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By L. D. Jaffe, M. R. Norton, J. H. Hollomon

IN the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermal? decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work. § Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. METHOD In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1946

By E. Ray Webb

A interest to geologists and to mining and petroleum engineers is a laboratory method for determining the dip and strike of sub- surface structures, as well as the direction of fault planes traversing them. The information is derived by making use of the magnetic properties of borehole cores which must show visible representations of bedding or fault planes. Complete knowledge of these factors aids greatly in the successful exploitation of both ore and petroleum deposits.

Jan 1, 1940

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959

By Lincoln F. Elkins, John T. Cooke

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By John T. Cooke, Lincoln F. Elkins

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By Lawrence Burkhart, S. B. Joo

Axially unsymmetric ordered circulation patterns on the surface of a hemispherical constant volume drop with forced Internal motion were considered as a manifestation of hydrodynamic instability, which was affected by internal flow as well as by the properties of the interface A simplified mathematical model was analyzed In order to study the mechanism of onset of interfacial circulation from a non-circulatory basic state. Values of the critical Reynolds numbers were obtained when the basic state became a fully developed rotational flow and the values changed for different interfacial properties. The work describes a heretofore unreported surface flow pattern on drop surfaces From a practical point of new, any motion in the interface of a droplet can have a significant effect of mass transfer rates in solvent extraction processes Although surface motion in droplets actual processing equipment is very complex, continued study of the fundamental nature of such phenomena should ultimately lead to more effective equipment design procedures.

Jan 1, 1981

By Franklyn Oatman

IN order that the conditions which obtain in an oil well may be readily understood, a brief description of a typical California well and. a number of the phenomena accompanying same will be given. That the necessity for the exclusion of water be realized, the effects of water intrusion, a description of methods of prevention, and a discussion of causes of failure will be presented, followed by a summary and recommendations. Fig. 1 shows a section of a typical well which illustrates the relation of oil sands to overlying strata. It indicates a deep water sand separated from the oil sand by shale, and the proper place for the final shutting off of water. In this well a comparatively thick stratum of compact shale protected the oil from overlying water so that the operation of landing the water string was a simple matter. In some wells the protecting stratum may be only from 3 to 5 ft. thick and very careful operation is necessary in order to land the water string of casing properly and not puncture through to the oil sand. The cases just cited are common, but occasionally, after excluding overlying water, productive oil sands are drilled through in the expectation of finding more productive underlying sand, and a water-bearing stratum is tapped. In this case the problem is the reverse of the normal; water must be prevented from ascending rather than descending. A discussion of well-drilling methods is not within the scope of this paper, except such operations as pertain to shutting off of water. A brief outline of the several conditions which may accompany drilling follows. Some or all may be present in any particular case. The direct relation of these to prevention of intrusion will he discussed in detail further on. In drilling, the hole. becomes more or less irregular in shape, and rough, and as the casing follows the bit into the well it does not fit snugly against the walls. As a result, water may descend between the casing and walls of the well. If a circulation pump is not used during drilling, the hole is simply punched through and the pulverized material removed from the well by means of a bailer. If circulation is maintained there is a continual flow of water down inside the casing and up around the outside between the pipe and the walls of hole. This keeps an open. space around the pipe.

Jan 3, 1914

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By Allen D. Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITON OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By Frederick Prime

