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By Frederick C. Pearson, Albert Brown, Emil R. Ermert

EARLY in 1946 the Shen-Penn Production Co., a subsidiary of the Philadelphia and Reading Coal and Iron Co., was organized to operate the Shenandoah Stripping, one of the largest open-pit anthracite mines in the world. This mine is located in the Western Middle Field near Shenandoah, Schuylkill County, Pa., and involves the removal of approximately 60,400,000 cu yd of overburden to permit the recovery of 9,200,000 gross tons of rough cleaned coal from an area 8000 ft long and 2700 ft wide, with a maximum depth of 400 ft. Operations began in August 1946, and within the next few years 31,811,000 cu yd of overburden and 2,994,000 gross tons of rough cleaned coal had been removed. During the early days of open-pit mining operations, steam was the primary motive power. However, as the size of the equipment increased, so did the problems of fuel, water, labor, and maintenance. Because of its efficiency and convenience, electric power rapidly replaced steam. Later the modern diesel engine was developed, and today practically all stripping equipment is either electric, diesel-electric, or diesel-powered. In locations where electric power is not readily available or where operations are scattered over a large area, diesel power is favored. At Shenandoah operations are highly concentrated in a relatively small area, and this fact, coupled with the availability of ample electric energy, indicated the selection of electric-powered equipment. Since this was a new company, it was necessary to purchase every item, from the smallest tools to stripping shovels. Although the organization period was hampered by the postwar scarcity of materials, an excellent opportunity was afforded to set up a thoroughly modern plant. This paper will describe the power facilities, with particular emphasis on the more unusual features. The substation is a major item in a power distribution system, and a simple arrangement utilizing high quality equipment is an excellent investment. With this in mind, a 3000-kva unit type substation was selected and installed. This unit is made up of three sections, which are assembled simply by bolting together the various sections and connecting the power leads, see Fig. 1. The transformer proper, rated at 3000 kva, is oil-filled and nitrogen-sealed, having a 66,000-v Delta primary and 4160-v Wye secondary with a grounded neutral and 46-ohm ground resistor. The function of this resistor will be described later. Electrical energy is purchased from a public utility and is delivered to the main substation at 66,000 v over one or the other of two incoming lines. These lines terminate on a high voltage switching section on which high voltage fuses and Thyrite lightning arresters are installed. The outgoing feeder switching unit is made up of the following: 1-An auxiliary compartment consisting of potential and current transformers with necessary terminal blocks for connecting to power company metering equipment. 2-Another auxiliary compartment containing a control transformer, battery, and battery charger for the furnishing of power for tripping and reclosing of power circuit breakers. The assemblies in these auxiliary compartments are mounted on carriages that can be rolled in and out with ease. Potential transformers are readily accessible for inspection and fuse replacement. When withdrawn from the operating position they are completely de-energized and grounded. 3-Two feeder breaker compartments, each with a 1200-amp, 5000-v, solenoid-operated magneblast air circuit breaker, voltmeter, ammeter, overcurrent relays, and a ground relay. These power circuit breakers can be quickly and safely withdrawn or repaired. A built-in isolating mechanism is used for lowering the breaker to a transfer truck for repair or inspection or as a means of disconnecting the breaker from the source of power as an added precaution when working on power lines. Thus inspec-

Jan 1, 1952

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By G. W. P. Rengstorff, H. B. Goodwin

