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By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

John G. Tripp-—The concept of converting fuel deposits in-situ to useful forms of energy and chemical raw materials has important possibilities as a means of stretching out our fuel resources. The authors have worked in this field for years and in fact are among the pioneers in developing in-situ techniques based on underground electrocarbonization. Their efforts have aroused great interest in this subject and their contributions will undoubtedly gain even more significance as time goes on. The 4 to 5 billion tons of petroleum are proved reserves, that is, they are completely defined and could be produced economically with present methods of recovery. Reserves of coal, tar sands, and oil shale shown in Table I are not equivalent to proved reserves as the term is used in the oil industry. Incidentally, the 4.3 billion tons of oil shown in the tabulation is equal to about 28 billion barrels of oil and, therefore, presumably does not include reserves of natural gas liquids estimated at about 5 billion barrels. The relative comparisons would be more complete if these liquids together with the reserves of natural gas were included in the tabulation. It is stated in the report that production costs of the order of 10c per million Btu's could be expected from a large industrial electrocarbonization installation. The authors state that the operation probably could be operated successfully and at a profit. I would like to express my view that for the operation to be profitable extremely favorable conditions would have to prevail. For example, the coal seam would have to be thick and close to the surface in order to minimize drilling costs; the deposit should be dry and so situated that there would be little, if any, inflow of ground water; and the seam would have to be relatively gas tight to avoid excessive gas leakage. Notwithstanding the tremendous strides that have already been made, it is my hope that the authors plan to continue their development work. Experiments on underground electrolinking and initial carbonization at Gorgas, Ala., indicate a need for improved control over the operation. Subsequent examination of the underground system at Gorgas has shown that the gasification zone did not always follow a direct path between the electrodes. Undoubtedly the control of the in-situ thermal processes can be improved by further development work. With respect to the electrocarbonization of oil shale it may be well to point out that the cost of mining oil shale is estimated to be 50c to 60c per ton. These are low mining costs as compared to coal. Thus it would appear that there is less economic incentive for applying in-situ thermal methods to oil shale than there is for applying these methods to coal. As is the case with in-situ methods for petroleum, the product from the shale having the most economic interest would be liquid oil rather than gas. The authors point out that for distances up to several hundred miles it is cheaper to transmit energy as electricity than it is to ship energy as coal. This is a very important point, and with coal shipping rates rising periodically, it could prove increasingly important in the future. I believe that the authors deserve great credit for their outstanding work on underground electrocarbonization. The knowledge resulting from their efforts is of great value to our fuels technology. James L. Elder—The experimental work conducted by the authors on the electrolinking-carbonization of carbonaceous materials in situ is of great interest. The method is of great importance in the development

Jan 1, 1955

By J. S. Ll. Leach, M. B. Bever

THE system copper-nickel exhibits complete solid and liquid miscibility1 The thermodynamic properties of such a system would not be expected to deviate greatly from ideality. Although the evidence is conflicting, anomalies in the composition dependence of various physical properties of solid copper-nickel alloys suggest that mixing may not be ideal.' From measurements of the Hall coefficient it has been concluded that clustering occurs in these alloys. ' Considerations involving the phase diagram of the ternary system copper-nickel-chromium have led Mei-jering3 to predict a positive heat of formation for solid copper-nickel alloys. An electrochemical investigation of the activity of nickel in copper-nickel alloys showed unexpectedly large positive deviations from ideality.4 wagner5 has proposed that if the entropy can be considered ideal, these measurements would yield the following equation for the heat of mixing at 700°C H" = 3380 x,vl (l-xVi) cal per g atom [I1 The heat of formation at 722°C of solid copper-nickel alloys of the equiatomic composition has been measured in a reaction calorimeter as 540 cal per g atom. This note reports calorimetric measurements of the heat effects on dissolution of some copper-nickel ndon: in tin. These measurements were preliminary to a larger investigation, which was later discontinued. From them the heats of formation of the alloys can be calculated, if certain assumptions are

