Search Documents

By R. W. Hyde, S. E. Eaton, B. S. Old

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides' In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By D. A. Dahlstrom

WITHIN the past decade, certain economic, legal, and technological changes have intensified the necessity for an efficient classifier or deslimer of particles at and below the 200-mesh point. First, mechanization of mining has increased the percentage of clays, silts, refuse, and high-ash material in the run-of-mine coal. Second, many washing plants must rely on smaller percentages of fresh make-up water because of shortages, economic factors, or legal restrictions on waste water disposal. Finally, the crushing of middlings and coarse refuse plus the trends toward the finer sizes in sales has further increased the amount of fines produced per ton of mine-run coal. A joint consequence of these circumstances has been the augmented percentage and build-up of —200-mesh material in the finer coal fractions and tipple circulating water. This results in the following disadvantages to the operator: (1) Higher ash percentages in the fine coal caused in large measure by the greater ash content of the —200-mesh material, (2) more difficult or expensive recovery of the fine coal from plant slurries, (3) lower filtration, drainage, and drying rates caused chiefly by lower permeability and the greater surface exposed per unit mass of the finer particles, (4) greater difficulty of beneficiatiing the fine coal because of lowered equipment efficiency and the partial "coating-out" of the —200-mesh fraction on the coarser coal particles. Obviously some cheap but effective fine-size classifier must be developed to aid in solving the above problems. To eliminate the generally unwanted —200-mesh fraction from coal slurries, several methods are in use. Probably the most popular with coal operators is the settling cone wherein the larger particles settle downward to the apex of an inverted cone while the slimes and fines are carried upward by vertical fluid currents caused by the overflow of the bulk of the water at the outer rim. The main advantage of the unit is the low initial and operating cost since no moving parts are involved. Disadvantages are primarily low capacity per square foot or floor space and the loss of good coal in the overflow above the 100-mesh size due to localized, high-velocity gradients and nonuniform, fluid-flow patterns, especially at high loadings. Also, when high slime concentrations are present, desliming efficiency is severely injured.', ' Other methods employed are the drag and spiral classifiers and the hydroseparator.' These involve mechanical separations achieved by moving parts and naturally result in higher initial costs. As they are all based on the settling velocity of the particles at the mesh of separation under operating conditions, area requirements are again large per gallon of throughput if they are to classify at the 200-mesh point. Usually the selection is made to operate at a higher throughput and thus sacrifice some coarser coal in the slime overflow. Cyclone Possibilities in Desliming To overcome the disadvantages of present deslirning methods, it is necessary to use a device that exhibits a very stable and uniform flow pattern while greatly increasing the settling velocity of

Jan 1, 1952

By R. W. Hyde, B. S. Old, S. E. Eaton

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides' In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By T. Glen Heslop, Dennis H. Laubscher