A method is described for purifying iron in batches of 150 Ib or more. Oxygen, carbon, nitrogen, and sulphur are removed from flakes of electrolytic iron by treatment in wet and then dry hydrogen. A special consumable-electrode arc furnace is used to remove hydrogen and to melt the flakes into ingots. A LTHOUGH iron and steel have been made and used for hundreds of years, there are still wide gaps in the knowledge of these metals. One reason for this is that the true properties of the base metal, iron, are not well known, simply because really pure iron has never been readily available for research purposes. Commercial iron, and even the "pure" irons which are readily available, are really complex alloys of iron with oxygen, nitrogen, hydrogen, carbon, sulphur, silicon, and other elements. With such materials, it has not been possible to prepare steels and other iron-base alloys in which all elements are present in exactly controlled amounts. It is an almost impossible task to determine the separate effects of each element or the intereffects of several elements unless alloys can be prepared containing only the desired elements. The ability to make controlled alloys of low impurity content is of far more than academic interest. It will assist in the study of such practical problems as the brittle failure of ship hulls or high pressure gas pipelines, determination of the factors which affect the deep-drawing properties of steels, the improvement of magnetic and electrical properties, the phenomenon of aging, and many others. In 1949, the American Iron and Steel Institute asked Battelle Memorial Institute to prepare high purity iron on a larger scale than had been attempted up to that time. The work was directed toward the preparation of iron as low as possible in carbon, oxygen, nitrogen, hydrogen, and sulphur because these are the contaminating elements of major interest in many research investigations on iron-base alloys. The initial goal was to prepare iron with not more than a few thousandths of one percent of each of these impurities. The purpose was to set up a "bank" of high purity iron on which researchers could draw when a supply was needed and which could be replenished from time to time as the stock became depleted. Of several possible purification methods, heating in hydrogen was selected as the most promising for the removal of both carbon and oxygen from solid iron. Metallic impurities are not removed by hydrogen. Electrolytic iron was chosen as a starting material because it is the most readily available form of iron low in metallic impurities. Decarburization and desulphurization were obtained by annealing in wet hydrogen at relatively low temperatures. The optimum temperature, as found by previous investigators,' is about 1400°F. This treatment also removes nitrogen. Deoxidation is favored by dry hydrogen and higher temperature. There is evidence from previous work that an anneal at 2200°F in dry hydrogen will deoxidize the iron, reduce the nitrogen content, and reduce the sulphur content. These facts suggested the use of a two-stage process: treatment in wet hydrogen followed by treatment in dry hydrogen. To carry out the purification process in a reasonable time, it was necessary that the iron be in thin pieces. Flakes of electrolytic iron were used. Because most research requires that the iron be in massive form, it was nccessary to melt the purified iron to consolidate it into large pieces. For this work, it was decided to prepare ingots weighing at least 15 lb by using a cold hearth arc-melting process in which the iron was melted in an inert atmosphere of argon or helium. This method of melting was selected because the water-cooled copper crucible is not wet by the iron and does not contaminate it as a refractory crucible would. Because the crucible is also the ingot mold, contamination from mold materials was also eliminated. Contamination from electrodes was avoided by making them from purified electrolytic iron. The melting procedure finally developed was an adaptation of the Kellogg electric ingot process.' Two batches of purified iron weighing about 100 Ib each in ingot form were prepared with analyses as shown in Table I. The remainder of this paper describes the procedures in more detail. In general, the process con-

Jan 1, 1956

By AIME

IN the following pages are described the history and present operations of one of the country's great mining and metallurgical organizations-the United States Smelting Refining and Mining Company. Though the articles are largely of interest to the technical man, the success of the Company as a business enterprise should not be overlooked. Almost immediately following incorporation 42 years ago payment of dividends began and the total to date has been about $140,000,000, roughly half to preferred and half to common shareholders. Founders of the Company were Boston businessmen and financiers interested in such diverse enterprises as shoe machinery manufacture, banking, newspaper publications, and stock brokerage. The legal profession also was represented. The Company is one of the few, among the leaders in the mining industry, that has resisted the urge to move its home office to New York and has always remained in Boston. Perhaps for that reason it has been regarded as a "conservative" company. Conservative or not, it has certainly spread out geographically and it has certainly put its eggs in many baskets. In addition to the precious metals and the major nonferrous metals it has ventured into coal and recently in a small way into the field of oil and gas. It seems to have a predilection for the North American Continent; for in addition to Alaska, Canada, and Mexico it has had important operations in California, Arizona, Nevada, Colorado, New Mexico, and particularly in various districts in Utah.