Jan 1, 1960

By Fred Chappell

Pyrophyllite, a hydrous aluminum silicate, physically similar to talc, receives its name from the Greek word Pyr, for fire and phyllite, a rock or stone. Firestone refers to its first recorded use as firestones or hearthstones. Composition and Properties Pyrophyllite is an aluminum silicate A12O34SiO2H2O (alumina 28.3 pct, silica 66.7 [ ] pct, water 5.0 pct) (Table 1). Vanderbilt1 gives pH value of pyrophyllite as 5.6 to 8.4. Pyrophyllite is usually white or cream, though it may be found in shades of pale green, pale yellow, buff or light gray, and in darker shades and other colors principally due to oxidation of contained iron minerals. It is opaque to translucent in thin sections. Its hardness is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. Its luster is pearly to dull; it is recognized chiefly by its micaceous structure and cleavage, and its soft greasy feel. Two other varieties occur, one in which there are radiated needles in the crystalline form, and there is also a massive homogeneous structure found. Fine grinding reduces pyrophyllite to fiat plates or scales but aggregates of minute foliated plates may be formed.1 Distribution of Deposits Pyrophyllite is found in metamorphic rocks throughout the world but it is only in comparatively recent years that it has assumed much commercial importance. The principal

Jan 1, 1960

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By G. R. Gray, T. S. Chapman, J. L. Foster

THE wall-building properties of salt-water drilling muds can be improved markedly by the addition of: (I) natural gums, such as tragacanth, karaya, and ghatti; (2) seaweeds, such as Irish moss; or (3) gelatinized starch. Results of laboratory tests have been confirmed by field trials. For drilling operations in which the mud becomes contaminated by salt, either through penetrating salt-bearing rocks or by addition of sea water to the mud, the added cost resulting from the use of one of the substances listed above is more than offset by freedom from stuck drill pipe and ease in running casing. INTRODUCTION It has been recognized for many years that oil production might be seriously hampered by infiltration of water from the drilling mud.1-4 As knowledge of the mechanism of the wall-building process advanced, methods were developed for evaluating the filtration characteristics of muds.5-11 The wall-building properties of fresh-water muds are commonly regulated by the addition of bentonitic clays, or of agents to promote the dispersion of the natural mud solids. When strata bearing soluble salts are encountered in the course of drilling, the salts are incorporated in the mud; the clay solids are flocculated and water loss is increased tremendously. Methods generally used in controlling filtration of fresh-water muds are no longer applicable. The problem of reducing water loss from salt-water muds is not confined to any particular area, but is acute in parts of West Texas. Salt beds several hundred feet thick must be penetrated before the oil-bearing formation is reached. Since the formation drilled does not provide mud-making material, it is necessary to use large quantities of commercial clays, and even the best commercial clay does not afford relief from the problem of high filtration. A laboratory study has been made of methods of improving the filtration characteristics of salt-water muds, and some of the methods have been used in field practice. LABORATORY INVESTIGATIONS Procedure Inasmuch as the immediate object of the investigation was the development of means of improving the wall-building properties of muds used in West Texas, an attempt was made to employ muds in the laboratory study comparable to those in field use. Samples of muds used in drilling the producing formations in six wells were secured. The properties of these samples are summarized in Table I, which lists the densities, viscosities, filtrations, and analyses of the filtrates for calcium, chloride, and sulphate. Viscosity was measured in the Stormer viscosimeter at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester' at a pressure of 10o lb. per sq. in. Filtration rates are considerably higher than those of usual fresh-water muds, which amount to about 20 c.c. in 30 min. Water loss was so rapid in samples 4, 5 and 6 that filtration was complete in less than 10 min. and the values for 30 min. were extrapolated from the rates at shorter

Jan 1, 1941

H. 0. HOFMAN, Boston, Mass (written discussion*).-The paper by Mr.. Pyne gives clear evidence of the difficulties the metallurgist is likely to encounter when he tries to recover in the blast furnace the metal from old chromite lining used as a refractory material in the copper reverberatory furnace. It appears that chromite cannot be fluxed at temperatures which usually prevail in copper blast furnaces. This calls to mind the freezing-point curve drawn by M. Simonis1 of mixtures of chromite and kaolinite. The chromite used in the experiments contained 52.9 per cent. Cr203, 22.6 FeO, 4.8 AI203, 9.6 Si02, .10.1-MgO; FIG. 1. the kaolinite was clay from Zettlitz with 98.5 per cent. clay-substance: The accompanying curve shows that the eutectic mixture with 35 per cent. kaolinite and 65 per cent. chromite freezes at Seger cone No. 15 (1435° C.), while kaolinite fuses at cone No. 35 (1770° C.) and chromite at cone No. 42 (2000° C.). The curve indicates that the difficulty in the blast furnace can be overcome by having at the smelting zone a temperature much higher than is usual in copper smelting; a charge composition similar to that prevailing at the Mansfeld copper smeltery -which gives with 23 per cent. coke a, slag of the composition Si02, .49.09; .(FeMg)0, 5.58; (CaMg)0, 16.02; A1203,-16.02-might flux and fuse chromite.