INTRODUCTION In all cave mining operations waste is drawn mixed in the ore, hauled, hoisted and milled. This waste usually contains some mineral which partly covers some of the costs of mining and milling it, but it still re- presents a loss of profits as the production rate from the mine is matched to the mill capacity - every tonne of waste milled replaces a tonne of profitable ore. Draw control aims to reduce the amount of waste drawn and to increase the amount of ore recovered. It is also used to regulate the grade of ore flowing to the mill and in block cave blocks to prevent potential stress build- up on the major apexes above grizzly drifts. This paper summarises what has been learnt about draw control in the forty years that cave mining methods have been used in the three largest underground chrysotile asbestos mines in the southern hemisphere. The four mining methods to which draw control has been applied are: a. Block caving. b. Shrinkage with overburden caving. c. Sublevel caving. d. Open stoping. Open stoping has been included because on a number of occasions severe falls from the back and side of these open stopes have occurred. Without full records of where and when ore is blasted, when and how much ore has been drawn from each of the drawpoints, it would be impossible to analyse the migration of ore and fallen waste in the stope. Several problems peculiar to chrysotile asbestos ore bodies affect the practice of draw control. Heterogeneous fragmentation, cavities, side pressures and the interaction of stresses in the caved ore affect the migration of ore under draw. Fibre is normally not developed uniformly throughout the ore bodies, values vary from place to place but there is usually a general decrease upwards and the hangingwall contact is an economic limit. The immediate hangingwall rock frequently looks like the ore body hostrock and is difficult to recognise in a drawpoint, and cannot be used as the marker for stopping draw. During caving or shrinkage, a large proportion of fibre becomes detached from the host rock and re- ports in the fines, which migrate differently to the larger rocks. The fines are not sticky, and flow easily if loose and dry, but compacted, the fibre and rock fines con- solidate the ore. During draw the proportion of fines in the ore varies considerably, as fines either flow relatively freely between the large rocks or become trapped and compacted above large rocks or hangups. This creates a large sampling error in drawpoint grade assessments, whether done visually or by bulk sampling, unless the assessments are done frequently. The method of draw control used is to regulate the draw rate in an attempt to lower the ore-waste interface as evenly as possible, and to finally stop working the drawpoint when a calculated tonnage has been drawn.

Jan 1, 1981

By C. L. Mantell

When considered from the viewpoint of world annual output, tin is one of the rarest metals. Its annual production is exceeded by that of iron, copper, lead, zinc. aluminum, magnesium; probably by that of the ferroalloys of manganese, chromium, and silicon, and possibly by the world production of sodium; while it exceeds only the output of such common metals as nickel, antimony, mercury, tungsten, molybdenum, silver, gold and the precious metals. Cassiterite, or tinstone, until the second World War was the only mineral that was an important source of tin. This mineral is frequently called "tin ore." The use of the term should be restricted to the ore containing the mineral, and not, in addition, to the concentrates of the mineral obtained from the ore or from stanniferous alluvial deposits. There is a general misuse of the term "tin ore" in the Malay Peninsula and adjacent localities, particularly where most of the mineral is obtained from secondary stanniferous deposits. The term "cassit-erite" is exclusively used in mineralogical, geological, and other scientific writings; it is unfortunate that it is not mole frequently used when referring to the occurrence of the mineral on an economic scale. Ores "Tinstone" js a very convenient old English term deserving a more frequent use. Tinstone is a dioxide of tin, or stannic oxide. When chemically Pure, as in the very rare transparent variety, it has a metallic content of 78.6 per cent tin. Frequently, however, the crystals and grains contain appreciable amounts of impurities, chiefly iron and tantalum. The impurities here referred to are those actually in the mineral itself. Tinstone usually has a deep brown or black color with an adamantine luster. Several other colored varieties are known, among them red ruby tin, yellow rosin tin, and yellow wax tin. the names jn each case being descriptive of the mineral's appearance. Ainalite is a variety of cassiterite con-taining almost g per cent of tantalum pentoxide. Sparable tin, tooth tin, and needle tin, as a result of their acute dite-tragonal pyramidal crystalline form, re-ceive their names from their crystallo-graphic appearance. Wood tin is a compact variety of cassiterite composed of radiating fibers resembling dry wood. Toad's-eye tin is a similar variety on a smaller scale in which the fibers appear to resemble the eye of a toad. Stream tin is water-worn tin-stone. Float tin is sometimes employed to describe the cassiterite occurring in soil derived from the weathered surface of a mineralized area. Stannite is an ore of tin of lesser impor-tance than cassiterite. It is a sulphide of tin, copper, and iron, sometimes known as tin pyrites or bell-metal ore. Its chemical com-position is sometimes expressed by the for-mula Cu,S.FeS.SnSz with zinc usually present in varying quantities. The tin con-tent varies from 22 to 27 per cent and there is about 29 per cent of copper, 13 per cent of iron, and 30 Per cent of sulphur.