Jan 1, 1948

By DULUTH ENGINEERS' CLUB

DULUTH ENGINEERS' CLUB The engineers of Duluth, Minn., have taken the first steps to form a Duluth Engineers' Club by a meeting on May 20, at the Kitchi Gammi Club. At present, Duluth has no club embracing all engineers, although the environment is splendid for the growth of an engineers' organization. Within reasonable 'distance of Duluth are over 100 members of the four large national engineering societies, a number of members of the lesser engineering societies, and many non-member engineers. Until the Duluth Association of Civil Engineers was formed, four years' ago, these engineers had no common ground of meeting, and a force representing education, experience, and high ideals lay dormant. About 70 engineers were present at the organization meeting, and favorable responses were received from others who could not be present. F. E. House, President of the Duluth & Iron Range Railroad, outlined the objects of the meeting, calling attention to the importance of the engineer in all lines of activity in the war and the splendid qualities of American engineers in France. W. H. Woodbury outlined the plan, stating the three objects of the club as professional, social, and civic. Four plans of membership have been considered: First, an organization for all professional engineers, junior engineers, and associates, with .different status for each; second, an organization of members of the four big national societies; third, an organization of members and a limited number of associates; fourth, professional engineers, only, all on equal standing.

Jan 8, 1918

By M. M. Fine

THE problem of producing a uniform, medium-fine sand for glass-furnace feed has been of interest to the glass-container industry for many years. In the present investigation of the problem, conducted by the Bureau of Mines in cooperation with the Owens-Illinois Glass Co., Alton, Ill., a satisfactory method of producing such sand was developed. The investigation involved continuous-grinding studies of glass sand with flint and porcelain pebbles, steel balls and rods, and a simultaneous study of classification. The most satisfactory procedure consisted of grinding in a pebble or ball mill followed by a double classification: hydraulic classification to separate the oversize for return to the grinding unit and mechanical classification to remove fines and impurities from the ground sand. The proper application of this flowsheet usually yielded a graded sand containing less iron than the feed even when grinding was done in a steel-lined ball mill. The amount of sand ground into the so-called "dusting" sizes was, in all cases, less than 10 pct. Experiments were made which showed that this very fine sand could be beneficiated to a usable material. Background The advantages in utilizing a uniform, medium-fine sand as a feed for glass furnaces has motivated a considerable amount of research on the ,problem of producing such sand by glass producers and others. For the glass producer, the faster melting rate of such a graded sand offers the possibilities of reduced fuel costs and increased furnace capacity. In addition, there is the likelihood of improving the quality of the melt and thereby reducing the number of seeds (air bubbles) and stones (unrnelted grains) in the finished ware. Although the melting rate of a glass batch depends on other factors in addition to the grain size of the sand, there is experimental evidence to show that grain size influences the melting rate considerably. Potts, Brookover, and Burch' found that when the raw materials (sand, soda ash, and limestone) were always matched in- size, there was a great decrease in the melting time as the grain size of the materials was decreased. They found, too, that when the grain sizes of the soda ash and Limestone were held constant at 40 to 60 mesh, the minimum melting time occurred when 40 to 60 mesh sand was used. The increase in melting time with decrease in grain size beyond 40 to 60 mesh was due, they postulated, to accelerated demixing or separation of batch during melting as the grain size of the sand decreased in relation to the grain size of the other materials. An earlier investigatora found that the highest rate of melting and purifying ordinary glass was obtained when medium-size sand (0.385 to 0.120 mm, correspondingly roughly to 40 to 120 mesh) was used. Although batches containing smaller-size sand were found to fuse more rapidly, the time required to remove air bubbles from such melts actually increased the total duration of the process. Coarsegrained sand, it was stated, increased greatly the times of both melting and purifying. Although the laboratory data are difficult to confirm on a plant scale, observations by the Owens-Illinois Glass Co. indicate a higher furnace capacity of better-quality ware when a medium-fine sand is used in the batch. During the recent war, the glass producer was inclined to overlook a considerable variation in raw materials in the interest of higher production. For instance, table I shows the wide range in the amounts of various screen fractions in sand supplied by one producer to the Terre Haute plant of Owens-Illinois. The sand, from the northern Illinois St. Peter sandstone, represented material used by that plant over a period of a few years during the war. Since the war, the glass industry has insisted on

