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By Michel T. Halbouty

South Texas, one of the world's important oil and gas-producing areas, continued to hold interest during 1939 as another scries of new fields and new producing levels was developed within its boundaries at a fairly continuous rate throughout the year. There were 1801 wells drilled in this area in 1939, compared to 1678 in 1938; of these, 1515 were drilled in established fields, or as extensions to proven areas (semi-wildcat), and 286 were drilled as rank wildcats, in search of new production. Among these rank wildcats, 22 produced oil, 7 produced distillate and gas and 257 were abandoned as dry holes (see Table 5). Of the 1515 field and cxtension wells, 1213 produced oil, or distillate and gas, 50 produced only gas and 252 were dry; 38 found new productive sand levels in proven ficlds. Jim Wells County led this district in discoveries, having had 9 new fields arid 9 new productive sands found within its border during 1939. Most activc of the 1939 discoveries were Reynold?; and Ben Bolt fields in Jim Wells County and Minnie Bock field in Nueccs County; among producing fields the most activc were: East White Point and Aransas Pass (McCampbell). Production from South Texas in 1939 totaled 55,105,506 bbl. against a total of 56,152,122 bbl. produced in 1938. South Texas should continue its present rate of developrnent and exploration and this should result in the discovery of many fields in its numerous oil-bearing zones, and should also lead to more knowledge of the possibilities of its deeper horizons, such as the Mt. Selman and Wilcox formations; with the latter holding particular interest at the present time. Tide Water Associated Oil Company's A. M. Bruni No. I, Cole-Bruni field, Webb County, the deepest well drilled along the Mirando trend, was carried to 8959 ft., where it started to blow out from a Wilcox sand topped at 8954 ft., making gas, distillate and mud under heavy pressure. After the well was killed, drill stem beeame stuck and was cemented in place in order to test a Queen City (Mt. Selman) sand logged from 5620 to 5675 ft. This and other shows found in other wells along this trend, but out of this district, have served to increase the importance of this but little explored Sparta-Wilcox trend of South Texas during the year, and more activity along it is to be expected in the near future.

Jan 1, 1940

By David J. Dunn

GENERAL NOTES Liner Design for Comminution Liners in crushers and mills are the mechanical link between machine and ore. The way liners transfer energy to media and ore determines to large degree the production rate, liner wear rate, maintenance cost, energy use, and availability of the comminution process. Plant capacity and mineral recovery economics, and return on investment, are thus strongly dependent upon these simple, low cost metal shapes of which so much is demanded. The complexity of dynamic relationships between liner configuration, material properties, ore characteristics, and operating parameters defy simplistic generalization. Rules-of-thumb and axioms of years past fall into disuse almost daily as new analytical methods, assisted by computers and sophisticated control systems, are applied to crushing and grinding processes. Recent literature is well supplied with references citing production benefits that improved liner designs produce. This chapter is intended to review especially promising liner designs and material developments and presents cameo case studies showing the benefits derived from their application to comminution circuits (Tables 1,2,4,5,7). Complete discussions of liner design and wear materials are beyond the scope of this chapter. Norman's comprehensive studies in references (1) and (2) and Mclvor's analyses of mill speed/configuration effects (3) are especially useful reading for designers and operators of crushing and grinding circuits. Changing trends in ore, product value, and costs of wear materials, interest, labor, and energy, make ongoing evolution of liner design equally important for existing mines and for projects still on the drafter's board. Original designs supplied as new equipment must, of necessity, be best estimates. These can usually be improved as operating experience replaces engineering forecasts. Advent of new materials or design concepts such as the Angular Spiral Liners (Korpi (4) ) or Norman's Bimetallic design (2) offer improvement potential that must be evaluated if a given circuit is to be kept competitive versus others making similar products.

Jan 1, 1982

By R. Floyd Farris

A THOROUGH knowledge of the behavior of cement slurries under elevated tempera-tures and pressures is necessary in order to solve properly the many problems pre-sented in deep-well cementing operations. In the earlier days of the petroleum indus-try the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being given, for the present, to details of tech-nique and equipment for oil-field use. More specifically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries.

