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By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By James Norman, Benjamin S. Lindsey

BaritE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the 'more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, II.II per cent SiO², and 2.85 per cent R²O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is scparated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1942

By Benjamin S. Lindsey, James Norman

BaritE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the 'more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, II.II per cent SiO², and 2.85 per cent R²O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is scparated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1942

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By Herbert D. Drechsler

The objective of this paper is to identify the components of income above that necessary to keep a mine in production and relate those components to the profits of a mining firm. This is a discussion of "Economic Rent". Economic rent is the payment to the factors of production -- capital, labour, entreprenuer and the owner of the mineral deposit -- above the minimum necessary to keep all of these factors cooperating in the production of minerals from a particular deposit. THE SOURCE OF ECONOMIC RENT IN THE MINING INDUSTRY In the mining business each mine has a unique cost of production unrelated to any other mine. The cost of production is developed from many factors such as the technical characteristics of the deposit: depth of deposit, depth of overburden, areal extent, and type of deposit. Furthermore, there are locational factors which also alter cost of production. For example, identical mineral deposits located in Zambia or in the southwest U.S.A. would have different capital and operating costs. These differences occur because of different qualities of labour, ease of acquisition of operating supplies or investment capital and other similar factors. To explain the source of rent, we shall use ideas developed by Alfred Marshall and Kenneth Boulding. Suppose a meteorite with special qualities exploded over earth and sent showers of small meteorites to the ground in various places. At some point in time, people learned of the special qualities of these meteorites and a demand arose and one mine was started. Suppose further that the cost of production to produce these meteorites was different for each deposit. Probably the lowest unit cost mine would commence production because if a higher unit cost mine started-up, eventually someone would discover a deposit that had a lower unit cost of production. The lower unit cost mine would take over the market and the high unit cost mine would cease production. The cost curve for the first mine would look like the following Figure 1. [ ] The output for the first mine is on the horizontal axis with the cost per ton on the vertical axis. The curve labelled AC I is the average total cost of production over the range of possible production that could occur at the property. The total costs are composed of variable costs, which are dependent on output and fixed costs, which are dependent on time. For example, the cost of operating supplies would be a variable cost and normal profit would be a fixed cost.1 The opportunity cost of the investment would also be part of the fixed costs. In our example, all factors of production, are receiving the minimum necessary payment that will keep the mine operating. The average total cost curve is U-shaped because at zero output, the meteorite mine has no variable costs, only fixed costs which, on a unit basis, obviously are very high. To produce a small output of meteorites, the mining firm adds