Jan 1, 1951

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By M. M. Fine

THE problem of producing a uniform, medium-fine sand for glass-furnace feed has been of interest to the glass-container industry for many years. In the present investigation of the problem, conducted by the Bureau of Mines in cooperation with the Owens-Illinois Glass Co., Alton, Ill., a satisfactory method of producing such sand was developed. The investigation involved continuous-grinding studies of glass sand with flint and porcelain pebbles, steel balls and rods, and a simultaneous study of classification. The most satisfactory procedure consisted of grinding in a pebble or ball mill followed by a double classification: hydraulic classification to separate the oversize for return to the grinding unit and mechanical classification to remove fines and impurities from the ground sand. The proper application of this flowsheet usually yielded a graded sand containing less iron than the feed even when grinding was done in a steel-lined ball mill. The amount of sand ground into the so-called "dusting" sizes was, in all cases, less than 10 pct. Experiments were made which showed that this very fine sand could be beneficiated to a usable material. Background The advantages in utilizing a uniform, medium-fine sand as a feed for glass furnaces has motivated a considerable amount of research on the ,problem of producing such sand by glass producers and others. For the glass producer, the faster melting rate of such a graded sand offers the possibilities of reduced fuel costs and increased furnace capacity. In addition, there is the likelihood of improving the quality of the melt and thereby reducing the number of seeds (air bubbles) and stones (unrnelted grains) in the finished ware. Although the melting rate of a glass batch depends on other factors in addition to the grain size of the sand, there is experimental evidence to show that grain size influences the melting rate considerably. Potts, Brookover, and Burch' found that when the raw materials (sand, soda ash, and limestone) were always matched in- size, there was a great decrease in the melting time as the grain size of the materials was decreased. They found, too, that when the grain sizes of the soda ash and Limestone were held constant at 40 to 60 mesh, the minimum melting time occurred when 40 to 60 mesh sand was used. The increase in melting time with decrease in grain size beyond 40 to 60 mesh was due, they postulated, to accelerated demixing or separation of batch during melting as the grain size of the sand decreased in relation to the grain size of the other materials. An earlier investigatora found that the highest rate of melting and purifying ordinary glass was obtained when medium-size sand (0.385 to 0.120 mm, correspondingly roughly to 40 to 120 mesh) was used. Although batches containing smaller-size sand were found to fuse more rapidly, the time required to remove air bubbles from such melts actually increased the total duration of the process. Coarsegrained sand, it was stated, increased greatly the times of both melting and purifying. Although the laboratory data are difficult to confirm on a plant scale, observations by the Owens-Illinois Glass Co. indicate a higher furnace capacity of better-quality ware when a medium-fine sand is used in the batch. During the recent war, the glass producer was inclined to overlook a considerable variation in raw materials in the interest of higher production. For instance, table I shows the wide range in the amounts of various screen fractions in sand supplied by one producer to the Terre Haute plant of Owens-Illinois. The sand, from the northern Illinois St. Peter sandstone, represented material used by that plant over a period of a few years during the war. Since the war, the glass industry has insisted on