Jan 3, 1918

By W. W. Coblentz

THE constants in question pertain to the total radiation and the spectral radiation of a uniformly heated enclosure, or so-called black body. These constants have been determined for the range within which temperatures can be measured with thermocouples. Conversely, using these constants and suitable instruments, such as an optical pyrometer, for example, it is possible to determine temperatures far above the range attainable with the most refractory thermocouples. The formula of Stefan Boltzmann for expressing the total radiation of a black body is R = kT4 in which k is the coefficient or "constant" under discussion. In view of the fact that total radiation pyrometers are usually calibrated on an arbitrary scale, there is no great demand for an exact value of the coefficient of total radiation in absolute value. However, it is intimately connected with the constant of spectral radiation; hence, an accurate determination of the constant k gives a check on the constant of spectral radiation. The distribution of radiation in the spectrum of a black body is represented by Planck's equation, E? = C1?-5 (e c/?T - 1)-'. The spectral radiation constant c, in this formula, is useful in optical pyrometry and in establishing a high temperature scale. The numerical value of the constant c has been determined in the range of temperatures measurable with thermocouples and, also, by extending the temperature scale to higher temperatures by means of total radiation measurements.

Jan 8, 1919

By H. L. James

THIS paper presents the results and analysis of field trials of various magnetic instruments over anomalies ranging from 20 to 5000 gammas of vertical intensity. The following instruments were used: Askania vertical magnetometer, Wolfson vertical magnetometer (model M-I), Hotchkiss Superdips (used both parallel to and normal to the magnetic meridian, with several settings of the "sigma" angle), Lake Superior dip needle, and the dipping circle for measurements of inclination. The change in inclination over the measured anomalies ranged up to 4°; this caused pronounced changes in sensitivity of the Hotchkiss Superdip oriented parallel to the magnetic meridian. The variable sensitivity not only gives apparent displacement of crests of anomalies, particularly at high sensitivities, but also makes the data difficult or impossible to use in preparation of iso-anomaly maps. This weakness in field performance of the Superdip is shown to be eliminated by orienting the instrument normal to the magnetic meridian and measuring vertical intensity only, which in the latitude of upper Michigan is equal to 97 pct of the total intensity. The dip needle is seen to be relatively ineffectual for location of anomalies of less than 400 gammas.

Jan 1, 1947

By W. A. Krivsky, R. Schuhmann

PREVIOUS papers in this series on the thermo-•t dynamics of copper-smelting systems have presented a survey of the field and an outline of the overall program: thermodynamic studies of iron silicate slags, 2-4 and thermodynamic data for simple mattes in the Cu-S system.5 Since this program was started, an excellent summary of the whole field of physical chemistry of copper smelting was published by Ruddle. The present paper represents a further step in the study of liquid mattes, and deals specifically with the Cu-Fe-S system. The importance of the Cu-Fe-S system to copper smelting is evident from the fact that these three elements constitute 90 to 99 pct of the totalweight of most commercial mattes. In copper mattes oxygen is an important fourth component. Oxygen was rigorously excluded in the work to be described in this paper. However, the behavior of oxygen in mattes was the subject of a companion research by Lander' which will be described in a subsequent publication. Several studies have been made previously of phase equilibria in the Cu-Fe-S system,8-10 so that the ternary phase diagram is fairly well established in most regions. Also, separate studies have been made of the phase diagrams and thermodynamic properties for the three binary systems: CU-S,5,12-15 CU-Fe,11,14,17 and FeS.11,14,16,17 However, no work has

