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By J. E. Warren, J. H. Hartsock

Because of the extensive utilization of hydraulic fracturing for the stimulation of low-productivity wells, the two related problems of fracture design and evaluation have become economically significant and, as a consequence, helve motivated this investigation. The producing characteristics of horizontally fractured wells were studied to determine the fracture configuration that should be employed as the basis for the design of the treatment and to develop a method that can be used to establish the degree to which the design objectives have been achieved. The equations which describe the steady-state flow of a single-phase fluid into, and through. a finite-capacity fracture were solved numerically for an idealized reservoir-fracture model. The numerical results were used to obtain an apparent skin effect for each combination of the parameters considered. Based on the computed results, subject to the limitcitions implied by the assumptions that were made, the following general conclusions were drawn. 1. For a radius of drainage at least four times us large as the radius of the fracture, an apparent skin effect that is independent of the radius of drainage can be calculated. 2. The productivity of the hydraulically fractured system, relative to that of the unfructured well, can be determined from the apparent skin effect and can be used to establish design objectives. 3. In the evaluation of a fracture job, it is not Possible to determine both the radius of the fracture and its flow capacity uniquely from the apparent skin effect; an independent determination of one of the quantities is necessary. lNTRODUCTION Although hydraulic fracturing has been employed as a method for stimulating the productivity of literally hundreds of thousands of wells during the past 10 years, it is only in the last few years that improvements in fracture design1-6 and fracturing technique' have combined to increase the probability of obtaining a successful treatment to such an extent that the mechanics of the method may be considered to be standardized. From an economic point of view, however, two related questions must be satisfactorily answered before hydraulic fracturing can be used in the most profitable manner. The two questions are the following. I. For a particular well in a given formation, what are the optimum design specifications for the fracture treatment? 2. Have the design objectives been achieved by the fracture treatment? The significance of these questions has been recoguized, and some attempts to obtain answers have been made. Howard, et al,8 endeavored to determine the optimum treatment, based on maximizing profits, for any given formation; unfortunately, this work was based on a crude method for approximating the productivity of a well. Carter and Tracy9 utilized the same approximation to study the effect of fracturing on the behavior of a well producing by virtue of a solution-gas drive. Electrolytic models were used by van Poollen10 to investigate the variation in productivity due to fracturing; however, only a limited number of results were presented. Later, from the same model results, van Poollen, et al,11 attempted to justify an approximate expression for determining the productivity of a fractured well. It is quite apparent that there is a definite lack of the practical information necessary for specifying the optimum fracture configuration to be considered for design purposes. The only detailed attempt to develop a procedure for evaluating the result of a given fracture treatment appears to be that of van Dam and Horner.12 These authors described a technique for analyzing pressure build-down data, obtained immediately after fracturing, to determine the final fracture volume, the final fracture porosity, the fracture area, the fracture thickness and the in situ fluid loss of the fracturing fluid. While this approach should be useful whenever acceptable pressure measurements are available, it does not yield a value for the flow capacity of the fracture. Since the problems of fracture design and evaluation are inversely related, it should be sufficient to study the effect of the fracture configuration on the performance of a well. The primary objective of this investigation is to evolve a technique for computing the desired solutions. The secondary objective is to analyze these computed results in order to prescribe a method for evaluating fracture treatments. Because this study is exploratory in nature, its scope

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

Secretary's NOTE—on page 176,of this paper, in the fourth line of the first footnote, " 4° " should, be " 1" )'; and on page 180, at the beginning of line 23, ('lined boot" should be " unlined boot." Discussion. Frank Owen, London, Eng. (communication to the Secretary) : In his very interesting and valuable paper, Prof. Snow