Jan 1, 1985

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By H. V. Welch

In this paper, as prepared for delivery at the Southern California regional meeting on Oct. 14, 1948, it was thought best to interpret the term "economics" in a rather broad manner and to include, in addition to the material losses and recoveries and associated monetary values (Part I), a limited discussion of the increased difficulties or the particular problem and the special requirements, as the particle sizes of the suspended particles range down from the relatively coarse to 100, to 10, to 1 micron or even to a fraction of one micron (Part II). Further, it is not quite in order to overlook entirely the community and individual health problems, although space requires the economics of this to be considered only very incompletely. Therefore, Part III, covering this phase of the subject, is very limited. This paper, then, is divided into 5 parts or headings as follows: I Losses and/or values in suspended solids. II Particle size. III Dust and fumes in community and individual living. IV Means and Procedures for dust and fume collection. V Description or examples of specific equipment in service and of the several types used for dust and fume collection. Because of the wide extent and wealth of subject material available and the space and time limitation imposed, presentation and discussion are less than originally planned. I—Losses and/or Values in Suspended Solids The weight involved in moving streams of industrial plant gases is commonly not appreciated, neither is their carrying power in the weight of solids maintained in suspension and moved with the gas stream from a point of origin or pick-up to a point of dissipation or settlement. These, however, are major weight figures; for example, in a modern iron blast furnace there may be five tons of gas for every ton of iron produced and by the time this blast furnace gas has been burned in stoves or under boilers the weight of gas discharged to atmosphere is on the order of eight times the weight of iron produced. Similarly for nonferrous metallurgy there may readily be from 10 to 20 times the weight of gases discharged to atmosphere as there is metal produced. A cement kiln in operation or a kiln in service to produce metallurgical lime may have on the order of 5 to 6 times the weight of stack gases as of clinker or lime produced, and at least the cement kiln, because of the very fine nature of its feed, is a very heavy dust producer. It may be noted that there have been two developments in progress for nearly three decades. Both are extraordinary in the industrial economics effected and in their ready availability to ever larger units of operation and their ever widening importance in industry, and both are productive of great quantities of finely divided material in furnacing. The first of these is the flotation process for ores, especially the metallics such as copper, lead, and zinc; and the second, powdered fuel combustion for power plant, industrial plants and metallurgical operations. Today, new developments, for example, flotation for the nonmetallics such as higher grade limestone for cement manufacture which requires still finer grinding and the powdered-coal-fired boilers with production ratings of over 1,000,000 lb of steam per hr, bring still more concentrated and hugely increased quantities of stack emission. Perhaps the honors for the greatest interest in the quantities and values escaping in waste furnace and equipment gases belong to the nonferrous metallurgical operations. Their record of achievement in the installation of dust and fume collection equipment, largely baghouses or Cottrell electrical precipitators, is exceeded by no other industry. Something of the magnitude and variety of equipment utilized in such recovery systems was covered by the writer in two papers presented to the Institute some 10 years ago.1,2 It is not intended to repeat the material of those articles, but it is thought that they complement this offering and should be noted. COPPER ROASTERS As the copper roasters are the first of the series of furnaces handling the copper-bearing concentrates in the usual copper smelter of today, it is in order to make them the first consideration. Multiple hearth sulphide roasters, not hard driven, often maintain their dust loss through exit gases at 3 pet or below of feed to furnace; in hard-driven or maximum-driven furnaces, exit gas losses often approximate 7 pet of charge with a ±2 pet variation for special conditions prevailing at some plants. A 5 pet loss of feed in a roaster gas exit, unless reclaimed, often makes the difference between a profit and loss operation, and in many cases substantial recovery is the very basis of dividend payments. As there is available very practical and successful equipment for the collection of the

Jan 1, 1950

By H. Brandhorst, C. G. Dunn

THE main purpose of the present note is to provide further information on the effect of orientation on strain-induced grain boundary migration in sheet material. A secondary purpose is to draw attention to the presence of a possible (hkl) dependent surface energy driving force, when the two grains of a bicrystal specimen have different (hk2) planes at the gas-metal interface, and to suggest means of eliminating this effect from the strain effect. If two grains A and B of a bicrystal have specific surface energies ? A and ? B respectively, there exists a driving force for grain boundary migration equal to 2(? B - ? A)/t, where t is the thickness of the specimen.' When t is quite small and the residual strain energy densities €A and €B of grains A and B, respectively, adjacent to the boundary are nearly equal, it is possible that the surface effect may be larger than the strain effect. he difference € B - € A gives a driving force per unit area of grain boundary due to an applied strain.)2 However, with increasing t the surface effect decreases while the strain effect presumably remains constant. Therefore, at some sufficiently large value of t, it is possible to ignore surface energy driving forces.* On the other hand, the surface effect is eliminated for all value of t when both grains have the same (hkl) orientation or have identical values of surface energy. Although the previous study provided information on the effect of orientation on strain-induced erain boundary migration,' no orientations with the (100) plane in the plane of the sheet were included. The present paper provides information of this kind. A seed crystal reorientation technique4 was used to prepare a large bicrystal of silicon iron (3 1/4 pct Si) consisting of two (100) grains in the (100) [001] and (100) [Oil] orientations. After a cold rolling strain (7 pct reduction to 3/4 mm final thickness), small specimens were prepared as before2 and then annealed in hydrogen. The boundary migration was such that the grain in the (100) [011] orientation always grew. After overnight anneals at 1100° or 1000°C, none of the initial (100) [001] grain remained. An anneal of 30 min at 950°c, however, provided information on the start of boundary migration. Fig. 1 shows both the initial position (lower line) and the final position (upper curved line) of part of the boundary, as revealed by thermal grooves. In a different area, part of the final boundary was not revealed by thermal grooves; the rate of boundary migration presumably was too high for the growth front to be defined by the time dependent thermal grooving process. In another area there was a vacated intermediate position connected to the initial position of the grain boundary. This indicates that only part of the boundary

