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By George W. Bain

Some problems concomitant with commercial exploitalion of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service department wants defects rectified and the cause determined to avoid recurrence The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character. Geological Problems The geological problems deal almost exclusively with the size of blocks. Size across the deposit is limited by thickness of individual beds. and along the strike by the space between crosscutting joints. Frequently the vertical depth of a block is reduced by exfoliation shells arising from spontaneous expansion. All these factors require consideration in developing a deposit to fill an order. Thickening of Marble Beds The limestone beds that became the marble deposits of the northern Appalachians and of the Yule locality in Colorado were seldom homo-

Jan 1, 1941

By George W. Bain

Some problems concomitant with commercial exploitalion of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service department wants defects rectified and the cause determined to avoid recurrence The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character. Geological Problems The geological problems deal almost exclusively with the size of blocks. Size across the deposit is limited by thickness of individual beds. and along the strike by the space between crosscutting joints. Frequently the vertical depth of a block is reduced by exfoliation shells arising from spontaneous expansion. All these factors require consideration in developing a deposit to fill an order. Thickening of Marble Beds The limestone beds that became the marble deposits of the northern Appalachians and of the Yule locality in Colorado were seldom homo-

Jan 1, 1941

By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By H. W. McQuaid

IT IS usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effect of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide can result in total unfitness of low-carbon steel for, case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 2, 1922

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

* Kennecott Copper Corp. gets Charles R. Cox as president on Jan. 1. Mr. Cox is resigning his position as president of Carnegie-Illinois to take the new post with Kennecott, left vacant by the death of Mr. Stannard in September. •The ECA signed a contract in December to advance X3,600,000 to Newmont Mining Corp. to aid development of lead and zinc mines in French Morocco. The funds are to be repaid in lead and zinc for the United States' stockpile over a period of seven years. The mines are owned by the Societe des Mines de Zellidja, with which organization Newmont is associated. • Under the direction of John M. Brooks, Jr., general manager, the Matahambra mine in Cuba, will probably produce sufficient tonnage to make 4 million lb of copper per month during 1950. The grade is presently running between 7 and 10 pet. •S. H. Ash reports that the fatality rate per million-man-hr for the anthracite industry for 1949, through November, is 0.78. This is 15 pct better than that achieved during 1948, which was the lowest fatal injury rate in coal mining history. The first full year on record without a major disaster was recorded in 1949 (p. 34). •The Atomic Energy Commission has authorized the production of 200 lb of uranium metal for use under AEC license in non-Commission research projects. •A national survey of projected 1950 purchases of new machine tools, machine tool accessories, materials handling equipment, etc., just completed by the American Society of Tool Engineers reveals that, of the companies reporting, 80 pct state that they plan to buy either more equipment or the same amount as in 1948. • Armour Research Foundation is conducting investigations for the use of clay and shale deposits to make lightweight aggregates. The material is heated until it expands and forms material suitable for mixing with cement which it is hoped will be lighter, stronger, have better insulating qualities and will lower the cost of concrete. •In the first six months of 1949 the bituminous coal miners' average hourly earnings were $1.94 -as compared with X1.392_ national average for all manufacturing. Average annual earnings of full-time employees in the bituminous coal mines in 1948 were $3387 as compared with $2809 for all industry. •LaSalle Business Bulletin reports: "year ends on a rising trend in industry and trade ... nearly record-breaking demand from almost all sources keeps business high... most indicators but little below postwar peak... forces keeping activity high arestill powerful--changes in general business conditions likely to be slow and moderate." •Office of Internal Trade of the Commerce Department requests that technical data significant to the national security which is to be sent outside of the United States be submitted to it for an official opinion on the desirability of transmitting such information. This voluntary compliance program is part of our national security control. • Blast furnace slag reduced to 12 to 16 mesh is being used for sanding track at the Mont Coal mines of Armco. The slag replaces silica sand which caused silicosis. It has proved so effective and cheap that tests are being made to use the slag for rock dusting.