Jan 1, 1900

By John O. Farmer

The wire-line tubing perforator is a mechanically operated tool that is run on an ordinary steel measuring line into the tubing of a well, under pressure, to drive into the wall of the tubing, and securely lock in place, a tapered, cylindrical insert containing an orifice. Use of the perforator obviates the necessity of pulling and rerunning the tubing to install jet collars or flow valves, reduces the cost, and simplifies the task, of placing an oil well on gas-lift operation. More important, however, is the use of the tool with a removable check valve and stop, to provide a means of washing drilling mud from the annulus between the tubing and casing, and to complete the well for gas lift operation without exposing the producing formation to the mud column and without moving the tubing string. This paper discusses the origin, development, and mechanics of the wire-line perforator, the various purposes for which the tool was designed, and the method of selecting orifice sizes for any depth, and gives the results obtained thus far in practical application. Origin and Development Several years ago, a tool that could be lowered on an ordinary steel measuring line into the tubing of a well under pressure was designed and constructed for the purpose of punching a hole in the tubing walls above a shale bridge that had completely plugged the tubing of a well in the Long Lake field, East Texas. The well was in a low, swampy area, which excessive rainfall had caused to be in- accessible by car or truck for about four months. The only equipment at the well site consisted of an ordinary steel wire line that had been carried there to measure the depth of the bridge. Since a pulling unit could not be moved to the well site, and as the pressure on the casing was 2100 lb. per sq. in., it became apparent that the only way out of the predicament was to make a perforating tool that could be lowered into the tubing on a measuring line and operated under Pressure. Thus, the first wire-line tubing perforator was designed and built as an expedient, and was not used extensively until it had been redesigned to meet more frequent and increasingly urgent needs. Until recently, it was necessary to pull the tubing to install jet collars or flow the when a well was to be placed On gas lift. Because most companies either maintained or had access to pulling units and crews for this work, little or no thought had been given to eliminating or even simplifying this task. When the manpower and steel shortage became so acute, however, many operators suddenly found themselves without facilities to equip their wells for gas lifting. The wireline tubing perforator already had been tried and proved successful, therefore operators immediately requested its use to punch gas-jet holes in the tubing, to eliminate the pulling and running of tubing strings. The first deficiency revealed by more general use of the perforator lay in the inability to regulate the size of the hole punched through the tubing. The size could not be controlled to any degree of

Jan 1, 1946

By John O. Farmer

The wire-line tubing perforator is a mechanically operated tool that is run on an ordinary steel measuring line into the tubing of a well, under pressure, to drive into the wall of the tubing, and securely lock in place, a tapered, cylindrical insert containing an orifice. Use of the perforator obviates the necessity of pulling and rerunning the tubing to install jet collars or flow valves, reduces the cost, and simplifies the task, of placing an oil well on gas-lift operation. More important, however, is the use of the tool with a removable check valve and stop, to provide a means of washing drilling mud from the annulus between the tubing and casing, and to complete the well for gas lift operation without exposing the producing formation to the mud column and without moving the tubing string. This paper discusses the origin, development, and mechanics of the wire-line perforator, the various purposes for which the tool was designed, and the method of selecting orifice sizes for any depth, and gives the results obtained thus far in practical application. Origin and Development Several years ago, a tool that could be lowered on an ordinary steel measuring line into the tubing of a well under pressure was designed and constructed for the purpose of punching a hole in the tubing walls above a shale bridge that had completely plugged the tubing of a well in the Long Lake field, East Texas. The well was in a low, swampy area, which excessive rainfall had caused to be in- accessible by car or truck for about four months. The only equipment at the well site consisted of an ordinary steel wire line that had been carried there to measure the depth of the bridge. Since a pulling unit could not be moved to the well site, and as the pressure on the casing was 2100 lb. per sq. in., it became apparent that the only way out of the predicament was to make a perforating tool that could be lowered into the tubing on a measuring line and operated under Pressure. Thus, the first wire-line tubing perforator was designed and built as an expedient, and was not used extensively until it had been redesigned to meet more frequent and increasingly urgent needs. Until recently, it was necessary to pull the tubing to install jet collars or flow the when a well was to be placed On gas lift. Because most companies either maintained or had access to pulling units and crews for this work, little or no thought had been given to eliminating or even simplifying this task. When the manpower and steel shortage became so acute, however, many operators suddenly found themselves without facilities to equip their wells for gas lifting. The wireline tubing perforator already had been tried and proved successful, therefore operators immediately requested its use to punch gas-jet holes in the tubing, to eliminate the pulling and running of tubing strings. The first deficiency revealed by more general use of the perforator lay in the inability to regulate the size of the hole punched through the tubing. The size could not be controlled to any degree of