Jan 1, 1958

By J. D. MacKenzie

THE world production of copper for the first eight months of 1927 shows an increase of 3 per cent over the same period in 1926. Since February of this year, however, production has been considerably curtailed. The United States reduction in the last four months has been offset by the increased South Ameri-can and Belgian Congo production. The United States is now producing 58 per cent of the world production, Chile and Peru 17.3 per cent, Belgian Congo 5 per cent. In 1926 the United States produced 54 per cent, Chile and Peru 16.3 per cent, Belgian Congo 6.3 per cent. Production, Tons 1917-largest war year 1,580,000 1925 1,581,000 1926-increase 3 per cent 1,628,000 1927-increase 3 per cent 1,670,000 Copper Producing Countries, 8 mo., 1927: Tons Per Cent United States 644,000 58.0 Chile and Peru 192,000 17.3 Europe 90,000 8.1 Belgian Congo 56,000 5.0 Japan 46,000 4.1 Mexico 30,000 2.7 Canada 23,000 2.1 Figures are not available for Spain and Portugal, which would probably precede Mexico.

Jan 12, 1927

By Martin J. Conway

DURING the past year, the intense interest shown by the metallurgical industry in the use of relatively pure oxygen has been evidenced by the number of papers dealing with its application and production. The reason for this interest is apparent when it is realized that, weight for weight, oxygen enters into the formation of steel equally with iron. In the manufacture of steel, approximately one ton of oxygen is required to produce one ton of ingots. Until the recent development of plants capable of producing oxygen at far lower costs than had ever previously been considered possible, the oxygen required for steel manufacture was used as it occurs in air, where it is associated with approximately four times its volume of nitrogen. Because of the diluent nitrogen more than 4 tons of total gaseous material per ton of steel must be handled rather than only approximately one ton required when pure oxygen is used. In addition, provision must be made to handle the large quantity of waste, gases resulting from the process. There are cases where the reduction in gas volume alone can justify the installation of an oxygen plant.

Jan 1, 1947

By W. J. Nelson, R. B. Nance

Detailed underground geologic mapping at a scale of 1:1200 has been carried out at the Crown II Mine of Freeman United Coal Mining Co., which operates in the Herrin (No. 6) Coal Member. The roof sequence, upward from the coal, includes (1) soft, medium -to dark-gray shale; (2) hard, black, fissile shale; (3) argillaceous nodular- bedded limestone, and (4) fine-pined, shaly, water-bearing sandstone. The first unit is highly lenticular, and any or all may be missing at a given locality. The sandstone has a sheet facies and a channel facies. The Herrin Coal is eroded in channels near the Crown II Mine. Structural features mapped at Crown II include normal and strike-slip faults and limestone "bosses." Less stable roof and wet conditions are encountered where the limestone is thin or missing or where it is broken by natural fractures or by artificial openings that intersect the water-bearing strata above the limestone. Geologic mapping of the underground workings has allowed us to predict faults, fracture zones, and channels ahead of the face for this mine. Some lithologic and structural pattern apparently are random and cannot now be projected. Conventional exploratory drilling is entirely inadequate to map faults or lithology of the roof, but it does indicate the range of lithologic variability, which can be used to project needs for roof supports. Drilling also is useful in locating channels and in mapping regional variation in thickness and facies of the sandstone.

Jan 1, 1983

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.' The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By Howland Bancroft