Jan 1, 1950

By N. F. Fiore, M. C. Mangalick

DISLOCATION damping in single crystals is orientation dependent.&apos; If dislocations are distributed uniformly over all the slip systems in a crystal, and if each dislocation contributes identically to the damping process, then a damping loss or decrement 6 arises. In fact, however, for a crystal of axial direction (hkl), dislocations on certain slip systems are oriented to make a larger contribution to the damping loss than are dislocations on other slip systems. Thus the measuring damping, 6 (hkl) is proportional to an orientation factor (hkl), which weights the ability of each slip system in the crystal to contribute to the total damping. If it is assumed that dislocations are distributed uniformly on all slip systems, then for a given orientation of an fcc crystal this factor is determined2,3 by the three nonzero elastic constants Cll, C12, and C44 and the density p. In this communication measured values of elastic constants for two Fe-18Cr-Ni alloys are reported, and the dislocation damping results on two different orientations of each alloy are analyzed for orientation dependence. Elastic constants were determined by measuring the ultrasonic velocities of one longitudinal and two shear waves in (110) direction of the fcc crystals.4 Variation of velocities with the change in orientation is very small for (110) orientation,3 and so this direction is ideal for orientation factor and comparative damping measurements. Experimental Procedures. The nominal compositions of the alloys studied are given in Table I. These alloys were vacuum-melted and vacuum-cast from high-purity materials at U.S. Steel Applied Research Laboratories. The single crystals were grown by the modified Bridgeman technique. The specimens were homogenized at 1350°C for 20 hr, cut to shape and size with a spark cutter, and then annealed at 1100°C for 20 hr prior to use. In the KHz frequency range, the Marx composite piezoelectric oscillator was used to obtain the damping. The ultrasonic pulse technique was used to measure the ultrasonic velocities and the attenuation in the MHz frequency range. M.c.mANGALICK,-- StudentMemberAIME,formerly Research Assistant, University of Notre Dame, is now with Casting Laboratory, Chase Brass and Copper Co., Cleveland, Ohio. N. F. FIORE, Associate Member AIME, is Assistant Professor, Department of Metallurgical Engineering and Materials Science. University of Notre Dame, Notre Dame, Ind. This communication is part of a Ph.D. thesis presented by M. C. MANGALICK to the Graduate School of the University of Notre Dame. Manuscript submitted May 20. 1968. IMD Elastic Constants. Table I gives the values of the ultrasonic velocities. Values of C11, C12, and C44 calculated from these velocities are also given in Table I, and it is evident that there is very little variation in C11, C12, and C44 with nickel content. This slight variation may be attributed to inaccuracies in velocity measurements and practical differences in the orientations of the specimens. For example, in B the time interval for vl was 2.4 ± 0.05 sec giving an error in v1 of 0.235 x or 0.005 in. per sec. The elastic constants obtained by pulse technique were tested by calculating E<110>, Young&apos;s modulus for the (110) direction, from the equation: This value was compared with the value computed from the resonance bar measurements in which where fr is the resonance frequency and I, is the length of the specimen. In all cases, the values calculated from the ultrasonic velocity measurements

Jan 1, 1969

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5&apos;6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.&apos; We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