Jan 1, 1946

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By F. Banemann

In discussing the problem of abnormal magnetic polarization, C. A. Heilandl† emphasized the unfortunate fact that our knowledge of the geological and physical conditions relating to such occurrences is very limited and that a more detailed insight into their physical causes would be extremely valuable for interpreting measured anomalies. He also pointed out that to arrive at quantitative physical formulas that would express the conditions that cause abnormal polarization many more occurrences of the kind would have to be recorded. The first part of this paper is a contribution to such descriptions. Abnormal Magnetic Polarization in South Africa The occurrence was mapped in the course of a magnetometric survey carried out about 70 miles to the east of Johannesburg and east of the Witwatersrand gold field, for the purpose of detecting the position of the suboutcrop of certain magnetite-bearing shales that occur in the lower portion of the Witwatersrand system of sediments, shales whose position in section in relation to the ore-bearing members of the same system of sediments are known. In this case the shales are covered by younger strata several hundred feet thick. Lines of magnetometric traverse were run at right angles to the strike for a strongly magnetic body. This body is a shale zone in the Witwatersrand sediments and has a strike of N.20°E. (magnetic) and dips 15" to the east. The field work was done by a vertical intensity field balance (A. Schmidt principle). The plotting is done in such a way that the sign is reversed from that usually employed in the northern hemisphere, so that a positive profile is obtained in abnormal cases while the same conditions in the northern hemisphere would give a negative one. This method of recording should be kept in mind in reading what follows.

Jan 1, 1940

By F. Banemann

In discussing the problem of abnormal magnetic polarization, C. A. Heilandl† emphasized the unfortunate fact that our knowledge of the geological and physical conditions relating to such occurrences is very limited and that a more detailed insight into their physical causes would be extremely valuable for interpreting measured anomalies. He also pointed out that to arrive at quantitative physical formulas that would express the conditions that cause abnormal polarization many more occurrences of the kind would have to be recorded. The first part of this paper is a contribution to such descriptions. Abnormal Magnetic Polarization in South Africa The occurrence was mapped in the course of a magnetometric survey carried out about 70 miles to the east of Johannesburg and east of the Witwatersrand gold field, for the purpose of detecting the position of the suboutcrop of certain magnetite-bearing shales that occur in the lower portion of the Witwatersrand system of sediments, shales whose position in section in relation to the ore-bearing members of the same system of sediments are known. In this case the shales are covered by younger strata several hundred feet thick. Lines of magnetometric traverse were run at right angles to the strike for a strongly magnetic body. This body is a shale zone in the Witwatersrand sediments and has a strike of N.20°E. (magnetic) and dips 15" to the east. The field work was done by a vertical intensity field balance (A. Schmidt principle). The plotting is done in such a way that the sign is reversed from that usually employed in the northern hemisphere, so that a positive profile is obtained in abnormal cases while the same conditions in the northern hemisphere would give a negative one. This method of recording should be kept in mind in reading what follows.

Jan 1, 1940

By Frank C. Canney

The word "other" in paragraph 4, line 11, column 1, page 205, should read "over;" the correct version of reason 2, this paragraph, is: 'L. . . 2) to evaluate the usefulness of certain geo-chemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and over veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; ...9 On page 206, in the top left hand corner of Fig. 1 (in the area bounded by 47°35' and 116°10), the reference to Fig. 3 is incorrect. The area of Pine Creek, South Fork Coeur d'Alene River, and portion of Big Creek (the area which includes, from left to right, Kingston, Pinehurst, Smelterville, and Kellogg) should be identified as that of Fig. 2A. The headings for columns 1, 3, and 4, Tables I and 11, page 209, column 2, were reversed when the paper was printed. The corrected tables are:

Jan 1, 1961

By Edward D. Peters

IT frequently occurs in the establishment of reduction works, in an entirely new and untried mining district, that the metallurgist in charge finds considerable difficulty in determining the process best adapted to the ores which he receives for treatment. At the first glance it would seem easy enough to decide what style of furnace is best adapted for beneficiating any one class of minerals. If the ore possessed a quartzose gangue and was comparatively free from base metals, while salt could be obtained at a reasonable price, one would naturally resort to a chloridizing roasting, and pan or barrel amalgamation for the extraction of its silver contents. If galena or carbonate of lead was the prevailing mineral, and charcoal could be obtained at moderate figures, the blast-furnace would beneficiate the ores most advantageously. But if, as is usually the case in Colorado, the ores consisted of an intimate mixture of galena, zinc-blende, copper-pyrites, and noble silver minerals, associated with an overwhelming mass of siliceous heavy spar, or limestone gangue, the common reverberatory furnace can be used to the greatest advantage; and, although the product is only a copper matte, I do not hesitate to affirm that it can be treated, and the silver, gold, and copper produced at nearly the same price for which silver and lead can be separated. In Germany, blast-furnaces are frequently used for this same purpose, both for argentiferous and non-argentiferous copper ores ; but any one who will take the trouble to examine the statistics of smelting at Fahlun, the Oberharz, and other Continental works of this description, will see that the expenses are far too great, and the production much too small to think of employing this method in our mining districts, where only the softest and most miserable kind of charcoal is obtainable. I propose in this paper to give an accurate account of the expenses incurred at the Mount Lincoln Smelting Works in treating the same kind of ore, and producing the same end-product in both blast and reverberatory furnaces. I have taken for comparison a favorable campaign of the blast-furnace, and a good average month's running of the reverberatory. In the blast-furnace estimate I have included the calcining and concentration of the matte produced during that campaign, as I always, when possible, concentrated the regulus made

