts of both phases (eta and beryllium) are not too different within this wide range of composition. With 60 to 65 pct Be

Jan 1, 1951

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,&apos; fractional crystallization,&apos; and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported&apos; to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman&apos; in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By James Boyd

In critical times such as the present, when the whole world is agitated by the aftermath of war and the road to peace is blocked by seemingly insurmountable obstacles, it is fitting that we should pause to take inventory of the material resources essential to our national security. Our status as a world power, in peace as well as in war, is intrinsically bound to the availability of minerals, for the foundation of our industrial and economic structurewhich in turn largely determines our military potential and our limits of national prosperity-rests on our ready access to economic sources of iron, copper, lead, zinc, manganese, bauxite, and at least threescore of other metals, minerals, and mineral fuels. By applying the well-known facts of mineral resources to recognized fundamental concepts of preparedness, we can obtain a- clearer picture of the essential needs of our country. Historically, the lure of minerals and other raw material resources has all too frequently led nations to policies of imperialism and war. For more than a century the staking of colonial territory for new sources of raw materials has been a primary objective of many nations. These national policies. of aggrandizement were accelerated by increasing industrialization. The nations, in their aggressive search for

Jan 1, 1948

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-&apos; had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.&apos; Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By Walter S. Tower

IN making comparisons of steel industries, one country with another, the convenient common denominator is annual capacity to make raw steel in the form of ingots. It is always necessary, however, to remember that there are different methods of figuring such capacity. For most countries no official figures on capacity are available, and the only authentic data on production are now six or eight years old. But in spite of those limitations on the accuracy of statistical comparisons, any flaws in the figures are probably not serious enough to alter materially the larger conclusions which may be drawn from them.

Jan 1, 1944