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By Arnulf Muan, W. C. Hahn

Activities of "FeO" in "FeO"-MgO solid solutions have been determined in the temperature interval 1100" to 1300"C by equilibrating oxide samples with pure metallic iron in atmospheres of known oxygen partial pressures. The end members "FeO" and MgO form a complete solid solution series. The system shoztls a considerable positive deviation from Raoult's law. A large amount of data has been accumulated during the past 50 years on stability relations existing among various crystalline and liquid phases in oxide systems of importance in metallurgical processes. By comparison, very little is known about the thermodynamic properties within the various homogeneous phases present in the systems, particularly the crystalline phases. The present paper deals with determination of activities as a function of composition in solid solutions of wüstite ("FeO") and periclase (MgO). Such solid solutions ("Magnesiowustites") have simple sodium chloride structure and are known to be continuous between the end members at elevated temperatures (> 1000°C) and strongly reducing conditions such as prevail in contact with metallic iron. Wiistite has a defect structure in which the ratio of oxygen to iron varies and never has as low a value as 1:1 corresponding to the simplified formula FeO. Within the range of stability of this phase, the composition changes between a maximum oxygen content of approximately 25.6 wt pct (corresponding to the formula FeO.83O) and a minimum oxygen content of approximately 23.2 wt pct (corresponding to the formula Fe0-96O). The activity data to be reported in the present paper are based on using as standard state the wüstite which is in equilibrium with metallic iron at a particular temperature, i.e., "FeO" of minimum oxygen content at each temperature. For sake of simplicity, the formula FeO will be used to represent the wustite phase in the remainder of this paper. Consider the reaction 2 FeO solid solution = 2 Femeta1 + Ozgas in which FeO dissolved in another oxide dissociates to metal and gas. The activity of FeO in the solid solution, relative to "pure FeO" in equilibrium with metallic iron as a standard state, is then expressed as Here Po, and po2 * are the partial pressures of oxygen of the gas phase in equilibrium with metallic iron and the oxide solid solution or "pure FeO", respectively. The equation holds only if the metal phase is essentially pure Fe. The oxide combinations used in the present investigation fulfill this requirement. Magnesia is so much more stable than FeO that for all practical purposes aFe = 1 in the metal phase present in all mixtures used in this investigation. I. EXPERIMENTAL METHOD 1. General Procedure. The experimental method used was analogous to that developed by Foster and Welch1 and used recently by Hahn and Muan.2 It consisted of four steps: a) Determination of the equilibrium between FeO and Fe. b) Determination of d-spacing change with composition in oxide solid solutions (FeO-WO). c) Equilibration of various members of the solid solution series with a metal phase and a gas phase of known oxygen partial pressure. d) Determination of compositions of solid solutions resulting from step (c) by means of data obtained in step (b). 2. Starting Materials. General Aniline and Film Corp. carbonyl iron powder, type HP, was used as the source of metallic iron. A representative analysis was as follows: Fe, 99.6 pct; C, 0.01 to 0.04 pct; 0, 0.1 to 0.3 pct; N, 0.00 to 0.05 pct. Other elements were present as traces only. Wiistite was prepared from "Baker Analyzed" Reagent grade Fe2O3 of reported analysis as follows: Assay (Fe2O3), 98.8 pct; insoluble in HC1, 0.02 pct; not precipitated by NH,OH, 0.02 pct; Zn, 0.003 pct. Production of wüstite was achieved by a two-step