Jan 1, 1940

By Thomas Egleston

The process of lixiviating silver ores, which do or do not contain gold, by means of hyposnlphite of soda is likely to assume a very great importance in the West, the conditions being such that while it is applicable to very rich ores which do not contain lead enough to smelt, it is also equally applicable to many ores that are either too poor or too impure to be treated by any other process. Western ores are generally divided into four classes: those which contain copper enough to be smelted for copper, from which the gold and silver is extracted in the wet way, as is the practice of the Boston and Colorado works; those in which there is a large quantity of lead, which can be smelted for lead, and the gold and silver extracted from it; ores in which there is neither copper nor lead enough to allow of a process of smelting, but which can be treated in pans, these ores being " free milling " if they require no metallurgical treatment, or '(rebellious" if they have to be roasted with or without the addition of salt; and ores which do not contain enough either of lead or copper for smelting, which are poor both in silver and gold, contain large amounts of sulphur, arsenic, and antimony, and cannot be treated in many places in the West by any of these processes. Roasting with salt would convert the base metals as well as the silver into chlorides, and would give in the amalgamation a very base bullion, and the expense of the process would be SO great that the margin of profit would be very small, the reason being that for the ordinary process of pan-amalgamation, which is the only one suitable for ores containing small amounts of the base metals, and poor in silver and gold, the cost of a plant for milling is so large as not to justify the expense of treating such ores. The electrolytic processes which have been partially successful in Europe have not been tried 'here. While in the near future they will undoubtedly be used, it is hardly possible to consider them now.

Jan 1, 1884

By B. F. Fackenthal

One of the practical questions presented to the blast-furnace manager, with regard to which little help can be obtained from existing technical literature, is the manner of filling and blowing-in. This operation is often performed according, more or less, to traditions which have come down from earlier practice, and which, if not positively detrimental when followed with the large modern furnace, may at least be greatly improved, just as the running of the furnace itself, while in blast, has been improved. It is not necessary, as many of the old furnace-men believed, to make a lot of white or silver-gray iron at the start, or to spend many weeks, or months even, in bringing the furnace to its normal burden. It has seemed to me that the publication of carefully-recorded data of practice on this point may be interesting to the members of the Institute engaged in the management of blast-furnaces. The enlarged blast-furnace at the Durham Iron Works, Riegelsville, Pa., owned by Messrs. Cooper & Hewitt, of New York City, was first put in blast February 21, 1876, since which time it has made seven blasts, and is now running on the eighth. A description of the furnace-plant, together with a record of the fifth blast, was given in my paper read at the Chattanooga meeting, May, 1885 (Transactions, xiv., 130). After some of the early blasts the furnace-lines underwent considerable change, and I have thought best to accompany this paper with drawings showing the lines and the tuyere-arrangement (see Plates I. and II.), and to give also the following summary of the conditions and results of each blast. During the first and second blasts no coke was used, and the furnace ran very irregularly, showing a constant tendency to scaffold, which was attributed, in great part, to the small hearth and other defective lines. The large proportion of air required at this furnace is accounted for by the fact that the engines are defective, and do not deliver into the furnace the amount of air indicated by the pistondisplacement.

Jan 1, 1890

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 Composition 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 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 Composition 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