Jan 1, 1944

By Victor Formanek, Paul Chataignon, Maurice Rey

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By D. R. Hay, E. Scala

STUDIES of structure-sensitive properties, especially mechanical behavior, have shown that grain and subgrain structure play an important role. The mechanical properties of tungsten, in particular, are sensitive to the nature of the intergranular structure. Substructure and dislocation networks in single-crystal and polycrystalline tungsten have been studied by Nakayama et al.' Various orders of substructure were observed ranging from a microscopic first order (grain diameter: 2 to 8 mm) to a microscopic second order (grain diameter: 50 to 300 p), and, within the latter, dislocation networks forming an even smaller order of substructure. In their single crystals, grown by arc fusion, the degree of misorientation in each order was small: 16'3OU, -11, and -10" for the first-, second-, and third-order substructure, respectively. To study the properties of polycrystalline tungsten, powder metallurgy tungsten is generally used. However, in a mechanical property investigation, the zone-melted or arc-fusion crystals are more desirable than the powder metallurgy product due to their higher purity and absence of porosity and other defects inherent in consolidation by powder metallurgy. Grain boundaries can also be produced in melted stock by working and recrystallizing. However, material with subgrain mis orientations of the order of several degrees (high-angle substructure) has not been reported previously and is the subject of this communication. Crystals were grown by electron-beam, floating-zone melting. The starting material, Sylvania Pure-tung welding rod, was given one zone pass at a traversal rate of -2 mm per min. Through control of the zone temperature, it was possible to influence the degree of crystal perfection. By maintaining the zone at a high degree of superheat, high-perfection crystals could be grown. However, at temperatures only slightly above the melting point, the zone-melted crystals contained a high-angle substructure. A sensitive control of the zone temperature was not possible due to the difficulty of estimating the temperature of the zone and of providing a constant supply of power to the sample. Therefore, an empirical method, using the shape of the molten zone as a criterion, was adopted as an indication of temperature. At high degrees of superheat, the surface tension of the molten zone decreases and a neck forms at the top of the zone, whereas at low zone temperatures the diameter of the zone remains reasonably uniform. Although it was not possible to obtain a continuous variation of misfit angle, the conditions could be directed toward the growth of either high- or low-angle substructure by maintaining only a slight neck in the zone (sufficient to establish that it was molten) or a well-necked zone, respectively. Mass spectrographic analyses of both types of material revealed no significant differences in the concentrations of their impurities. The degree of misorientation at high angles was obtained by measuring the angular spread of spots corresponding to a single reflection on a Laue back-reflection photograph. Fig. 1 shows a typical Laue back-reflection photograph of a crystal with a 3-deg spread. By measuring the angular deviation of the spots corresponding to a single reflection from the mean center of the spots around which constant angular deviation contours were drawn, an average angular spread of misfit could be calculated. The angular average was weighted by the number of spots observed in each angular interval. At angles greater than 5 to 6 deg the spots from different reflections begin to overlap, and cannot be associated with a particular reflection. Laue back-reflection photographs taken at different locations on samples .with approximately 3-deg spreads showed only a small difference in angular misorientation, less than 8' of arc, within individual specimens. The microstructure was examined using Berg-Barrett X-ray extinction contrast microscopy. Berg-Barrett photographs taken directly on the as-grown surface, Fig. 2, show an essentially equiaxed subgrain structure of -0.1 mm in average grain diameter in both high- and low-angle crystals. Fig. 2(a) is a photograph of a sample with a low misfit angle and Fig.