Jan 1, 1874

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author's presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author's presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

El Indio, eighty percent -owned by Compania Minera an Jose Inc., a subsidiary of St. Joe Minerals, and twenty percent-owned by private Chilean investors, will open their new flotation and Carbon -In -Pulp plant near La Serena, 480 km (300 miles) north of Santiago, Chile, in early 1981. The underground mine, at an altitude of 4,270 m (14,000 ft), will produce about 1,270 mt per day (1,400 st per day) of ore containing about 2. 2570 Cu, and gold and silver to the extent of 16 and 254 g per mt (0.47 and 7.4 oz per st) respectively. While construction of the plant was underway, development ore, containing some 1,400 kg (45,000 oz) of gold, was shipped to the United States for recovery in a copper smelter. At El Indio the underground ore is rail-hauled to the mill a short distance from the portal where it is crushed, ground, and floated to produce a copper concentrate containing both gold and silver. The crushing plant also crushes waste for use as mine backfill. Approximately 92% of the copper and 60% of the gold and silver are recovered in the flotation concentrate. Flotation tailings, at a grade of 19 g Au and 116 g Ag per mt (3.4 oz Au and 0.55 oz Ag per st), are cyanided for 72 hours in six Pachucas with auxiliary air lifts for pulp transfer. Lime, cyanide, lead nitrate, and a phosphate are also fed to the cyanidation Pachucas. After cyanidation, the pulp is treated in four air lift Carbon-In-Pulp tanks equipped with external vibrating screens for carbon advance. Loaded carbon is stripped in two pressure vessels in parallel. Pressure stripping must be used because of the high altitude. Stripped carbon is dewatered in a spiral classifier before being reactivated in a rotary kiln and returned to the C. I. P. circuit. Pregnant solution is then sent to four banks of four Zadra cells for gold and silver recovery on steel wool. Zadra cell cathodes.are washed with the slimes being captured in a plate and frame filter. The filter cake and the washed cathodes are then dried on an infrared dryer and smelted in two stages to bullion bars. Published reports indicate that the total investment for this unique operation was in the neighborhood of $80 million.

Jan 1, 1981

By Russell W. Mumford

LITHIA compounds have a place in pharmaceutical and other chemical industries and lithium minerals in glassmaking and ceramics. The metal, although rare, is used to a minor extent in alloys. During the nearly 50 years of production of lithium minerals in the United States, the silicate mineral spodumene has continued as the chief source of raw material for the manufacture of lithium salts. Although twice as much lepidolite, a lithium mica, has been mined, most of it has been used in the making of certain types of glass. Amblygonite has been an additional but minor source of lithium compounds. Triphylite, petalite, and zinnwaldite have also been utilized in the past. All of these commercial lithium minerals contain low percentages of lithium (Table 1). In 1938, a new raw material for manufacture of lithium compounds made its appearance. This product was crude dilithium sodium phosphate (Li2NaPO4), obtained as a by-product of manufacture of potash and soda chemicals from the brine of Searles Lake, California. Searles Lake, which is now dry, lies in the extreme northwest corner of San Bernardino County, California, and consists of a large mass of salts. It was estimated by the United States Geological Survey that the crystal body contained about 25 pct voids, which are filled with a saturated brine. The brine consists mainly of the sulphates, chlorides, carbonates, and borates of sodium and potassium. Several other acid radicals, including phosphates, are present. Lithium is present in the brine in an amount corresponding to 0.01 15 pct Li2O. In the course of evaporation of water from the brine, during the process of manufacture of sodium and potassium chemicals, dilithium sodium phosphate crystallizes out and is recovered by a flotation operation. The lithium concentrate is filtered and dried and is then ready for shipment. It analyzes from 19 to 21 pct Li2O and now constitutes the highest known grade of crude lithium material. It is and will continue to be a major source of lithium for manufacture of lithium products. The variation in lithia content of the commercial minerals as mined is due to replacement of the lithia by soda and potash, to partial alter-