AMERICAN investment in foreign mining interests today faces its greatest task. U. S. dollars must make possible the. steady procurement of the minerals our defense effort consumes in huge quantities. The two most vital factors involved in foreign procurement are time and the continued good will of the nations from which minerals are purchased. The Point IV program was formulated to care for the second item, but it has failed to do the job. Its lack of success has not been from intent or from basic failure in formula. Foreign Investment, Four Eras Foreign mineral development, in so far as participation by private capital from the United States is concerned, may be divided into four main chronological categories: First: The period prior to the first World War when people, capital and products moved with relative freedom across international boundaries, and London was the recognized mining seat of the world. By the end of 1919 the United States direct investments abroad amounted to $3.9 billion of which some $900 million were in mining and smelting and $600 million in petroleum. Investment climate throughout most of the world was excellent. Second: The period between the end of World War I, when the international economy had been shaken from its foundations, and the beginning of the great depression of the 1930&apos;s, which still further disrupted the world economy. By that time the world mining center had moved across the sea and the United States direct investments abroad had increased to $7.7 billion of which mining and smelting accounted for $1.2 billion and petroleum for $1.1 billion. Investment climate was good in most parts of the world. Third: The period of the depression of the 1930&apos;s and the beginning of World War II during which foreign trade was still further disorganized and the international economy collapsed. Nazi barter agreements were initiated in many parts of the world, and Soviet propaganda commenced to make its, influence felt in many countries. During this period United States direct investments abroad decreased to $7.3 billion. Mining and smelting investments during the same period decreased some $200 million, though direct investments in foreign petroleum areas increased an equal amount. Investment climate became less and less hospitable in all parts of the world affected by economic nationalism. Fourth: The period since the beginning of World War II during which total direct investments abroad increased from $7.3 to $13.7 billion. Of this sum, at the beginning of 1950 investment in foreign mining and smelting is reported to have been $1.2 billion-back to where it was in 1929, and in petroleum to have reached $3.7 billion. Investment climate remained favorable in the countries respecting contractual obligations and fair in their treatment of invested capital. [ ] As noted above, the relative freedom of passage across international boundaries by people, capital and products ended with World War I and the situation remains unchanged in a greater part of the world. While this same war upset international economy, the depression of the 1930&apos;s caused the collapse of world trade, and exports from all countries fell to an alarmingly low figure. Some countries almost ceased to export. Chile, for example, reported a drop of 88 pct in exports. Countries with

Jan 1, 1952

By James M. Schopf

Gilbert H. Cady (Senior Geologist, Head of Coal Division Emeritus, Illinois State Geological Survey, Ur-bans)— Those coal mining and preparation engineers and operators who read this article will probably be most concerned with those parts which deal with the applied aspects of coal petrology in the fields of mining and technology. Actually the two categories overlap to such a degree that they are essentially one. The article appears to suggest that there are two points of veiw in the field of applied coal petrology. From one viewpoint the interest is in the attributes of the various macerals (Fig. 4)—vitrinite, exinite, and inertinite—-in terms of utilization (when the coal is burned, coked, gasified, hydrogenated, etc.). From the other point of view, assuming that the macerals do possess individuality in behavior, interest attaches to the possibility that coal of a particular type (maceral composition) can be prepared by discriminating methods of preparation and blending. Most of the 29 items listed for mining and technology can be assigned to one or the other of these two categories. Somewhat the same simplicity that resides in the items of the proximate chemical analysis is desirable for the petrologic analysis. This simplicity appears to be fairly well achieved by the group maceral device provided mineral matter is also included. At present, without fully adequate experimental substantiation, the three types of material represented by the group macerals vitrinite, exinite, and inertinite are regarded as sufficiently different in composition and properties so that the preponderance of any one type gives the coal distinctive properties provided it is not too high in rank. This appears to be increasingly true with coals of decreasing rank from medium volatile bituminous coals downward. The article reflects the great emphasis placed on the technique of descriptive coal petrology in America. Such description has resulted in a good understanding of the nature of the fundamental variability in the physical composition of bituminous coals. Such understanding has been attained very largely by the thin section technique used in coal bed profile analysis introduced by R. Thiessen after the manner suggested by the data assembled in Table 11. In contrast, the group maceral concept of coal analysis in terms of the categories indicated on the left hand side of Fig. 4 is particularly useful for broken coal analysis and applied coal petrology, in which evaluation is largely based on quantitative concepts. It is inadequately emphasized in this article that although the Thiessen procedure is suitable for the purpose of petrologic description in which texture and orientation are of critical importance, it is less well adapted to the technological uses of applied coal petrology. No doubt those persons whose interest may have been aroused in the possibilities of more refined coal preparation by this and other recent contributions to the literature of coal petrology will understand that certain technical aspects of coal petrology, particularly in the field of descriptive petrology, are still a matter of some controversy among the coal petrologists, but they will also appreciate that Schopf has made an important contribution to the field of coal petrology in America by pointing out that such petrology requires consideration of disoriented or broken coal samples and that results are expressed less in descriptive terms than in quantitative values with respect to the four types of material composing coal—-vitrinite, exinite, inertinite, and mineral matter. Unfortunately because so much American coal petrology has been descriptive of the coal in the bed there is a dearth of literature on applied coal petrology. Research and experimental data in this field are greatly needed.

Jan 1, 1959

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation&apos;s supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation&apos;s need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation&apos;s supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation&apos;s need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951