Jan 1, 1968

By Maurice Rey, Victor Formanek, Paul Chataignon

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By J. Gurland

The effects of variations of carbon content on the constitution and properties of sintered WC-Co alloys were studied. The grain growth of tungsten carbide during sintering was measured and it was shown that it takes place mainly by solution and reprecipitation of the carbide in and from the binder at the sintering temperature. It was found that the decomposition of W3C03C by carburization during sintering is responsible for the formation of very large grains. THE properties of sintered WC-Co alloys are critically dependent upon their final composition and structure. Slight changes of cobalt and carbon contents and small variations of grain size result in marked changes of mechanical properties and performance of products. Previous investigators have studied the microstructure as a function of composition' and have dealt with the influence of cobalt upon properties.' The present work is concerned with the effect of carbon content upon constitution, microstructure, and grain growth during sintering, as well as upon the physical properties of sintered compacts. Phase Boundaries at the Sintering Temperature The WC-Co section through the ternary diagram W-Co-C has been studied by Wyman and Kelley,' Takeda,V andford and Trent," and Rautala and Norton." Two phases, namely WC and a cobalt-rich solid solution (P), appear in the sintered structure if the carbon composition corresponds very nearly to the theoretical carbon content of WC (6.12 pct C). But small deviations from the ideal carbon content will bring about the occurrence of either graphite or the double carbide W,Co3C (7) . The 7 phase was long believed to be metastable, this conclusion being based mainly on the work of Takeda. More recent studies have shown that it is a stable phase of the ternary system,"5 but the actual phase boundaries have not been established and there has been some discussion as to whether or not the 7 phase occurs at some stage of sintering in the fully carburized alloys." In view of this uncertainty it was thought advisable to undertake an investigation of the phases present during the sintering of WC-Co alloys. Commercially available tungsten, cobalt, and carbon powders were used in the present study. A typical analysis of impurities in a sintered compact is reported in Table I. The desired carbon compositions were attained by varying the amount of carbon added to the tungsten during carburization and controlling the composition during sintering by packing the compacts into beds of mixed alundum-carbon powders of suitably selected ratios. The alloys were sintered in a hydrogen tube furnace at 1400°C, then brought to equilibrium at the temperature under investigation and quenched in water. The high temperature phases were identified by metallographic and X-ray diffraction techniques. The samples were etched with a 10 pct solution of alkaline potassium ferricyanide. The phase boundaries, established by metallo-graphic examination, are shown in Fig. 1, which is a vertical section through the ternary diagram at 16 pct Co. The temperatures of the invariant planes, at 1298" and 1357°C were established by Rautala and Norton. The vertical section shows that the three-phase field, WC + 7 + L, extends into the two-phase field, WC + L, but does not include the stoichiometric composition of WC. In practice this means that the 7