Jan 1, 1962

By Dorsey Hager

North Central Texas has recently become a center of interest for the oil men of America. The bringing in of the McClosky well at Ranger, Eastland County, and the shallow pool at Brownwood, Brown County, in 1917, has stimulated interest in this area to fever pitch. Oil men from all over the United States are now investing there. The area of present interest is shown by the accompanying map (Fig. 1). The money spent in leases runs into millions of dollars. It is no exaggeration to say that a strip of country 200 miles (321 km.) long and 125 miles (201 km.) wide, comprising some 15,000,000 acres (6,070,310 ha.), has been leased practically solid at a cost for rentals and bonuses of at least $1 per acre. The test holes contracted for will certainly number 400, at a cost of at least $5,000,000. From what has been done in the past six months, $20,000,000 at least will be spent. To pay returns on this amount of money, new production to the extent of at least 12,000,000 bbl. must be obtained. At present, the production from new fields will not average over 5000 bbl. per day; three wells at Ranger are producing 3000 bbl.; 250 wells at Brownwood produce 1000 bbl.; and the Gray well, Coleman County, is as yet an unknown factor. However, at Ranger there is every indication of developing a good pool covering from 1500 to 2000 acres (607 to 809 ha.), more or less, but the wells are deep, 3400 to 3800 ft. (1036 to 1158 m.), and cost $35,000 to $40,000 to drill. Large wells are necessary to pay for such expensive holes. As new wells are drilled, the gas pressure will be lowered rapidly, and large production need not be expected. For those oil men who expect a second Cushing or an Eldorado, Ranger holds little of promise. At Brownwood, Brown County, there are some 250 shallow wells (depths from 200 to 350 ft.) averaging 4 to 7 bbl. per day. There is a chance of an extensive producing area for these shallow sands to the southwest, and the opening of several thousand acres of shallow oil territory, and also some promise of deeper oil horizons in the Ranger horizon, but probably all under 2500 ft. At present, the lease brokers and speculators, and only a handful of oil men, have made any money. More fields must be developed, and it is more particularly with these possibilities that this paper deals. Lack of water for drilling purposes has undoubtedly held back development so far this year; this part of Texas has had a drouth for two years and there is an actual scarcity of water. Geological investigations so far undertaken cover nearly all the area outlined, and while pakt of the

Jan 1, 1920

By Benjamin S. Lindsey, James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent Si02, and 2.85 per cent R203. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder ,was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941

By A. E. Back

A method is described in which particulate iron, as distinguished from high purity iron powders used in powder metallurgy, is a precipitant for copper contained in dilute solutions. A new precipitation apparatus utilizes particulate iron precipitants to recover copper more efficiently than is possible in a conventional launder precipitation plant. In the search for lower cost methods of recovering copper from mine water, the use of sponge iron or particulate iron (as distinguished from iron powder used in powder metallurgy) as precipitants in place of tin cans, detinned scrap iron, or scrap iron is an intriguing possibility. The relatively faster copper precipitation rate obtained with particulate iron as compared to scrap iron promises economic and processing advantages when, and if, particulate iron becomes competitive cost-wise with available scrap iron. Kennecott has developed a precipitation cone,' see Fig. 1, utilizing various particulate iron precipitants and has demonstrated the process successfully in a prototype at a flow rate of approximately 1000 gal of solution per min. Essentially complete precipitation of copper is obtained, the cone overflow solution is clear and contains no particulate copper, and the iron factor is more favorable than in a conventional launder plant. Initially, sponge iron produced at the Ray Mines Div. Kennecott Copper Corp. for use in a Leach-Precipitation-Flotation process was used in exploratory tests to develop a suitable apparatus to take advantage of the rapid precipitation rate and efficient iron utilization for the recovery of copper from dilute solutions. Here it was demonstrated that, when sponge iron was added to a launder, the particles of iron collected in the bottom of the launder and tended to cement together. This resulted in incomplete precipitation of the copper and inefficient utilization of the iron. Next, sponge iron was suspended in glass columns to study the dynamics of the precipitation reaction. Again it was observed that the particles tended to cement together at low solution flow rates, while at higher flow rates large amounts of the precipitant overflowed the column, resulting in loss of precipitant and an inefficient process. Next, the precipitant was suspended in an inverted cone in a rising column of solution. Dynamic suspension of the solids was maintained at relatively rapid solution flow rates with instantaneous and complete precipitation of copper and with improved iron utilization. The first tests were conducted on a batch basis and it was determined that a dynamically suspended bed of precipitant was necessary for satisfactory operation. More than 99% of the metallic iron could be converted to metallic copper by careful control of the residence time in the cone and copper precipitation was essentially complete, even when the available iron precipitant was almost depleted. Several cones were built, ranging in capacity from 1 to 200 gal of feed solution per min, and finally, a prototype cone was constructed which was 20-ft high