Your committee's secretary submits the following report, or summary, to the- members of the committee, in an endeavor to lay before them a general review of the information so far received and also his own knowledge .of the work as carried on at a number of plants, this being done in part to secure further information and suggestions from members and lead to a more effective means of furthering the work of the committee. It is suggested that more detailed data be compiled regarding engineering features involved, and that papers be contributed which will deal with the safeguarding of underground electrical installations. There are few operating companies which have not started a more or less systematic campaign to safeguard their employees from accidental injuries and unhealthful surroundings, but a great deal is to be gained by experience. All may welcome the advice and cooperation of those who have been actively engaged in the work and have demonstrated the results obtainable by organized effort, and it is, therefore, exceedingly gratifying to note the ready assistance and hearty cooperation rendered by the companies that may be truly termed pioneers in the movement. No solution of the safety problem is to be found in a strict standardization of methods, rules or devices, as' the various mining, milling and metallurgical practices present too' many conditions differing broadly in general principles, but some standard system embodying principles, already proven to be efficient should be created, which may be modified or elaborated to meet specific requirements of each individual. company, or to fit working conditions as they exist in the various mining camps throughout the country. An industrial plant is -primarily a business undertaking, therefore the economic side-of a safety or welfare campaign is of importance. Many small operators have been deterred from undertaking the work by their belief that it involved an expense beyond their means, and one that could not be counterbalanced by greater efficiency or saving along other lines. This idea is generally clue to a lack of knowledge of the actual costs of such work, and of the results secured by judicious selection of a method commensurate with the. size and nature of the opera-

Jan 1, 1917

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be ' parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By Henry U. Ross

The behaviour during reduction of iron-ore pellets and sinters was investigated. Several methods for the preparation of agglomerates and their reduction were tried. Commercial agglomerates from world-wide sources as well as experimental samples were tested. The effect of coke additions to pellet and sinter plant feeds was given special consideration. An analysis of the test results has helped to explain many of the phenomena associated with the reduction of iron-ore agglomerates such as swelling, loss in strength and wear resistance, changes in porosity, changes in mineralogy and the formation of metallic iron and slag. A double-layer pellet with all of the coke concentrated in the core proved particularly interesting. Although large quantities of coke showed that partially reduced agglomerates containing metallic iron could be produced in the laboratory, the problem of producing reduced pellets and sinters by the existing agglomerating processes still remains.

Jan 1, 1977

By John Gross

The study of the energy used in crushing operations has advanced from a period of perplexing confusion to one of greater clarity. Only within the last few years has any true conception of the work in crushing been possible, owing to the chaotic state of theoretical knowledge. For some 20 years a controversy existed between those advocating the Rittinger law and those advocating the Kick law. The Kick law now appears to be definitely out of the picture, and crushing efficiency may be based confidently on the Rittinger theory. There also seems to be a generally crystallized conception as to the meaning and nature of sub-sieve material. There is needed a simple, direct method for determining surface on a crushed ore product, and also a simple and accepted method for size determination on minus 400-mesh material. The Crushing Law The Rittinger(l)‡ theory of crushing was advanced in 1867 and the Kick(3) theory in 1885. While the Rittinger theory might have been accepted without much question and actually had been accepted by many investigators, a serious doubt as to its validity was raised by Stadler(10) who upon purely theoretical grounds proclaimed the Kick "law" as the true law of crushing. According to Rittinger the energy required in successive steps in reduction increases geometrically, while according to Kick the energy increases arithmetically. These "laws" therefore are at variance, and the establishment of the true law was recognized as of first importance. Many simple experiments have been made to demonstrate the application of the Rittinger theory to crushing, and it would seem that its simplicity should favor its acceptance. Experimental evidence, however, was not convincing, as no reliable data could be obtained on the finer material from a crushing or grinding operation. Gates,(13) Bell,(19)