Jan 1, 1955

By N. K. Chen, R. Maddin

In the extension of molybdenum single crystals at room temperature, the slip planes were found to be of the type (1101; the slip direction <111>. Theories of plasticity of body-centered cubic metals have been examined, and an explanation based upon planes of highest atomic density seems plausible to explain the plastic behavior of molybdenum single crystals. IN body-centered cubic metals, slip has been reported to occur on several planes; these are of the type {110), {112), and (123). Andrade has correlated&apos; the operative slip planes in body-centered cubic metals with the testing temperature relative to the melting point. In this correlation, if T is the absolute temperature at which slip takes place and Tm the absolute melting point, then the acting slip planes in body-centered cubic metals may be arranged as shown in Table I. However, deviations from this correlation have been reported in iron and iron-silicon alloys2 and also in molybdenum deformed at a temperature around 2400°C." In the case of iron and other body-centered cubic metals or alloys in which all three slip planes have been reported to be active at any one temperature, the crystallographic mechanism of slip is not well understood. Numerous investigators in this field have assumed that the resolved shear stress is a deciding factor. Such considerations were given by Gough in his experiments with repeated torsion of iron single crystals4 and recently by Opinsky and Smoluchowski in their study of iron-silicon alloys," and will be dealt with later in this report. A third possibility is that slip lines in body-centered cubic metals may be formed by alternate slip on nonparallel (110) planes and not by slip on any plane of higher indices. This was advanced by Elam in the case of ß brass." Since (1101 planes are planes of highest atomic density in the body-centered cubic structure, this hypothesis would be in accordance with the plastic behavior of metals in other systems, namely, face-centered cubic and hexagonal close-packed. Experimental evidence in support of this hypothesis is lacking. Nevertheless the work of Barrett, Ansel, and Meh12 has definitely demonstrated that the slip resistance on {110} planes in iron is very much smaller compared with that on (112) and (123) planes. In the present investigation, molybdenum single crystals were carefully documented as to the operative slip planes and lattice reorientations after plastic extension at room temperature. In three crystals studied, (110) planes were found to be active invariably rather than the (112) planes, which were previously reported for molybdenum at this temperature&apos; and predicted by Andrade&apos;s theory.&apos; In two other cases (112) and (123) planes seemed to operate together with (110) planes as active slip planes. However, it is believed, after careful analysis of crystallite and lattice rotations, that slip on (112) and (123) planes may be spurious. Particular reference will be made to the formation of asterism, lattice rotation, and crystallite rotation in an attempt to show that slip apparently observed on {1121} and (123) planes is actually slip on nonparallel {110} planes. Materials and Treatment Sintered molybdenum rods ? in. in diam, obtained from the Fansteel Metallurgical Co., were reported to have a purity of 99.9 pct.* One specimen, Mo-13, ¼ in. in diam, was supplied by Westinghouse Electric Corp. Single crystals were prepared, using the technique devised by Chen, Maddin, and Pond." Mo-13 was ¼ in. in diam x 7 in. long with a reduced gage section of 0.200 in. in diam x 3 in. long. The center of

Jan 1, 1952

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. &apos;This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir&apos;s producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.&apos;.&apos; The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,&apos; experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958

By J. L. Brimhall, R. A. Huggins, M. J. Klein

IN a recent paper1 it was shown that small additions of magnesium, copper, and oxygen decrease the stacking fault probability in plastically deformed silver. Correlation of :X-ray data with measurements of the twinning frequency and metallographic observation of slip lines indicated that this effect may be due to an increase in the relative stacking fault energy. It is the purpose of the present note to report experiments on these alloys of known stacking fault probability that relate to the stacking fault contribution to electron scattering in silver. There has been a considerable amount of disagreement in the literature concerning the contribution of dislocations to electrical resistivity in metals. Calculations relating to the scattering of conduction electrons by the dislocation core, its strain fields, and related effects have been made by several authors.2-5 In addition, experimental work on Cu,3,6-10 Ni,11 and Ni-Co alloys1:! has shown that dislocations in those materials exert an anomalously large effect on resistivity, this effect being related to the presence of extended dislocations. The problem of the scattering due to the stacking fault region between partial dislocations has been treated theoretically using several different procedures.13-&apos;0 The results of these calculations show a wide range of predicted values, from rather large to completely negligible, due to the models and the approximations involved. Almost all of this work has been applied to the specific problem of scattering in copper. The more complete theoretical treatments depend rather critically. on the shape of the Fermi surfaces and the effective mass parameters. The scattering from stacking faults might therefore be expected to vary significantly from one metal to another. Unfortunately, sufficiently accurate information is not available .which would allow one to have any confidence in a theoretical prediction of the scattering in the case of silver. Resistivity measurements were made on small wire specimens of vacuum melted high purity silver and several dilute alloys. These measurements were made at approximately 20°C, with great care being given to temperature measurement and corrections. At such temperatures phonon scattering is significantly greater than imperfection scattering. However, the experimental technique was such that measurements on similarly treated samples were reproducible to better than 2.4 X 10-9 ohm-cm, which was satisfactory for this work. Values of the stacking fault probability and the increase in resistivity after severe plastic deformation are given in Table I. The increases in resistivity resulting from plastic deformation agree quite well with previous work on silver.14,21-26 In addition, it has been previously found that interetitials and vacancies in silver anneal out well below room temperature, so that the residual imperfection scattering in these experiments could be expected to be primarily associated with dislocations;. It is seen from the data in Table I that large changes in stacking fault probability are accompanied by differences in resistivity due to imperfection scattering of only a few percent. If the scattering of conduction electrons by extended dislocations is primarily due to the area of the stacking fault region independent of the stacking fault energy, and not the core and strain fields associated with partial dislocations, the resistivity increase should be proportional to the product of the dislocation density and the stacking fault width, as is the stacking fault probability. Therefore, the imperfection scattering caused by plastic deformation of the alloys should be considerably smaller than that found in the pure silver. Since this was not observed, these results sugegest the possibility that stacking faults do not themselves contribute appreciably to the electrical resistivity of silver deformed at room temperature. An alternative explanation of these observations is that the scattering by the stacking fault is roughly proportional to the stacking fault energy, rather than being determined by the total area of such faults. Sufficient evidence is not yet available to separate these two possibilities. This work was supported by the Office of Naval Research.