Jan 1, 1949

By Oliver Bowles

SUPERFLUOUS varieties and standards which are meriting the critical scrutiny of the manufactur-ing industry have a special significance in the non-metallic mining industries, where, many of the final or intermediate products are manufactured at the mine or quarry. Such processes of manufacture must be considered an integral part of mining in its broader sense. Improvements may be either elimination or standardization. - The chief requirement of elimi-nation is an agreement between consumers and pro-ducers based on facts deduced from: statistical data. Standardization is much, more complex. Standards .may be established only when a very; thorough knowledge has been gained of the physical and chemical properties of the products, and the requirements of consumers. The activities of the Bureau of Standards are. largely directed toward such determinations. Paving-brick manufacturers, together with highway engineers, representatives of certain engineering socie-ties, and Government bureaus, have agreed that of the 66 styles of paving brick on the market 11 only are, essential and 55 are superfluous. Steps have been taken to reduce the output of -all but the 11 standard types. It is customary for manufacturers of structural slate to prepare it in sizes specified by builders and architects. Thus the material cannot be manufactured in advance and the result is irregular activity of mills, delays in filling orders, etc. To improve this condition, the Structural Slate Co. has issued a series of pamphlets giving complete specifications of structural slate for various purposes. Architects find it so much easier .to, order slate from these sheets that standard sizes are specified in preparing plans for new structures. Slate switchboards are usually manufactured after. the order has been received. One manufacturer claims that 80 per cent. of all switchboards are of standard sizes, and he keeps such sizes in stock. The facility with which orders may be filled from stock, and the improved quality of seasoned switchboards, will undoubtedly influence electrical, companies toward a more uniform standardization in size. Simplicity, could be further attained by the elimination of minor irregularities in .style; for example, in the beveled. edges.

Jan 2, 1922

By Franklin J. Kay

Introduction The methods used in surface, mining vary throughout the world, depending on many variables such as: the types of over- burden materials, the depth of the overburden, the thickness of the seam, and other operational choices, both financial and functional. However, the stripping machines are typically draglines, stripping shovels, excavators, scrapers, loaders, and bulldozers. In all cases the economic feasibility of mining thin seams depends on the market needs, the market location, the equipment used, the mine management, the quality of the coal, and the labor market. Slight negative combinations of these parameters have closed many mines while positive combinations allow others to exist. The limited mobility or slow movement of large stripping shovels, draglines, and bucket wheel excavators make them more economically fitted to areas where large quantities of overburden are to be moved. This is necessary to keep the transfer and setup time between pits a negligibly small percent of the total operational time. Equipment such as the scrapers, loaders, backhoes, trucks, and bulldozers that are either very mobile or can be trailered is more versatile and can be used in the smaller area mines.* Mobile equipment is also more practical in areas with shallow overburden because of the constant movement required while removing overburden. In thin coal seams the equipment is usually paired such that the operational equipment can be listed as: (1) dragline-loader, (2) shovel-truck- loader, (3) scraper-loader. (4) loader-truck-loader, or (5) loader-loader. In these operations the overburden is removed with the first machine(s) of the pairing and the loader or loaders are used for coal production. Recent articles in Coal Age (Chironis, 1978) and Mining Engineering (Wiebmer, 1978) have discussed varying philosophies in mining similar seams of coal. One operator uses draglines for competitive mining while the other uses scrapers for the same purpose. Both cite strong cases sup- porting their choice of equipment as good sound economic decisions and their success supports their choices. The drag-line operation is adding new larger draglines to decrease the cost of mining, rather than to increase coal production. The scraper operation has also gone to more and larger scrapers for basically the same reasons. These operations and all