Jan 1, 1935

By D. F. Kaufman, V. V. Damiano, G. J. London, L. R. Aronin

Beryllium bicrystals were Prepared by a seeding and floating zone-melting technique from high-purity beryllium single-crystal material. The starting material was given six floating zone purification passes prior to producing the bicrystals. Symmetric, asymmetric, and antisymmetric bicrystals were tested in tension. Included were bicrystals with boundaries both parallel and perpendicular to the tension axis. Modified symmetric bicrystals were also examined in detail. In these cases, the angles made by the slip planes with the boundary were not equal. Failure by (0001) cleavage, (1180) cleavage, and boundary separation were all observed depending on the orientation of these cleavage planes and the boundary with respect to the tension axis. Failure occurred on whichever system experienced the greatest normal stress. The origin of the fractures observed and the operative dislocation mechanisms were investigated by frac-tography and transmission electron microscopy. The results indicate that low-angle boundaries form in close proximity to the bicrystal boundary and act as sites for crack nucleation. It has been concluded that, although macroscopic compatibility was satisfied in many of the bicrystals examined, the bicrysta1 boundary was effective in Producing "early" failure by local bend plane formation as plastic deformation proceeded, followed by cleavage initiation and crack propagation. SINGLE crystals of high-purity beryllium oriented with the basal plane inclined 45 deg to the tension axis exhibit a critical resolved shear stress of about 300 psi and 200 pct extension by slipping only on the basal plane before failure by cleavage on that plane. Single crystals, oriented with the basal plane parallel to the tension axis, deform by prism slip at a critical resolved shear stress of 9000 psi and exhibit an extension of over 100 pct before failure in a ductile manner.' In contrast to the behavior of single crystals, poly-crystalline beryllium deformed in tension or bending exhibits little or no ductility at room temperature. Beryllium's lack of ductility at room temperature has been attributed to its lack of a sufficient number of independent slip systems. Beryllium has only four independent slip modes at room temperature and according to the Taylor2 and von Mises3 criteria at least five independent shear modes are necessary to completely satisfy the strain compatibility conditions at all the boundaries in a random polycrystalline sample. Studies of beryllium bicrystals thus appear to provide a convenient way in which to determine whether the condition of strain compatibility is a necessary and sufficient condition to prevent failure and whether obviously incompatible boundary conditions result in boundary separation. Bicrystal studies, although not providing all of the constraints encountered in polycrystalline samples, do allow one to select very specific orientation relation-

Jan 1, 1969

By Gordon E. Agar

Several correlations have been proposed to relate energy consumption and size reduction in comminution, and although these are arrived at from different starting points, it is postulated that they are all statements of the same basic concept. To test this postulate, the dry ball mill grindability of langbeinite was determined, and the results were analyzed according to the various methods. An examination ' of the energy-particle size relationships proposed in the recent past revealed that they had much in common. In fact, the conclusion was tentatively drawn that these expressions were essentially the same, even though they were arrived at from quite different basic premises. The equations attributed to Charles2 and Holmes3 were shown to re- duce to the same single equation, W - A K-3, and the simulated continuous test used by Maxson et al.4 was shown to give the best experimental value of the required empirical parameter, ß. Furthermore, the size distribution parameter a in the Schuhmann equation, y - (x/K)2, was shown to be equal to ß in many cases. The kinetic approach used by Arbiter and Bhrany5 should give the same results as the Maxson test procedure; however, the batch operation used by Arbiter and Bhrany could not produce data that would be as precise as the simulated continuous technique. To test the validity of these conclusions, the simulated continuous method was used to obtain data on the dry grinding of langbeinite. The results are discussed in terms of the various equations and approaches. APPARATUS AND MATERIAL A ball mill with internal dimensions of 17.5 cm (6 7/8 in.) in length by 19.4 cm (7 5/8 in.) in diam was loaded to 50% of its volume with balls 3.2 cm in

Jan 1, 1969

By Virgil Kirkham

NORTH AMERICA has for many years led the world in phosphate production, but with development of African deposits and their marketing conditions with respect to European countries, this leadership will shortly pass to Africa. Algeria, Egypt, Tunis, and Morocco have large phosphate reserves and a correspondingly large production because of easy mining and a ready European market, which was developed during the war. An increase in home consumption is destined to develop for the eastern American fields, and the countries of the Pacific will provide a market for the western producers. New processes indicate a decrease in fertilizer costs, which will encourage a more widespread domestic use and assure better marketing conditions. The African deposits, although benefited by a water haul, have the disadvantage of being isolated from a source of acid so that the crude rock is shipped from Africa to its destination, whereas in the United States the chief product shipped is acidulated rock or various types of superphosphatic fertilizers. The principal types of phosphate deposits used in the manufacture of fertilizers are guanos, apatite, phosphatic marl, phosphatic limestone, phosphatic shale, and phosphate rock which is also known as phosphorite. Some of these deposits are found on each of the continents; Table 1 gives their occurrence, age, location, character, extent, etc. Most of , the information found in this table represents a compilation of information published elsewhere in a different form and widely scattered.