Jan 1, 1962

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer&apos;s organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3&apos; phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou&apos; zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß&apos; was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß&apos; phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13&apos; was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß&apos; which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß&apos; on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß&apos; phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß&apos; and to structures, and the 4, structure can be derived from the 0&apos; structure by a small movement of atoms mainly in the direction of the cube diagonal.4&apos;5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p&apos; structure and transformation from ß&apos; to requires a large fraction of the atoms to change position. It has been shown that the ß&apos; transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By Charles C. Towle, Irving Rapaport

URANIUM mineralization along the north flank of the Zuni Uplift, in the vicinity of Haystack Butte, was discovered by Paddy Martinez, a Navajo Indian, in the spring of 1950. The find was reported to the Santa Fe Railway Co., which initiated a program of exploration upon its holdings in the district in December of 1950. The Anaconda Copper Mining Co. secured numerous leases in January and February, 1951, and began an intensive exploration and development program in March 1951. The district was extended into the Lucero Uplift in August of 1951 by the discovery of uranium mineralization in Todilto limestone by Joy Sinyella, a Supai Indian living on the Laguna Reservation. Initial reconnaissance was performed in the district by the Atomic Energy Commission in November 1950. A field office under the direction of the Denver Exploration Branch of the AEC was established at Prewitt, N. Mex. in January 1951 to study regional and detailed guides to ore, to evaluate the ore deposits, and to promote the development of the district by providing geologic services for the companies and individuals engaged in exploration. With the development of sufficient ore to warrant construction of a mill, the Grants area of New Mexico has come of age as a full fledged uranium mining district. The carnotite-type deposits of Grants, the first of major economic importance found in limestone, have extended the Colorado Plateau carnotite field into the more complex structure of the Basin and Range Province. General Geology The Grants uranium district is in northwestern New Mexico, along the southern flank of the San Juan Basin, between the cities of Gallup and Albuquerque. The region is at a mean altitude of about 6800 ft, vegetation is sparse, and outcrops are excellent. Mt. Taylor volcanic peak, at an elevation of 11,400 ft dominates the surrounding area. The overlying cliff-forming Dakota sandstone is the most resistant formation in the Grants District and characteristically erodes into dissected mesas as much as five miles wide. The principle uranium ore-bearing horizons are found in the underlying Morrison formation, and the Todilto limestone of the San Rafael group. The Morrison weathers into. a series of steep slopes and precipitous cliffs near the lower part of the Dakota-capped rims, while in contrast, the relatively resistant underlying. Todilto [ ] limestone forms broad benches extending out from the base of these Dakota rims as much as five miles wide. The Todilto benches are covered with overburden to an average depth of about 5 ft in the first thousand ft away from the Dakota rim, but increases to about 200 ft at the base of the rim. In many places however, a thick mantle of upper Cretaceous sediments and Tertiary volcanics "obscures the ore-bearing Jurassic, and precludes exploration. . The known uranium deposits of the Grants District are distributed throughout a zone 85 miles long and about 10 miles wide. Stratigraphy Rocks from pre-Cambrian through Tertiary are exposed in the uplifted areas, but uranium appears to be restricted chiefly to two zones in Jurassic sediments. The Jurassic sediments of the Colorado Plateau have been subdivided into three units, in ascending order: (1) Glen Canyon group, (2) San Rafael group, (3) Morrison formation. The Todilto limestone zone within the San Rafael group has produced the bulk of ore to date, but the promise of the Morrison zone is rapidly increasing. The Todilto formation extends about 300 miles east-west and about 100 miles in a north-south direction. It is composed of a lower, extensive, limestone member and a central, more restricted, thick, pure gypsum member. The Todilto is believed to be of lacustrine origin. The Morrison formation in this area is subdivided, rather arbitrarily, into three members: Recapture Creek, Westwater Canyon, and Brushy Basin. Ore