Jan 1, 1968

By James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to loo per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941

By W. L. Chen

The Batac jig was first introduced in the US for fine coal cleaning in 1973 (Tackett, 1977; Hake, 1976). Since then, a total of six such jigs of various sizes have been installed in five US plants for a total capacity of 2346 t/h. The raw coal size ranges from 19 mm x 0 to 9.5 mm x 0-fraction sizes previously fed to heavy medium cyclones, Deister tables, or water only cyclones. Growing interest in the Batac jig as a replacement for the above equipment is due to the following reasons: • Unlike heavy medium cyclones, no magnetite is required. As a result, the operating cost of the plant is reduced. • The compactness of equipment is unique on a unit ton per hour basis as compared to other equipment. • Solid state electronic control of jig stroke length, frequency, and jig bed depth makes the equipment highly efficient. Installations of Batac jigs in the US as of June 1980 are shown in [Table 1]. Use of the Batac jig is even greater outside the US (Anonymous, 1980; Chen, 1980). Its use is not limited to fine coal but is applied to coarse coal as well, with 102 mm size in the feed (Zimmerman, 1975). In countries where consumption of magnetite associated with the heavy medium system of coal cleaning is considered a waste of iron ore resource, the Batac jig is regarded as the primary choice in the selection of cleaning equipment (Chen, 1980).