Jan 1, 1951

By P. K. Weimer

Coinpletely integrated thin-film circuits inco?,porating more than 1000 active and passive elements have been fabricated reproducibly in the laboratory by evaporation of- all components. A 180-stage modified shift register comprising 540 CdSe TFT's, 360 resistovs, and 180 capacitors was deposited upon a glass substrate during one pump-down of the vacuum systeitl. Experimental units have been operated for more than 5000 hr at temperatures uP to 85°C without failure of any slages. The present pupper reviews the charvactevistics of evaporated thin-film transistors (TFT's) and discusses their application to integrnted circuils. INTEGRATED circuits most widely used today are based upon silicon technology, with the circuits formed on the surface of a block of single-crystal silicon1 or on a block of sapphire 2,3 upon which a thin layer of silicon has been deposited. Transistor patterns and interconnections are defined by photographic procedures using photoresist masking. Large groups of transistors are produced in batches which undergo many processing steps, some of which are carried out at elevated temperatures. Passive elements are formed by treatment of the semiconductor surface or are deposited by evaporation alongside the active elements. The size and complexity of the circuits are limited by defects in the devices and by the size of the available single-crystal chips. Capacitative coupling to the semiconducting substrate may also limit useful size and frequency response of the circuits. An alternative approach to integrated circuits is based upon the deposition by evaporation of all circuit components upon a noncrystalline, insulating substrate such as glass.4 Thin-film field-effect transistors,1'6 known as TFT's, can be deposited in large arrays on glass or plastic substrates at the same time the associated passive elements are being deposited. Although still in the research stage the all-evaporated approach is expected to offer certain advantages for many applications. In particular, the use of thin films upon a noncrystalline substrate offers the prospect of producing complex, large-area circuits not now feasible with single-crystal silicon. Important applications of this type include memory arrays for computers and imaging devices for television. The ease with which the evaporated TFT's can be deposited may permit continuous, automated production methods not possible with high-temperature batch processing. Recent advances7'8 in the fabrication of thin-film transistors have led to greatly improved reproduci-bility and life of the TFT's. Experimental circuits having over 1000 active and passive elements deposited upon a common glass substrate are currently being produced in the laboratory. The present paper reviews recent progress in the development of the TFT and in its application to integrated circuits. I) DESCRIPTION OF THE THIN-FILM FIELD-EFFECT TRANSISTOR The TFT is a field-effect transistor of the type having the control gate separated from the semiconductor by a thin insulating spacer. Although its operation resembles that of the silicon MOS transistorg its construction is based entirely on thin-film techniques. Fig. 1 shows a cross-sectional view of an evaporated TFT deposited upon a glass substrate compared with a silicon MOS transistor deposited upon single-crystal sapphire.3 The semiconductor in the TFT is a poly crystal line layer, of a material which can be readily evaporated, such as cadmium sulfide, cadmium selenide,l0 or tellurium." Silicon monoxide layers have usually served as the gate insulator, but other oxides, sulfides, and fluorides may be used. Film thicknesses range from a few hundred to a few thousand angstroms. The source, drain, and gate electrodes in the TFT are of metal. Qpical source-drain gap dimensions are 0.0003 x 0.030 in., with a gate strip whose width slightly overlaps the source and drain. The source and drain electrodes should make low impedance contacts to the semiconductor. With cadmium sulfide films, gold is a satisfactory material for underlying electrodes, while aluminum is preferable for overlying electrodes.12 Considerable variation in design of the TFT is permissible, with the electrodes being

Jan 1, 1967

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured' into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By S. M. Purdy