Jan 1, 1981

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By James Terry Duee

No important producing developments took place in Colombia during the year 1928. This was at least partly due to the paralysis of operations by the passage, during the latter part of 1927, of a law which was regarded by the oil companies as confiscatory and unjust, and the promulgation of exceedingly stringent regulations of this law under decree No. 150, published Jan. 28, 1928. This decree, which contained 24 articles, practically prevented not only producing operations by the oil companies but even such activities as geological explorations and surveying, as severe fines were imposed for the possession of maps not registered with the Ministry of Industries. Both this regulatory decree and the law were subject to attack in the courts by several of the oil companies. The regulatory decree was suspended May 22 by Presidential proclamation, until the suits against it are decided by the Supreme Court and Council of State. Though another law was introduced into the Colombian Congress at a later date, no action was taken on it, and at the time of the writing of this paper, it would appear that no oil bill will pass the Colombian Congress during the present session. The Barco concession, which was revoked in February, 1926, still continues an unsettled matter, although there have been rumors that the government was attempting to come to some decision on this rather difficult question. A hopeful sign toward the close of the year was the settlement of negotiations with the Tropical Oil Co. over the acceptance of the payment for royalties due the government from that company. This settlement, which covered a royalty on crude oil produced from June 30, 1926 to June 30, 1928, represented a cash payment for approximately 3,000,000 barrels. It is to be hoped that during the coming year the Colombian government will see its way clear to clarify its position on petroleum legislation. A good augury for the future was the statement made by President Abadia Mendez on New Year's Day, in which he courageously admitted the errors of previous legislation and said, regarding oil, "Very soon

Jan 1, 1929

By C. Gatlin, M. E. Chenevert

The effects of bedding plane orientation on the elastic constants and the yield strengths of three laminated rocks (one sandstone and two shales) and one isotropic rock (a limestone) were studied. The directional dependence of the elastic properties of these rocks was experimentally evaluated using a triaxial compression cell and auxiliary stress-strain measuring equipment. Symmetry of Poisson's ratios within the bedding plane suggested that horizontal isotropy exists, but the bedding planes do give rise to an appreciable difference between properties in the horizontal and vertical directions. For the three bedded rocks studied, Young's modulus was lower normal to bedding than along bedding. Yield strengths were determined at confining pressures from 0 to 12,000 psi in a triaxial compression cell. The rocks studied showed strength reductions as high as 40 per cent when the test specimen was oriented at 20°-30° to the bedding planes. The mechanical behavior of these rocks suggested that the rock properties of shear strength and/or coefficient of internal friction can vary with direction, depending on the particular rock tested. Tensile strengths were also measured and found to be lowest when failure occurred along bedding. This work shows that bedded formations exhibit sizable directional variations in both their elastic constants and yield strengths. It is suggested that these variations may be accounted for by using the "elastic laminate" model and the "variable coefficients" failure model. INTRODUCTION The nature of rock deformation at elevated pressures has been studied by many workers; papers by Handin,l,2 and Robinson3 illustrate the present state of knowledge. Most investigators have either chosen rocks which were as isotropic as possible (in order to avoid complications of data interpretation and analysis) or they have oriented their samples so that the effects of anisotropies (such as bedding planes) have been avoided. Of the studies performed, few were concerned specifically with mechanical anisotrop-ies. Griggs4 has presented limited data for specimens cut parallel, normal, and 45° to the bedding plane; he relates the strength anisotropy observed to the fabric (bedding) anisotropy. His tests were primarily concerned with large deformations (20 per cent strain); thus, no directional values of the elastic constants were reported. Handin has reported the results of similar experiments. Bott5has discussed rock strength anisotropies due to faults, cleavage, or bedding. He was concerned primari ly with determining the shear stress on such planes and did not mention the effect of friction. Jaeger6 later generalized Bott's work by taking friction into account and presented a limited theory for the failure of rocks having a "single plane of weakness", and also for rocks having a constant coefficient of friction, and a shear strength which varies with bedding plane orientation. Donath and Cohen,7 and Donathg have evaluated rock strengths from shale and slate specimens cut normal and parallel to bedding. A dependence of cohesive strength (7,) on the specimen orientation was also shown. Adler9 has also studied this problem and lists similar results. He assumes that all bedded rocks behave according to Jaeger's single-plane-of-weakness theory. Kalinin and Belorussov10 list results for strength tests parallel and perpendicular to bedding and use this information as a basis for hole deviation analysis. From the literature it is apparent that sedimentary rocks have been tested under widely varying conditions of stress; however, the assumption of isotropy is generally, but not always, made. Since geologic sedimentation often deposits sediments in very definite lavers.,. it seems that more svstema tic attention should be given to the possible effects of this natural bedding. Bedding, as used here, refers to visible regularities of grain size or orientation resulting from depositional processes. The mechanical strength anisotropies, which bedding may present, is not the only anisotronic property to be considered, since the elastic

Jan 1, 1966

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962