In this second supplementary list no titles to which an * is pre fixed hare been seen by tlie compiler; and he will be most thankful to have any omiesisne or inaccuracies in the list sent to hiin to be ptiblisi~cd as a third supplement in the next volume of the actiotra. The author is indebted to Prof. J. J. Stevenson, of New Tork, Prof. P. R. Uhlcr and John 'CV. M. Lee, Esq., of Balti more, and Lloyd P. Smith, Esq., of Philadelphia, for valuable assistance. office, allkntorn iron compaxy, 30 South Third Street, Philadelphia, September 5th, 1881. Alabama. Geologiml Survcy of Alabama. report of Progress for 1879 and 1880, by Eugene A. Smith, State Geologist. Montgomery, 1881. 8vo., 158 pp., and 2 maps. California. Omit Report of Hon. T. Butler Ring, iu sopplemeut I. For Trask's Geology and Illdustrial honrecp, etc., in Supplenlvut I., read Tyson's, etc. Fremont's Menloir on Upper Califijrnia, is also published as XXXth Congress, lat Session. Senate Ms. Doc., No 148, and has a map. For Randall's Report in Supplement I, rend Report of the Special Committee in favor of a Geological Snrvey, subrn-itted by Mr. Randall, April 24th, 1861. n.d., 1851. 8cWo., 19 yp. XXXIst Congress, 1st Session, Sen. Ex. Doc., No. 47, Part 2 [Part 1 is Tyson's Report.) RejW of the Secretary of War in further compliance with the Resolution of the Senate?, calling for Colbies of

Jan 1, 1881

By Arthur Baker III

The orebodies are long bedding-plane lenses of chalcopyrite and sphalerite, associated with garnetite masses. Most of the orebodies are within a 50-ft thickness of Cambrian limestone; other Paleozoic limestones and dolomites are locally metamorphosed but only slightly mineralized. Pre-mineral faults are numerous, but shallow folds were the main ore-localizing structures. JOHNSON camp is in the northwestern part of Cochise County, Ariz., about 50 miles east of Tucson. The nearest major mining districts are Tombstone and Bisbee, respectively 27 and 50 miles to the south, and the Superior-Miami-Globe-Ray porphyry copper group, about 90 miles northwest. Like many mining camps of the Southwest, Johnson camp is said to have been worked by the Spaniards. The first production on record was in the early 1880's, when an unknown amount of oxidized copper-silver ore in the Peabody mine was mined from replacement orebodies in the Pennsyl-vanian Naco formation. From 1904 to 1911 outcropping oxidized ores in the Cambrian Abrigo formation were worked, and an estimated 100,000 tons of copper ore were shipped. In 1912 the first large sulphide orebody of the district, the Republic Manto orebody, was discovered, and in the following few years some 250,000 tons of predominantly sulphide ore were shipped. The average grade of this ore was approximately 4.5 pct Cu, 6 pct Zn, 0.8 oz. Ag, and 0.001 oz Au. The Republic, Copper Chief, and Mammoth mines were the principal producers during this period. Mining ceased in the district after 1920, and until 1943 only small-scale leasing operations were carried on. In 1943 all the mines that had been productive were acquired by the Coronado Copper and Zinc Co., the present operators, and in the 10 years since that time the district production has amounted to approximately 350,000 tons of milling ore averaging 2 pct Cu and 6 pct Zn. Most of this ore was produced from the Republic and Mammoth mines, but since 1950 a large part of the production has been from the new Moore mine. The total known production from the district, then, is about 3/4 million tons of copper and copper-zinc ore of low grade. All of this ore was produced from orebodies associated with garnetite in the middle member of the Cambrian Abrigo formation. In addition to this known production, an unknown tonnage of ore was extracted from the Peabody mine orebodies that lie in the Pennsylvanian Naco formation. Published information on the geology of the district is limited. Aside from brief references in various mining journals, only three papers on the district have been published.1-3 One of these is a U. S. Bureau of Mines report on a diamond drilling program, one is a brief paper on the general geology of the district, and the third is a report on geochemical experiments, with a section on the occurrence of the orebodies. The last two are by John Cooper, of the United States Geological Survey, who has done much detailed work in the area. Stratigraphy The rocks of the mineralized area are Paleozoic sediments ranging in age from Cambrian to Penn-sylvanian. Several disconformities are present in the stratigraphic column, the most important one being between the Cambrian Abrigo formation and the Devonian Martin formation. There are no angular unconformities. Within the district, the Paleozoic sediments lie in a fairly uniform monocline, striking northwest and dipping 30" to 50" northeast. This local monocline is part of a domal struc-ture centered in the Little Dragoon mountains to the southwest. The Texas Canyon stock, a quartz monzonite body intruded probably during the Laramide revolution, lies south of the mineralized area (Ref. 2, p. 33). The Paleozoic rocks dip away from the stock, and on the surface are separated from it by at least 1500 ft of Pre-Cambrian rocks. The outcrop pattern of the northeastern edge of the stock suggests that it may dip gently northeastward, passing below the mineralized area at moderate depth. No quartz monzonite has been found in mine workings or diamond drill holes, which reach to depths of 1000 ft. The only igneous rock found in the mineralized area is a lamprophyre dike cutting the Naco limestone in and near workings of the Peabody mine. With the exception of the lowermost beds—the Bolsa quartzite and the shaly lower member of the Abrigo formation—the Paleozoic sediments are predominantly carbonate rocks, Fig. 1. The middle member of the Abrigo formation, which contains the principal ore-bearing beds, is limestone, with thin shale partings throughout most of its 250-ft thick-ness. Near the top of this member is a sandy bed some 25 ft thick. The upper member of the Abrigo formation and the lower half of the overlying Devonian Martin formation are dolomitic, with num-

