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By J. A. Hafford, J. K. Kerver, J. G. Richardson, P. M. Blair, J. S. Osoba

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By Walton J. Greer, System By John E. Owen

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.' The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By R. J. Towner

Tensile properties of Aluminum Powder Metallurgy (APM) products at 600°, 800°, and 1000°F were lowered by cold reductions of as little as 10 or 20 pct. The detrimental effect of cold work on yield strength at elevated temperatures increased with temperature. Heating cold-worked products at 850° to 1150°F removed the structural effects of cold work through the process of recovery and restored, at least partially, the strength at 600°F to the level of hot-worked material. Material containing 5 pct A1203 was recrystallized by cold reductions of 97 pct or more followed by annealing at 1100°F. Recrystallization lowered sharply the strength at room temperature, but raised the strength at 600°and 800°F relative to that of the cold-worked state The high strength of Aluminum Powder Metallurgy (APM) products at elevated temperatures'-4 is well-known. In this paper, some conditions of processing that can affect this important characteristic are presented. The following nomenclature will be used to identify different alloys: All of the above alloys are of the aluminum-aluminum oxide type made from milled powders of commercially pure aluminum with the exception of M486, which is fabricated from atomized A1-Fe alloy powder. The products made from milled powders are hardened by a dispersion of aluminum oxide par- ticles in the aluminum matrix, while the intermetal-lic compound FeAL is the dispersion hardening agent in M 486.' The process used for making all APM products involves the application of heat and pressure to form a compact from powder which is fabricated into an extrusion, sheet, strip, or wire by standard techniques. Probably the most common cold-worked APM product is sheet. Cremens, Bryan, and rant' determined the room-temperature tensile properties and the 600°F stress-rupture properties of XAPOOl and XAPOO3 sheet and reported that there was little difference between the as-extruded, cold-worked, and annealed at 1200°F conditions. On the other hand, Emmons6" found that the tensile and stress-rupture properties of XAPOOl and XAPOO3 sheet at 600" and 800°F were lower than those of extrusions. The tensile properties of XAPOO3 sheet were also determined at elevated temperatures by Doyle' and ~ayward.' According to Friske" and Kendal et a1.," cold working by swaging, rolling, and tube drawing reduced the tensile and creep-rupture strength of XAP 001 Recrystallized aluminum powder metallurgy products are rare because the dispersion in the aluminum matrix is usually too fine, uniform, and concentrated to permit recrystallization. However, Lenel12 was able to recrystallize wires made from aluminum powders containing about 1.75 and 3.0 pct oxide and found that the tensile properties at room temperature remained higher than those of annealed commercially pure aluminum because of the dispersed oxide particles. Westerman and Lenel13 found the kinetics of recrystallization of the powder products were very different from those of cold-drawn commercially pure aluminum wire. The alloy containing 3.0 pct oxide recrystallized to a very coarse grain size was more creep-resistant at 400" to 600°C (752" to 1112°F) than in the as-extruded, fine-grained condition, according to Ansell and weertman.14 Ansell and aenel" further studied creep at 500" to 620°C (932" to 1148°F) of recrystallized 1.75 pct oxide wire and confirmed the creep model of Ansell and Weertman. The present work is being reported for the fulfillment of the following objectives: 1) to show the effect of cold work on tensile properties at elevated temperatures;

Jan 1, 1964

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By R. D. Satterley

THE Sherwood mine is an iron-ore mine owned and operated by the Inland Steel Co. in the Iron River district of the Menominee Range in Michigan. The property consists of an 80-acre tract in the village of Mineral Hills, about a mile north of the city of Iron River. The ore mined is a reddish brown, nonbessemer hematite and limonite. The ore bodies lie in a large syncline having an east-west strike and are associated with a rock structure that is folded in a complex manner. The two 40-acre tracts run north and south and the shaft is at about the center of the north forty. The shaft is 1286 ft. deep, with the principal operating level at a depth of 1000 ft. from surface. A new level at a depth of 1200 ft. is in process of development. The ore body at the 1000 ft. level is east and west at approximately the line between the north and south forties and at this elevation is from 50 to 250 ft. wide and extends above the level at varying heights of from 50 to 250 feet. The 1000-ft. haulage drift extends south from the shaft, through the east-west ore body to the slates on the south side of the body. The ore body was intercepted in the drifting at about 800 ft. from the shaft and was about 200 ft. wide at that point. A crosscut was extended to the east and west property lines along the south boundary of the ore body. This east-west ore body is laid out in areas 80 ft. wide for stoping with pillars 40 ft. wide. With this plan a stope is approximately 80 by 200 ft. and has a pillar on both sides that is approximately 40 by 200 ft. The ore has a height of from 50 to 250 ft. above the elevation of the level, therefore the height of the stopes varies in accordance with the height of the ore body at each location. From the crosscut, two main raises, each 6 by 7 ft., are put up into each 80 ft. stope area (Fig. I). One of the main raises serves as a manway and the other as an ore raise, through which the ore is transferred from the stope to the tramming equipment. The original layout was for scraping of the ore from under the stopes into the ore raises. The ore raise is put halfway (east and west) along the 80-ft. stope area and usually is in iron formation. The manway and ore raise are on approximately 15-ft- centers. These main raises are put up to a height of from 22 to 30 ft. above the level floor, then from the top of the ore raise a scraper drift (8 X 8 ft.) is driven across the width of the ore body, which is in the neighborhood of 200 ft. From the scraper drift, mill raises are put up at 12 ½ -ft. centers, staggered on opposite sides of the drift, and these are extended 23 ft. above the elevation of the scraper-drift floor. The sublevel connecting the top of these mill raises is called a mill "sub." Other sublevels are developed parallel to the scraper and mill subs at 25-ft. vertical intervals above the mill sub. The mill sub and the other subs above the mill sub are known as sublevels or dog drifts, and are 4 ft. wide and 6 ft. high. These dog drifts