Jan 1, 1952

By Edgar F. Cruft

INTRODUCTION It is sometimes said that "mines are made, and not found." I rather doubt that the exploration geologist would be overly sympathetic to that statement, and, of course, like most one-liners it is only partly true. Access to different financial markets are important at the mineral prospect stage. The modern mine financier has a much more complex, and interesting, job than the financiers of an earlier era, for example, the Canadian financiers of the 40&apos;s and 50&apos;s who had one simple set of options; i.e. float a company, promote it, and sell an equity stock issue, and then promote it some more. QUALITIES OF A FINANCIER Because technical people are seldom taught financing in their basic training, and because they are usually not involved in it until at quite a senior level in their careers, the whole field often acquires a certain mystique. The engineering professions have too often believed financing is the province of the accountant or financial executive and just as we in the technical world are often too quick to bristle if the latter try to tread on our domain, the opposite can just as easily be true. Unfortunately, this is another example of a compartmentalized individual, and that is one thing the successful financier cannot be. However, to be a successful financier one does not need extensive training or experience in accounting or finance. In fact it can sometimes be a disadvantage to get too buried in working only from the standpoint of discounted cash-flow analyses, ROI&apos;s, etc. It must be stressed, however, that one had better know how these analyses are made, and be knowledgeable in understanding a balance sheet, and have a good understanding of financial terminology. The difference between a simple project-type debt financing with a commercial bank and a more inventive and creative financial package comes from an intuition and an experience relating to risk-reward factors. The most important element is "common-sense", based on knowledge and experience. The goal is structure a financial package that fits the project, and in so doing it is important to recognize that it must fit within the limitations of the group supplying the money. I find insensitivity to recognize these constraints the most common mistake made in the field. Put yourself in the other person&apos;s place and understand his sources of funds and financing limitations. The engineer has an advantage in financing, as he or she has (or should have) a better idea than anyone of the value of the product, be it the mine, prospect, or company i.e. the intangible or potential worth which cannot be put on a pro-forma. He also knows, or should know, the risks involved. Two projects might look the same on paper, but a good financier must have a sense of when to take whatever deal he can get, and when to hold out based on his evaluation of future developments. It is essential to have a good sense of commodity values and trends, trends affecting the general economy (money supply, interest rates, effects of energy costs, etc.), and political considerations. He must also have a good understanding of the science and art of taxation as deals can often be financed using the government as a silent and unwitting partner by proper use of the tax laws. WHEN TO SEEK FINANCE The first critical decision to make in financing a mineral prospect is "when". At the exploration level, when it is only a dream in the geologist&apos;s eye, the alternatives are more limited than when it is a fully-engineered project. The "when" decision depends on how much in internal funds the company has to play with, and how desirable it is to invite financial participation to spread the risk. Assuming that decision is not taken out of lack of money, no one can categorically say when to do it. There is

Jan 1, 1985

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.&apos; , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961