Jan 1, 1981

By Hsun Hu, R. S. Cline

The annealing behavior and the mechanism of re-orientation during recrystallization of iodide titanium cold-rolled 94 pct have been studied in detail. Results indicate that recrystallization occurs by the nucleation and growth of new grains, as in other common metals. Recrystallization nuclei form by the coalescence of subgraim, and the change in texture as a result of recrystallization is largely due to selective growth among the nuclei formed. The annealing of titanium is characterized by a wide range of overlap of the various stages of the annealing process, which may be responsible for a range of activation energies observed, and for the apparently gradual change in the annealing texture as a function of time or temperature. The deformation and recrystallization characteristics of titanium and zirconium are very similar. In cold-rolled strip, the deformation texture consists of two symmetrically oriented components, each having the basal plane laterally tilted at about 30 deg from the rolling plane and the [1010] direction parallel to the rolling direction. Upon annealing for recrystallization, the change in texture can be described, for simplicity,* as rotations around [0001].2'6'8 According to McGeary and Lustman,' recrystallization occurs in zirconium through normal growth of the subgrains, which they called "domains", without the nucleation of new grains; and the magnitude of rotation around the [0001] axis increases gradually during the progress of recrystallization. If these conclusions were true, the mechanism of recrystallization in zirconium would be basically different from that in most metals, since it is commonly known that recrystallization with reori-entation always involves the migration of high-angle boundaries. In an attempt to clarify the situation, the mechanism of reorientation during recrystallization in iodide titanium cold-rolled 94 pct was studied in detail. The structural and textural changes upon annealing at various temperatures were examined by optical and transmission-electron microscopy, X-ray pole figures, pole density distribution measurements, and micro-beam techniques. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. An iodide titanium crystal bar was are-melted and solidified in a cold-hearth crucible under a purified argon atmosphere. The solidified ingot had dimensions of approximately 3 by 1/2 by 3 in. One face of the ingot was somewhat uneven, but was as clean and shiny as the remaining parts of the ingot. Large grains with a Widmanstatten internal structure were clearly shown on the shiny surfaces, indicating the occurrence of P — a transformation upon rapid cooling from the melt. Analysis of the are-melted ingot indicated C 0.033, N 0.010, H 0.013, 0 0.002 in weight percent, and traces of iron, copper, and silicon as detectable impurities. The ingot was cold-rolled -40 pct to 0.300 in. thick with a reduction of 0.005 in. per pass. The defects on the uneven side of the ingot were then removed by machining. This reduced the thickness to 0.285 in. The piece was then recrystallized by annealing at 800°C for 1 hr in a fused silica boat charged into a fused silica tube furnace under a vacuum of 10~5 mm Hg. To refine the grain size, the recrystallized metal was again cold-rolled 40 pct to 0.170 in., then annealed at 700°C for 1 hr. These treatments yielded a strip with a uniform equiaxed grain structure, having a penultimate average grain diameter of 0.04 mm and a hardness of approximately 90 Dph. Final rolling reduced the thickness from 0.170 to 0.010 in., corresponding to a reduction of 94 pct. The strip was rolled in both directions by reversing end for end between passes. Surface lubrication was provided by oil-soaked pads attached to both rolls. Specimens of 1 in. length (for X-ray examinations) and +in. length (for hardness and microstructure examinations) were cut from the rolled strip, and a width of & in. was cut from the edges of each specimen by a jeweler's saw. These specimens were then etched in a solution of 10 cu cm HN03, 5 cu cm HF, and 50 cu cm H,O to 0.008 in. thick to remove the surface metal, as well as the distorted metal at the saw cuts, prior to annealing or measurements. To minimize any surface reaction with the atmosphere, all specimens were kept in an evacuated desiccator. Isothermal Anneals. All annealing treatments were conducted in vacuum in a fused silica tube furnace as described earlier. The temperature of the furnace was controlled to within *2"C. The specimen was placed in a fused silica boat, then pushed into the hot zone of the furnace. It took about 5 to 6 min for the specimen to reach the furnace temperature. After the specimen was held at temperature for a desired length of time the boat was pulled to the cold zone of the furnace; the heating-up period was excluded from the isothermal annealing time. Thus, the uncertainty in annealing time is higher for very short anneals, but negligible for long anneals.