Jan 1, 1945

By J. K. Kerver, J. S. Osoba, J. G. Richardson, P. M. Blair, J. A. Hafford

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs' scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

By H. R. Brannon, F. M. Perkins, Weldon O. Winsauer

Both the abnormal resistivity exhibited by shaly reservoir materials and their potential are due to adsorption of ions. Interrelationships between the two have been derived and verified by laboratory results. These relations which have resulted from this work may be used in a qualitative manner to estimate whether or not a particular shaly reservoir contains hydrocarbons, and also to estimate the porosity of shaly sands. INTRODUCTION In spite of the progress which has been made in the last decade toward a better understanding and utilization of the electric log, there remain a number of problems in the interpretation of the log. One of these which is often troublesome is that of divining the nature of the fluids in sandstones or carbonate rocks which contain appreciable amounts of shale. It was shown by Patnode and Wylliel in 1949 that shaly rocks exhibit an abnormally low resistivity when saturated with solutions of low ionic concentrations. This phenomenon has been demonstrated to be due to the adsorptive properties of shale or clay in the rock.' In estimating the fluid content of shaly sands or carbonates from the electric log, it is desirable and sometimes necessary to correct for the abnormally low resistivity. A similar correction is likewise often necessary if attempts are made to estimate the porosity of a stratum from resistivity measurements. The correction may be made from data obtained on core samples and from information on salinity of interstitial water. Cores, however, are not always available. Moreover, even if cores are at hand, their examination is time-consuming. It would be most desirable, therefore, to make corrections of this nature from the log itself. Since both the abnormal resistivity and the potential' are consequences of the adsorption of ions on shale, it should be possible to utilize the potential curve to give better interpretation of resistivity data obtained in logging shaly materials. The work described in following sections was directed toward this end. THEORY Relation of Resistivity of Shaly Reservoir Rock to Adsorpttve Properties In discussing the effect which the presence of shale or clay exerts on the resistivity of a reservoir rock, it is convenient to make use of the resistivity factor.4,5 This quantity has been defined as the ratio of the resistivity of the rock when it is completely saturated with an electrolyte to the resistivity of the electrolyte itself. When the rock, such as a clean sand or carbonate, is free of shale the resistivity factor is virtually independent of the ionic concentration of the electrolyte used to saturate the sample, so that F = R0/Rw = constant for a clean rock . . (1) where F is the resistivity factor, R0 is the resistivity of the rock saturated with electrolyte, and Rw is the resistivity of the electrolyte. When the rock contains argillaceous material, the resistivity factor as defined above is no longer independent of the concentration of the electrolyte used to saturate the rock, but decreases as the ionic concentration of the electrolyte decreases. In explanation of this behavior, it is instructive to consider a sample of shaly porous rock placed in contact with a large volume of a dilute electrolyte. The sample is considered to become saturated with the electrolyte, and to attain equilibrium with it. As a result of adsorption by the shale surfaces within the rock, there is a greater concentration of ions in the solution adjacent to the shale particles in the interstices of the sample than there is in the external solution with which the