By Pol Duwez, Spencer R. Baen

A LTHOUGH the practical importance of Fe-Cr--iV Mo alloys has long been recognized, constitution studies have been limited to a few alloys within rather narrow ranges of composition. The purpose of the present study was to establish the phase boundaries in the ternary diagram at a temperature of 1200°F (650°C).* The identification of phases and the determination of phase boundaries were based primarily on X-ray diffraction measurements and occasionally on microscopic observation. The methods used for locating the phase boundaries were essentially those described in detail by Andersen and Jette,&apos; and by others.&apos;, The compositions of 180 alloys, prepared by powder metallurgy techniques, are shown in Fig. 1. The chemical analysis and mesh size of the powders which were used for the preparation of the alloys are given in Table I. The powders were mixed for 48 hr or longer, then compacted under 80,000 psi in a %-in. diam steel die. Each specimen weighed approximately 5 g. The compacts were sintered for 4 hr at 2500°F (1371°C) in an atmosphere of pure dry hydrogen (dew point near the temperature of liquid nitrogen). An open tray of chromium powder was placed upstream of the compacts to act as a "getter" for the last traces of oxygen or water vapor. In many cases this chromium powder was bright after sintering. Occasionally the upstream side of the powder was slightly greenish, but in all cases the downstream side was metallic. Some of the alloys contracted during sintering and some expanded as much as 20 pct. The latter alloys, which in all cases were brittle, were crushed in a tool steel mortar, repressed, and resintered for 4 hr at 2500°F. After sintering, the alloys were aged for ten days at 1200°F (650°C) in evacuated (105 mm Hg or better) fused silica tubes and were cooled rapidly to room temperature following the aging treatment. The use of the powder metallurgy technique in preparing alloys for structural investigation offers a simple method &apos;of avoiding contamination or non-homogeniety which could result from a melting operation. It is very often possible to dispense with chemical analysis of the alloys which have been prepared by the powder metallurgy method. In lieu of chemical analysis, it is necessary to determine the weight of the compact before and after sintering. The chemical composition of the alloy may be considered as that of the green compact, within the limits of accuracy determined by the loss of weight during sintering. In phase-diagram studies it is important to achieve homogeniety in structure, whether the alloys are prepared by powder metallurgy or by melting. Homogeniety means complete diffusion during the sintering of the alloys which are prepared by powder metallurgy. It has been found from experience that the best criterion for establishing the completeness of diffusion is the sharpness of the X-ray diffraction patterns. This criterion has been used throughout the present study. The X-ray diffraction data were obtained using powder cameras of either 214.86 or 71.62 mm diam. Copper, cobalt, or chromium Ka. radiation was used, the choice being based on the alloy composition. The powder samples were obtained by filing or crushing, depending on whether the alloy was ductile or brittle. In some cases, the powder was annealed for 4 to 6 hr at 1200°F in vacuum. The measurements were corrected for film shrinkage and absorption. The large camera, in which the film is mounted

Jan 1, 1952

By C. A. Siebert, O. S. Duffendack, A. W. Herbenar

IN metallurgical problems involving the study of equilibrium in binary systems, the ,existence of an additional vapor phase, due to the presence of a volatile component in the alloy, has often been neglected. This is well indicated by the modified form of the phase rule, usually accepted in condensed systems in which pressure is not considered as a degree of freedom. In many cases the vapor pressure of the volatile component is exceedingly small and for all purposes can be considered negligible, in which case this form of the phase rule is applicable. However, alloys containing Hg, Cd, Zn, or Mg, tend to show very marked equilibrium vapor pressure, even in the solid state, and therefore present cases where the modified form of the phase rule no longer holds true. A quantitative determination of the vapor pressure of zinc in alpha brasses is not only of practical interest because of the loss of zinc in the processing of these alloys, but also of theoretical interest in that such measurements provide a means of applying the principles of theoretical physics and physical chemistry to problems of applied metallurgy. A number of investigators have reported vapor pressure measurements of zinc in alpha brasses. Hargreaves1 made extensive measurements which were used by Birchenall and Mehl² and Guttman³ for the determination of activity coefficients of zinc in alpha brasses. Hargreaves1 used a differentially heated quartz tube and measured the condensation temperature at one end corresponding to the temperature of the heated brass at the other end. Birchenall and Cheng outlined the condensation method of obtaining vapor pressure of zinc and Cd over some of their silver alloys." The primary object of the present investigation was to increase the range and accuracy of the vapor pressure data for the alpha brasses. Preparation of Alloys: Six alloys were prepared from Bunkerhill zinc and O.F.H.C. copper, both of 99.99 pct purity. The cast ingots were annealed for 24 hr at 550°C, scalped, cold rolled 40 pct and annealed for 50 hr at 550°C. The annealed bars were then surface ground and degasified for 30 min at approximately 550°C in an induction heated vacuum furnace. The surface of the bars was removed before milling the bars into relatively fine chips for chemical analysis and samples for the equilibrium cell. The analyses of the six alloys are given in table I. Experimental Method: The vapor pressure of zinc over the various alloys at a number of temperatures was determined from absorption spectra data. The spark source was produced by means of a high tension discharge between two electrodes of pure zinc. The design of the absorption vessel is shown in fig. 1. The vessel was constructed of transparent quartz which transmits the whole of the visible spectrum and the ultraviolet down to a wave length of 2000 A. The thickness of the vapor space was set at 0.8 mm so as to permit a relatively wide range of measurements without altering the vapor space, and thereby necessitating recalibration of the vessel. The furnace used for heating the absorption vessel consisted of a split wound furnace as shown in fig. 2. The spectrograph used in obtaining the transmitted zinc spectra was a double prism type especially designed for a region of 2500-3500 A. A step diaphragm used in conjunction with a tungsten filament provided the necessary intensity patterns required for calibration of the photographic plates.