Under certain conditions of hot rolling and air cooling from the hot-rolling temperature, bars of a high carbon (0.40 pct C) chrome-nickel austen-itic alloy were found to show magnetism even though no ferrite or martensite could be detected by microscopic or X-yay methods. The appearance of magnetism in such alloys may come from chromium impoverishment of the austenite grains near the precipitated carbide particles. SPORADICALLY, hot-rolled bars of Silchrome 10, an exhaust valve steel, have been found to be magnetic. Because of the analysis of the alloy—0.40 pct C, 18 pct Cr, 8 pct Ni, 3 pct Si —magnetism is unexpected. Preliminary investigation showed neither martensite nor ferrite to be present; only austenite and Cr23C6. Since a literature search was fruitless, a brief study was made of the appearance of magnetism in this alloy. The only basic difference between the two heats is the nitrogen content. Permeability was measured using a Severn magnetic gauge. This instrument consists of a magnet mounted on a counterbalanced arm. A set of calibrated plugs is placed in contact with one pole of the magnet. The specimen is placed close to the other pole of the magnet. If the specimen pulls the magnet away from the plug, it has a permeability greater than that marked on the plug. This technique is swift and reproducible. Previous experience has shown that the permeabilities obtained corresponded to those obtained on a permeater with a field strength of 100 oe. Specimens from both heats were annealed at temperatures between 1700 and 2300°F. One set of specimens was water cooled and another furnace cooled. All the water-quenched specimens were non-magnetic; the furnace cooled ones were magnetic as shown in Table I with no difference being observed between the two heats. Microstructural examination of the specimens showed the expected increase in carbon solubility with increasing temperature. Carbide solution was complete at 2200°F. The specimens heated to 1900°F or below showed some carbide precipitation from the hot-rolled structure. A furnace cooled specimen from a given temperature showed less carbide out of solution than the water-quenched specimen from the next temperature below; e.g., the specimen furnace cooled from 2100°F showed less carbide out of solution than the water-quenched specimen from 2000" F. These studies indicated that the appearance of magnetism was not related to the quantity of carbon in or out of solution and it was related to precipitation at temperatures below 1700" F. A set of samples annealed and water-quenched from 2100° F was aged for 4 hr at temperatures between 1000" and 1600°F; all were non-magnetic. A second set of samples, similarly annealed, was aged 1 to 24 hr at 1200°F with the results shown in Table II. None of the latter set of specimens showed magnetism until they had been aged about 8 hr. Magnetism was quite strong after aging 24 hr. X-ray diffraction studies on several of the magnetic specimens showed that the austenite had a lattice parameter of 3.58A and that the carbide was Cr23C6. Several of these samples were electrolytically digested in 10 pct HCl in ethanol, with a current density of 0.1 amp per sq cm. None of the particles in the residue were magnetic. Accidentally, one cell was run at 1 amp per sq cm; e.g., magnetic particles were found in this residue. After careful separation, the magnetic particles were mounted on a quartz fiber and their diffraction pattern determined using a 5.73-in. Debye-Sherrer camera with CrK radiation. These particles showed a fcc structure with a lattice parameter of 3.57A. Prolonged exposure, up to 16 hr, produced no other lines on the film. The following facts seemed to be established at this time: 1) Austenite was the magnetic phase. 2) Neither ferrite nor martensite could be detected. 3) Magnetization could be produced by aging at 1200°F. One explanation of these data is that the carbide precipitation impoverishes the region immediately around the carbide particle of carbon and chromium and increases the proportion of nickel. All of these serve to increase the Curie temperature of the region around the carbide particle. If the composition change is enough, the Curie temperature will rise above room temperature. If the volume of the affected region is great enough, the magnetism will become detectable. At low aging temperatures, composition changes are great enough but the overall volume of impoverishment is quite small

Jan 1, 1962

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By Robert H. Richards

Jan 1, 1883

The question, Who won the war?, has been the text for innumerable newspaper, and magazine articles, the answers running from "bread and butter" to "poison gas," in a material sense, and from the "Y. M. C. A." to the "boys in the front lines," humanly speaking. Personally, I think the margin by which success was secured was so narrow that none of the complex, interdependent factors could have been .spared, and that, as Admiral Sampson said after the battle of Santiago: "There is glory, enough for all." But if any one human factor can be said to have been absolutely indispensable, I think all will agree that it was the engineer. The engineer, as a rule, is a modest fellow, so modest in fact and so averse to publicity of any kind that, referring to him as a class, he was hardly occupying the place he should in public estimation before the war. By way of illustration, in the early history of a mine in Bisbee, the chief owner was also the proprietor of a saloon and spent most of his time there. When asked why he did not pay more attention to the mine, lie replied: "Oh! I can hire a boy to look after that; it takes a man to run this bar." Comparisons of the position and pay of engineers with other occupations are sometimes made to show that the engineer is not getting all that he should, considering the time of preparation and the qualifications required. Perhaps at least a part of the cause may be his aloofness from many of the practical affairs of everyday life. Whether he won the war or not, the part played by the engineer has certainly placed him on a sort of pedestal in the public estimation at present and it is very desirable to keep him there and maintain the position he has made for himself.