Jan 1, 1955

By D. Mills, G. B. Craig

The defortnaliotz of zirconicltt single crystals conlaining osygen in the range 740 to 6800 atom parts per nilllion was esanined oc7er the range 77" to 950°K. An anctlsis of the dqfarmaliotz parameters leads to the cotcllsiotr that the rale -cotzfrolling thermally activated dqivr,irrtion process oe-r /he range 77" to 560°K is oc.crco,ling osvgen alotns. A thermally actitaled defor,ilntion process is not found between 600" and 800", but does occur aboz%e 800°K. THE present investigation was undertaken to measure the effects of controlled amounts of oxygen on the deformation parameters of a zirconium single crystals over the temperature range 77" to 950°K and to determine the rate-controlling mechanisms. Although there is no doubt that the mechanical properties of the group IV metals, titanium, zirconium, and hafnium, are strongly influenced by the interstitial impurities oxygen, nitrogen, carbon, and hydrogen, there are many conflicting theories as to the role played by the interstitials during the deformation proess.'- There is general agreement that the mechanisms which control plastic flow in a metal impose characteristic values on such parameters as the flow stress and its temperature dependence, the activation volume, and the activation energies. These parameters will be used to analyze the deformation mechanisms. eltham,' Sargent,16 and ibbs' have shown that the stress relaxation technique allows the activation volume characteristic of the deformation process to be found during the course of a simple tension test. In many cases it is found that the relaxation of stress is logarithmic with time and obeys a relationship of the following form: T-T = AT =S logl0(qt + C) [I] where t, is the shear stress at the start of the relaxation test, t is the shear stress at time t, and S. q, and C are experimental constants, and S is the strain rate sensitivity of the stress t as shown in the appendix. The slope found from a semilogarithmic plot of At vs time is approximately equal to S. The activation volume u, association with the deformation process, is found from the following relationship: The theoretical treatment of thermally activated plastic flow due to schoeck18 shows that the activation volume when combined with the temperature dependence of the flow stress gives the activation energy for the process according to equations: seegerZ3 considers that the flow stress at lower temperatures ld is composed of two parts such that Tapplied = tinternal + Teffective , where Teffective 3 ff , is the stress necessary to overcome the local obstacles to deformation and Tinternal, ri, is the stress necessary to overcome the long-range elastic stress field of dislocations on other planes. ri is considered to be largely elastic in origin and can be estimated from the stress value at the temperature independent portion of the flow stress-temperature curve. EXPERIMENTAL The crystal bar zirconium used in this investigation was supplied by Wah Chang Corp. whose certified analysis gave the following impurity contents in parts per million by weight: oxygen, 150; nitrogen, 10; iron, 180. All others were less than 100 ppm. The oxygen and iron contents were confirmed by neutron activation and chemical analyses, respectively. Single crystals were grown in an electron beam furnace according to the method of Wilson and Pickle-simer'' and ills.'' The orientation of the crystals was such that the specimen axes were located in the lower third of the standard section of the basal plane stereographic projection for zirconium. This orienta-

Jan 1, 1969

By System By John E. Owen, Walton J. Greer

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By A. A. Bauer

The ?-to-? transformation has been studied in zirconium alloys containing 22 to 70 wt pct U. In this range of compositions the ? phase can be retained by quenching. Transformation to ? occurs by a nucleation-and-growth process. The diffusion of atoms to preferred lattice sites to yield a partially ordered structure apparently controls the rate of reaction. Alpha uranium and a zirconium precipitate from the supersaturated E phase initially formed in alloys outside the equilibrium E phase composition limits. ZIRCONIUM-Uranium alloys have long been of interest for reactor-fuel applications because of the low thermal-neutron cross section of zirconium. Considerable information is available on the various properties and behavior of these alloys1 although there had been a number of areas where information was incomplete. As part of a program to provide more detailed knowledge in these areas, the presently reported investigation was undertaken. The constitutional diagram of the zirconium-uranium system is shown in Fig. 1.' The system is distinguished by a region of complete solid solubility between the body-centered cubic ß-zirconium and ? uranium phases and the existence of an intermediate phase in the vicinity of 50 wt pct U. This intermediate phase, designated as E, is reported3 to have a primitive hexagonal structure with a = 5.03 and c = 3.08A. The structure is partially ordered with zirconium atoms at the 0, 0, 0 position and zirconium and uranium atoms located randomly at the 1/3, 2/3, 1/2, and 2/3, 1/3, 1/2 positions. While the E phase may be nominally designated as of UZr2 stoichio-metry, the random distribution of uranium and zirconium atoms permit a considerable range in composition. Of interest in the research performed were alloys in the range from 20 wt pct (10 at. pct) to 70 wt pct (47 at. pct) U. In this range of compositions the body-centered-cubic ? phase can be retained either completely or partially on quenching. The nature and kinetics of transformation of the ? phase were the subject of study. Proceeding concurrently with the presently reported work was an investigation by Kearns4 which has since been reported. Kearns studied alloys containing 50 to 60 wt pct U prepared from sponge zirconium. While the work reported here is for alloys prepared from crystal-bar zirconium and the techniques of study are to some extent dissimilar to those employed by Kearns, general agreement so far as results and interpretation can be reported. Experimental Techniques—Alloys were prepared and the transformation of the ? phase studied during interrupted-quench and quench-and-temper isothermal heat treatments by means of hardness measurements and X-ray diffraction and metallographic techniques. The isothermal transformation of the ? phase on quenching and tempering was investigated further employing dynamic-modulus measurements. Electrical resistivity and limited Hall coefficient measurements were also obtained as part of the study. Alloy Preparation and Heat Treatment— Alloys containing 15, 20, 22, 30, 40, 45, 50, 55, 60, and 70 wt pct U were prepared from as-reduced uranium and crystal-bar zirconium. The alloys were double arc melted by consumable-electrode are-melting techniques. The final ingots were forged and rolled at temperatures between 790" and 840oC to 1/4-in. rod and 1/8-in. sheet. Chemical analyses of the fabricated alloys were

Jan 1, 1961

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967