Jan 1, 1951

By J. G. Richardson, K. H. Coats

During the initial growth of a gas bubble in an aquifer storage reservoir the injected gas tends to override the water. The resulting low displacement efficiency and high rate of gas travel down-structure make it difficult to maintain water-free production. This paper illustrates the use of two-dimensional, two-phase calculations to simulate this gas-water displacement. Calculations were performed for a stratified aquifer and for several homogeneous sands differing in permeability, porosity and thickness. Results are discussed and compared with performance predictions obtained from the simpler Buckley-Leuerett and Dietz formulas. This comparison indicates the necessity for the two-dimensional calculations in realistically simulating the gravity override of the water by injected gas. INTRODUCTION In recent years natural gas has been stored near markets in aquifers where insufficient storage capacity is available in depleted fields. Operators of these aquifer storage reservoirs have encountered technical problems relating to the gas-water displacement accompanying initial growth of the gas bubble. Injected gas tends to override the water, with a resultant low displacement efficiency and high rate of gas travel down-structure toward spill points. Low displacement efficiency makes if difficult to sustain water-free gas production. Sometimes the fingering of gas down-structure may be so pronounced that the injection rate must be severely curtailed, which excessively lengthens the time required for bubble growth. This paper is concerned with estimating — for given aquifer characteristics and fluid properties — the displacement efficiency, rate of gas movement down-structure and rate of gravity drainage of water behind the gas front. Several published articles relate to simulative capability necessary to handle this problem. The Dietz formula1 and Buckley-Leverett2 method have some applicability to the problem; Woods and comer3 reported one-dimensional, radial calculations which accounted for the two-phase flow of gas and water. Most recent research directed toward understanding aquifer behavior in relation to gas storage has concentrated on single-phase flow in aquifer.4 Douglas, Peaceman and Rachford5 presented a method for calculating multidimensional two-phase flow in reservoirs; their method has been applied in work reported by Nielsen and Tek,6 Blair and peaceman7 and Goddin.8 Refs. 5 and 7 show comparisons between experimental data and calculations similar to those employed here. One purpose of this paper is to illustrate the use of two-dimensional, two-phase flow calculations in simulating the difficult problem of water displacement by gas in a vertical cross-section. The pronounced fluid density and viscosity differences combine with the disparity in horizontal and vertical dimensions of the cross-section to pose one of the more difficult problems in reservoir simulation. The calculations described account for capillary and gravity forces, relative permeability and reservoir heterogeneity. An example reservoir is described and calculated results are presented for a variety of injection rates and values of permeability, reservoir thickness and dip angle. A second purpose is to compare the two-dimensional calculations with results obtained from the Buckley-Leverett and Dietz formulas. For this reason most calculations were performed for a simplified example reservoir to which the latter techniques might reasonably be applied. However, the computer program employed applies equally well to cases involving arbitrary spatial variations of permeability, porosity, reservoir thickness and dip angle.