Jan 1, 1969

By I. A. Lesk

The various materials utilized in the construction of integrated circuits, and the resultant materials interfaces, are discussed with emphasis on a materials system that is compatible with all types of integrated circuits and minimizes the number of different interfaces. Problems with interfaces may originate in the silicon, on its surface, and between other materials within the integrated-circuit package independent of the silicon. ThE difference between integrated-circuit theory and practice may generally be spelled out in terms of the difficulties in fabricating a desired structure. There are, of course, problems in forming the requisite materials, of the necessary composition and geometry, where needed. A distinct class of problem, however, is associated with interfaces— generally between different materials, but occasionally between regions of the same material. We require that each interfacial system perform its proper electrical, mechanical, and thermal function, and do so in an unchanging manner with time under the most severe operating conditions. In a practical sense, we deal in nonideal systems, such that it is generally not possible to form an interface exactly the way it was intended, even if we allow for a knowledge of the practical limitations of the fabrication system. Another way of looking at this situation is to realize that, when we form a group of interfaces under apparently the same experimental conditions, there are often differences of important consequence between them. Very high-magnification pictures, such as are obtained by an electron microscope, reveal fine structure that often differs over the area of a given sample, as well as from sample to sample. Low-magnification pictures look better, but don't eliminate the problem. The trend towards integrated circuits, and away from circuits fabricated utilizing separate components, is very strong in many areas of electronics. A typical silicon monolithic integrated circuit, still in place in the wafer on which it was fabricated, is shown in Fig. 1. The increased reliability which is being experienced through the use of integrated circuits can, to a large extent, be credited to the reduced complexity of the interface system that is present in the electronic system. A glance at Fig. 1, however, with all of its epitaxial and diffused p-n junctions, and interconnect system, shows that interfaces have been far from eliminated. Fig. 2, depicting a schematic cross-sectional view of a (partial) typical integrated circuit, illustrates in detail the numerous interfaces that occur in this type of structure. Besides the individual circuit elements, there are interfaces for isolation, and, Fig. 3, even a crossover requires a series of interfaces. What has been accomplished, however, irrespective of whether or not the total number of interfaces in the circuit is increased or decreased, is that the variety of interfaces is very much reduced. This is because there are fewer materials involved. Since the expense incurred in an R & D program to improve reliability is pretty much directly proportional to the variety of interfaces involved, it is economically advisable to work with integrated circuits for highest reliability. That is not to say that circuits built using standard components could not be made as reliable as integrated circuits, but that the expense involved because of the more complex over-all interface system would be much greater. Although electronic performance utilizing integrated circuits with all silicon elements (i.e., transistors, diodes, resistors, capacitors) is adequate for many applications, there are numerous instances where thin-film passive elements must

Jan 1, 1965

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By E. D. Glass, R. C. Hessing

The volume of gas in storage reservoirs may be compuled from estimates of hydrocarbon pore volume and gas density. However, both are dificult 10 estimate accurrately. Further, no adequate method has been presented for estimating reservoir performance during operation for Volumetric gas-storage reservoirs. Normally, gas-storage reservoirs exhibit small pressure gradients in the area conr(zilliitg the storage wells, even under conditions of maximum injection or withdrawal. A zone of low permeability usally surrounds, and is in communication with, tile permeable zone which causes the storage reservoir to exhibit a definite pressure lag, as evidenced by lack of pressure stabilization after extended periods of shut-in. An analysis is presented for determining pore volume and gas in place, and for predicting future reservoir behavior of such reservoirs. The mathematical development is presented and a solution is shown for an operating storage reservoir. INTRODUCTION Depleted gas reservoirs arc often used for gas storage. The reservoir usually contains a permeable area in which numerous storage wells arc located. The permeable zone permits high deliverability and injectivity with relatively small pressure loss. However, pressure equilibrium may not be attained even after long periods of shut-in because of the fact that the permeable zone is in communication with an adjacent tight section. Most of these gas-storage reservoirs are sand lenses, such as ancient beaches or offshore bars. The areal geometry of these reservoirs is normally such that flow in the tight zone will be approximately linear, and the solutions presented here should apply. DISCUSSION For purposes of this paper, a gas-storage reservoir is considered to consist of a volume of permeable rock in communication with tight rock, all of which is surrounded by an impermeable barrier. Pressure gradients across the permeable zone are small due to low flow resistance and well density. Hence, the permeable zone is considered to be at a uniform pressure which is only a function of time as gas is injected or withdrawn. The tight zone is considered to be linear with uniform permeability and porosity, and the pressure in the tight zone is a function of both position and time. l&apos;wo solutions for flow in this system are used to define the reservoir and determine its properties. The first solution is for an infinite linear tight zone in communication with the permeable zone. The expression for constant gas-withdrawal rate is Eqs. I and 2 ore superposed to account for varying rates of production or injection and are used to fit gas-storage field reservoir history. The solution for the infinite case, Eq. 1, is first applied to field data for early times following a shut-in period. Constants BDa and c are ohtained by a least-squares fit of pressure and rate data. After the pressure wave from gas injection or withdrawal reaches the external boundary of the tight zone, the infinite solution will no longer apply and pressure behavior should be more nearly represented by Eq. 2 for a gas reservoir in communication with a finite linear tight zone. The values of the constants found from curve-fitting Eq. 1 to the early time data may then be used in Eq. 2 that only the coefficient- L containing the unknown