Jan 1, 1954

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960

By Warren Howes, C. O. Anderson, Robert E. Illidge, M. D. Harbaugh, S. J. Burris

The Tri-State zinc-lead mining district embraces an extensive area, including the northeastern part of Ottawa County, Oklahoma, the southeastern part of Cherokee County, Kansas, and adjacent portions of Missouri, mainly in Jasper County. The Oklahoma-Kansas portion of the district, in the vicinity of Picher, Okla., has been the principal producing area since 1917, and the present milling practice in that section is the subject of this paper. This district is the largest zinc-producing field in the United States. In 1926 it produced 55 per cent of the nation's zinc and 15 per cent of its lead, and in 1933 it produced 35 per cent of the zinc and 10 per cent of the lead. From 1842 to 1933, inclusive, the total output of the district was 18 1/2 million tons of zinc and lead concentrates valued at 818 million dollars. Of this production, the Oklahoma-Kansas, or Picher, field yielded over 9 million tons valued at over 400 million dollars. Mining operations in the Oklahoma-Kansas field near Picher and Baxter Springs began in 1915. The mills built it that time consisted merely of gravity concentration plants employing jigs and tables and the same flow sheets as had proved satisfactory with the free-milling ores such as were mined in the Joplin-Webb City fields in Missouri. The Kansas-Oklahoma ores proved to be much richer but also more refractory to treatment than those in the Joplin area, and contained a considerable percentage of zinc mineral not freed by the amount of crushing usually practiced in preparing the ores for jigging. Thus the old Joplin type of mill, with its usual two or four jigs and a few tables, proved inadequate and resulted in excessive tailings losses sometimes as high as 50 per cent

Jan 1, 1935

By John Wellington Finch

In August, 1927, the writer examined certain copper deposits in New Mexico1 which occur in beds of sandstones and shale, and in connection therewith reviewed the literature upon deposits of this type. Such deposits are known and have been reported upon at various points in Texas, Oklahoma, Arizona, Colorado, Wyoming and Utah, but in New Mexico they have been given more development than elsewhere and apparently occur there more conspicuously than in the other states. Some 25 years ago the writer examined deposits of similar origin in northern Arizona and more recently other deposits in western and southwestern Colorado, and these examinations have led him to realize how widely scattered are the deposits and how generally noncommercial they are. On superficial development, to one without a comprehension of their geologic nature, they are alluring on account of occasional small amounts of high-grade ore and much misplaced capital has been expended upon them. This paper, therefore, aims to present briefly certain theories of genesis, some details of which may possibly be new, and to lead up to practical conclusions which may be useful to other geologists and engineers. A bibliography of the more important literature upon such deposits is given below.2 Coffin's Bulletin upon the Radium, Uranium and Vanadium Deposits of Colorado, published in 1921, is a particularly clear discussion. The most comprehensive recent statement is Butler's.

Jan 1, 1928

By E. R. Parker, D. L. Martin

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944