By R. A. Ritter, J. P. Batycky

A numerical technique has been developed to permit estimating the pressure gradient associated with laminar flow of thixotropic liquids through long Pipelines. For this purpose the pipeline is divided into a number of radial and longitudinal increments within which rheological properties of the fluid may be considered as constant at any time. Then, provided only that the fluid flow curve is defined at every duration of shear, it is possible to predict the instantaneous pressure gradient at any cross-section along the pipeline for each desired flow rate and pipe size. The technique consists of an iterative integration of shear rate to establish the appropriate value of the wall shear stress at each location. Consistency of fluid in the increment is determined by the flow history of that increment, while the radial flow associated with variations in velocity profile is accounted for by adjusting the width and radial position of the increment. A number of pressure profiles, computed at each of several flow rates, provide a convenient basis for pipeline design and pump selection. INTRODUCTION In recent years considerable attention has been given to predicting pressure drop associated with the isothermal laminar flow of time-independent non-Newtonian fluids in pipes and annuli. 6,11,12 The approach generally has been to develop analytical relationships between flow rate and pressure drop based on simple constitutive models which hopefully provide an approximate description of the rheological properties of the fluid. Analytical solutions are highly desirable since the influence of all pertinent parameters can be readily determined. Unfortunately, however, this approach is restricted to simple flow geometries and- frequently leads to erroneous results due to inadequacies in the model. In certain cases a solution may be obtained through applying appropriate numerical techniques.l,14 For example, a digital computer program is available for predicting the velocity profile and pressure drop encountered by any Newtonian or time-independent non-Newtonian fluid flowing under laminar conditions in a cylindrical pipe or annulus.l In this paper the consistency behavior of the fluid need only be described in terms of basic rheological data. Analyzing flow systems involving fluids with time-dependent rheological characteristics is considerably more complicated since substantial changes in consistency may occur because of sustained shear action. This sensitivity to shear frequently persists for several hours. Consequently, variations in pressure drop and/or flow rate resulting from the aging process and addition of unsheared or partially sheared fluid to the system must be considered for purposes of pipeline design. This paper outlines a numerical method for predicting the transient and steady-state laminar flow behavior of a thixotropic liquid in a pipeline of arbitrary length (i.e., at a specified constant flow rate, the instantaneous pressure gradient may be determined at any time after start up and at any location along the pipeline). Several such pressure gradient profiles, computed at several flow rates, may be combined to produce a complete portrait of the system response. This flow portrait provides a reasonable basis for pipeline design and for selecting a suitable pump characteristic. TIME-DEPENDENT RHEOLOGICAL BEHAVIOR The most familiar time-dependent rheological properties are those exhibited by thixotropic liquids. Many of these materials, particularly thixotropic crude oils, generally display an apparent yield stress in that a finite pressure gradient is required to initiate flow. Then, under the influence of sustained shear at a constant shear rate, the consistency systematically decreases to some final limiting value. The shear stress obtained at

By David Cornell, Yusuf K. Sukkar

The fundamental differential equation for fluid flow has been rearranged, integrated numerically for natural gases, and the results presented in tabular and graphical form suitable for the direct calculation of vertical gas flow problems. The integration is rigorous except for the use of a constant average temperature. Both static and flowing bottom-hole pressures may be calculated by (his method without resort to trial and error procedures. INTRODUCTION Bottom-hole pressures can be determined either by direct measurement with a bottom-hole pressure gauge or by calculation. Since measurement with a bottom-hole pressure gauge is costly, calculation of bottom-hole pressures is to be preferred when possible. Calculation involves knowledge of the wellhead pressure, the properties of the gas, the depth of the well, the flow rate, the temperature of the gas, and the size of the flow line. These quantities must be combined in a suitable equation for vertical flow. Several equations have been developed for the purpose of calculating gas flow through both horizontal and vertical pipes1,2,4,5,6,7,8,9 These equations all have the basic differential equation for flow as their starting point. They differ only in the assumptions which are made in order to simplify the integration step. The bottom-hole pressures calculated using any of the better known equations are in good agreement with bottom-hole pressures calculated by a more rigorous but considerably more tedious stepwise integration method. All of these methods, however. require a trial and error solution for the calculation of flowing bottom-hole pressures. The purpose of this paper is to present a method which provides a direct solution of static and flowing bottom-hole pressures without use of a trial and error solution. At the same time the method involves fewer simplifying assumptions than any of the previous methods used, except lor the lengthy stepwise method. The derivation of any practical flow equation begins with the basic differential equation which is rigorous for almost all flow problems. The five terms in Equation 1 represent the potential energy, the potential energy of position, the kinetic energy, the shaft work done, and the energy losses due to motion of the fluid respectively. Equation 1 reduces to Bernoulli&apos;s theorem for the case of horizontal flow of an incompressible fluid, no work done, and no energy losses due to friction. In the present case, the term (v) (dv)/(g,.) can be shown to be quite negligible compared to the other terms, and is therefore neglected in the derivation. The term — dws includes work done by a pump or turbine in the system and is zero in this case. The frictional losses in the pipe are included in the term — d(lw) which is expressed in terms of the Moody friction factor as in Equation 2. (f) (v2) (dL) d(lW) = (f)(V2) (dl)/(2) (g) (d) The specific volume of a gas can be expressed in terms of the temperature, pressure, molecular weight, and compressibility factor. The velocity of the gas can be expressed in terms of the weight rate of flow, the specific volume, and the dimensions of the pipe.The reduced pressure Pr is to be used because z can be expressed as a function of Pr and Tr alone for most natural gases:

Jan 1, 1956

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the &apos;ultimate recovery somewhat increased&apos; The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3&apos; per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb&apos; has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- &apos;&apos; watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,&apos; it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.&apos; An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100&apos;~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the &apos;ultimate recovery somewhat increased&apos; The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3&apos; per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

DEVELOPMENT of a chemical process for the extraction of pure metals from mill concentrates or metal scrap has progressed beyond the pilot plant stage and may prove an important adjunct to present smelting and refining methods if initial commercial operations prove economically successful. Developed by the Chemical Construction Corp., the new process involves the treatment of oxide and sulphide ore concentrates by chemical methods, instead of the usual smelting and refining techniques. Several of the many applications are now scheduled for commercial use. Refiners using the new process will prepare ore concentrates by standard flotation methods, introduce the concentrate as a slurry into an autoclave along with water and an acid or ammonia. From the resulting leach solution, recovery of individual metals is made by use of suitable reducing agents. By varying conditions during treatment, different metals in the ore are produced separately as pure powders, which may be pressed into forms ready to market, or in the case of copper, extruded as rods or pipe. The reagents are generally recovered. By manipulating the variables during reduction, selective separation of nickel, and/or cobalt, and/or copper can be made simultaneously. The separation is a continuous operation. Low metal prices are not immediately in view because of the tremendous demand at this time. However, reduced metallurgical treatment costs will allow economical mining of orebodies with lower metal content, permitting increased production to meet demand. Although the practical horizon for use of the new process appears to be limitless, one factor may enter into its employment. Just how low grade a concentrate can be economically used is unknown. In addition, for present practical considerations, only metal below zinc in the electromotive series may be processed. Each commercial application requires specific technique adaptation and pilot-plant data for engineering design. A nickel-cobalt-copper process has been researched and piloted in collaboration with Sherritt Gordon Mines, Ltd., for the firm&apos;s Lynn Lake properties. In addition, processes were tailored for cobalt concentrates of Howe Sound Mining Co., and National Lead Co., in view of the urgent need for this specific metal. Major General William N. Porter, president of Chemical Construction, says of the new process, "piloting experience has shown that production cost, from ore concentrates to pure metals should be considerably below current costs." Other savings may be realized by cutting transportation and personnel costs, and by reducing the time lag between mining and pure metal from months to a matter of hours. First commercial use of the process will start sometime this summer. Chemico is slated to finish building a $2.5 million cobalt refinery for Howe Sound Mining near Salt Lake City. The plant is expected to raise world cobalt production by 40 pct. The plant will process 35 tons of 20 pct cobalt concentrates from Howe Sound&apos;s Blackbird mine near Cobalt, Idaho, daily. Yearly production is expected to reach 2000 tons of pure metal, about one half of U. S. consumption in 1950. Steps in the Howe Sound application of the process are: 1. Acid oxidation leach. 2. Filtration (residues thrown away are insoluble compounds-gangue, iron, arsenic). 3. Cementation (for Cu removal because Cu content is too low for recovery). 4. Reduction from ammoniacal solution. 5. Separation of Co and Ni as mixed metals (95 pct Co and 5 pct Ni). 6. Recovery of ammonium sulphate. Under construction at the Fredericktown, Mo., mine of National Lead is a $5 million refinery sched- [ ]

Jan 1, 1952