Jan 9, 1919

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"' an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)', four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By W. N. Poundstone

The mining and ventilating system used in development work in the Pittsburgh Seam in northern West Virginia is discussed. The seam conditions and the nature of the accompanying methane gas are described. The type of equipment and the mining cycle will be discussed, showing how they are well suited for very gaseous development work. Face ventilation in development work is possibly the fastest growing problem of the industry. The coal mines of the future will be faced with the prospect of mining from under increasing depths of cover. Consequently, larger and larger amounts of methane gas probably will be found. The Pittsburgh Seam, in northern West Virginia, is an example of an area already faced with this problem. At the present time, most of the development work being done in this seam lies beneath 500 to 1200 ft of cover. The Pittsburgh Seam in this area has always been very gassy—even near the outcrop—and the recent development work has been accompanied with extremely large volumes of gas. In many cases, a single development section has liberated in excess of 1,000,000 cfm in 24 hr. This problem of heavy gas liberation was the chief concern, several years ago, when continuous mining equipment was first considered at Christopher Coal Co. All of us were apprehensive about the liberation that would accompany rapid extraction in a single working place. However, the experience during the past few years has shown that this ability to mine only one place at a time, is actually the key to working this type of coal. With all of the mining or advancement concentrated in one place, the ventilation can also be concentrated. By this it is meant that continuous mining permits the active working place to be ventilated with a maximum amount of fresh air, taken directly from the intake source without first passing another working place. Continuous mining (and a good ventilating system) also permits a much greater concentration of attention or vigilance to the actual working place. There are two things that are very important to the mining of coal having high rates of liberation. First, adequate volumes of air are necessary. Second, and perhaps more important, a mining and ventilating system must be used that will provide an uninterrupted flow of air to every portion of the working section. Liberations of this magnitude take only a few seconds of interruption for a dangerous accumulation of gas to occur. With adequate volumes of air available, the ability to concentrate ventilation more than offsets the concentration of gas emission that is inherent with continuous mining. The mining system used with continuous mining equipment at Humphrey Mine is similar to the system used at many mines in the area for development work. This system is designed to favor ventilation, realizing that other efficiencies are meaningless if the equipment must stop because of ventilation difficulties. This plan is especially well suited to minimizing ventilation interruptions. Basically, the overall plan of mining is to develop headings into virgin coal and encircle or block out large areas. These blocks are generally at least 2000 ft sq. The purpose of this blocking out is to bleed gas from the area before pillaring. Experience has shown this method to be quite effective, even in the most gassy areas. The gas in this field seems to migrate or flow readily from the solid coal into the outside return headings of the development work. The numerous clay veins and slips that are found in the area are extremely good avenues for gas flow. A block of coal, surrounded with development headings, usually bleeds off readily; and since it is cut off from the virgin coal, it is not subject to gas migration, through the seam, from this source. However, the outside return of the encircling development work, adjacent to the virgin coal, may liberate gas for years. This liberation from the outside ribs in the virgin coal is the reason split ventilation is used in development work. If split ventilation were not used, there would, in many cases, be a serious build-up of gas in the intake before it could reach the working face. Fig. 1 shows a typical development section having seven headings. The two outside places on each side are returns, and the three center headings serve as intakes. This section is equipped with a ripper-type continuous mining machine. An off-track loading machine is used to load from a surge pile on the

Jan 1, 1961

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965