Jan 1, 1925

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By O. N. Carlson, H. A. Wilhelm, H. E. Lunt, J. M. Dickinson

On the basis of data obtained from microscopic examination, melting observations, cooling curves, X-ray analyses, and resistance measurements, phase diagrams have been proposed for the Th-Cb and Th-Ti alloy systems. Both are simple eutectic systems and have no terminal solid solubility or intermediate phases. The eutectic between thorium and columbium occurs at a composition of about 8 wt pct Cb and a temperature of 1435°C. The Th-Ti eutectic occurs at 1190°C at the composition 12 wt pct Ti. No change was observed in the transformation temperature of thorium in either system or in the titanium transformation. RECENT study of thorium and its alloys has been promoted because of the possibility of employing this metal in nuclear reactors. Their corrosion resistant properties, nuclear characteristics, and high melting points put columbium and titanium among the many metals being employed in the study of thorium alloys. Since a knowledge of the phase relationships would be important in the application of such an alloy, investigations were undertaken to propose phase diagrams for the Th-Cb and Th-Ti systems. Experimental Procedures Thorium metal sponge was specially prepared for use in this investigation. Carbon in a quantity less than 0.04 wt pct was the principal impurity. There was also less than 0.01 pct each of iron, calcium, zinc, aluminum, and nitrogen in the thorium. Columbium, both as a powder and sheet metal, was obtained from the Fansteel Metallurgical Corp. The manufacturer's specifications indicated that the metal contains less than 1 wt pct total impurities. An analysis of the metal showed approximately 0.18 pct C in the powder and less than 0.05 pct C in the sheet. The titanium used was commercial sponge, reported to be 99.5 pct Ti. An analysis showed that this metal contained 0.2 pct Fe. Preparation of Alloys—Since the metals used in this investigation are reactive and might become contaminated on melting in a refractory crucible, the alloys were prepared by arc melting. The titanium sponge was employed in the form of small lumps while the columbium additions were made either as pressed pellets of powder or as clippings from sheet. The alloying material and the thorium sponge were melted together under argon in conventional arc melting equipment employing a tungsten electrode and a water cooled copper crucible.

Jan 1, 1957

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By Lawrence Wright

THE occurrence of gold, gold-silver, silver-lead-zinc ores in the post-Cambrian sediments in the Black Hills of South Dakota, and their genetic relationship to the Tertiary intrusives, is well known and accepted, but the occurrence of gold in the pre-Cambrian rocks at the Homestake mine, which underlie this Tertiary gold mineralization, has given rise to differ-ences of opinion as to the period of major gold introduction into the older rocks. Fig. 1 illustrates. the distribution of mineralization along the axis of the Tertiary uplift in both pre-Cambrian and post-Cambrian rocks. The following possibilities have been presented: 1. The Homestake gold deposit was formed in pre-Cambrian time and the deposits in the overlying Cambrian sediments formed during Ter-tiary time. 2. The Homestake lode existed at the beginning of Cambrian time, but was enriched by the passage of Tertiary auriferous solutions. 3. The Homestake lode was represented by pre-Cambrian quartz-chlorite sulfide mineralization, very low in gold content and the gold superimposed on the older nearly barren mineralization during the Ter-tiary metallogenic epoch. 4. The sulfides and sulfarsenides as well as gold were deposited in both pre-Cambrian and post-Cambrian rocks during the Tertiary period. Those favoring the first proposition feel that the question is pretty well settled, while the proponents of the second theory are more flexible in their view, feeling that the amount of gold introduced in either period is still an open question. The third and fourth theories, with some modifi-cations, are supported by the proponents of the Tertiary theory, who feel that the evidence strongly favors that period. The following pages are intended to present the evidence and to give the reaction of various observers with my own comments and conclu-sions; also, the accumulated facts of observation gathered over a period of close association with the area under discussion, beginning in 1919.

Jan 1, 1936

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.' The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-' at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970