Jan 1, 1962

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

R. M. Raymond, New York, N. Y.—The filling and drawing down of the overhead material was done at considerable depth, which is not the usual method in which it starts at the surface.. R. J. Mechin.— It is a little more than 1000 ft. at El Bordo. The vein above had been caved practically to the surface and some of the ore had been excavated, using underhand and overhand square-set methods. This was far enough away from the shaft to prevent any bad effects. When the sill floor was taken out, to insure the old cave material following down well, we put chutes in the square sets for several weeks until we were sure that the material from above was moving down; on each level above, several crosscuts were driven into the old fill by which we could see the material coming down and thus be sure it was following the first. We had to dynamite it very little because it was dry and dusty. The only trouble was that timber starting from the old square sets would get across the chute and hang up. R.. M. Raymond.—HOW many floors did you operate at once? R.. J. Mechin.—We would operate one floor through the whole length and prepare for the second. F. W. SperR, Houghton, Mich.—Could you have worked it in steps? R.. J. Mechin.—Yes; but working it all on one floor was much better for ventilation. The passage between steps would tend to become heavy and blocked and, as the passages from the mining floor down are usually filled with ore, there would be no way for the air to pass up. By means of doors and fans, air was driven to the extreme end of the orebody through the stope and up the other end; but it could have been worked in steps. F. W. SpeRR.—D the following-up material ever become so heavy that you could see weight on the caps before you had to take out the posts?

Jan 1, 1927

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By L. W. Kesler

Kansas produced 41,966,773 bbl. of oil in the year 1927, thereby taking fourth place among the oil-producing states of the Union. The daily average production decreased from 121,609 bbl. in January to 110,244 bbl. in December. Due to excessive flush production and the resulting decline in the price of crude during the year, operations, both in proved and outlying districts, were reduced materially from those of 1926. There were 2338 completions in 1926, but only a total of 1333 in 1927. Regardless of this decrease in the total number of completions, Kansas made a slight gain in total production for the year, producing 620,262 bbl. more than in 1926. This is accounted for, in part, by the comparative long life of the settled production from the Bartlesville sand areas to the east of the Nemaha granite ridge, and by prolific production in eastern Summer County from horizons new in their importance in the state, productive here at two localities along the axis of the granite ridge (Table 1 and Figs. 1, 2 and 3.) For convenience in further consideration, the state is divided into Eastern and "Western" Kansas. Special emphasis will be placed on those areas in the state of which but little is generally known, and which have not been given detailed consideration in previous publications.

Jan 1, 1928

By Paul Weir

DURING the past decade, methods of producing bituminous coal in the State of Illinois, which ranks third in production among the states in which bituminous coal is mined, have undergone great changes. From less than one million tons in 1923, the strip-mine production has gradually increased to a high of 11,725,870 tons in 1937. From a negligible amount prior to 1927, the amount of coal mechanically loaded underground had increased to a high of 28,374,362 tons in 1937. The amount manually loaded in 1937 reached a low of 12,332,023 tons. In this same year, this state ranked first in strip-mine production, also in mechanically loaded production. For this reason a study of the influence of mechanization on location of production in Illinois may be helpful in anticipating what may happen in other producing states. The reason for the changes in methods lies in the differences in costs of production. The Bureau of Research and Statistics of the National Bituminous Coal Commission has made public the following costs of pro-duction by various methods in the State of Illinois (district 10) for the last nine months of 1937: all mines, $1.7602 per ton; strip mines, $1.4319; mechanical loading mines, $1.7457; hand loading mines, $2.1793; all underground mines, $1.8703. These are weighted averages for the entire district. Inasmuch as production in 1937 was reported from 58 counties scattered over two-thirds of the area of the state and from five different seams varying in thickness from less than 3 ft. to as much as 12 ft., it is apparent that the location of production must be influenced by the extent of mechanization possible in the various producing counties.

Jan 1, 1939

By D. L. McElroy, J. L. Schroder

Although the earliest use of rubber-tired haulage was in Illinois in 1936, the first unit of this type of equipment used in West Virginia was shipped into the state in 1938. All units placed in West Virginia mines have been of the shuttle-car type. The Katherine Coal Mining Co., at Lumberport, W. Va., was the second company in the United States to install shuttle cars and the Gay Coal and Coke Co., at Mt. Gay, W. Va., was the first company in the country to install the thin-bed type of shuttle car. On Oct. 8, 1940, nine companies in the state were using 41 shuttle cars, of which 10 cars at three mines were of the thin-bed type. All shuttle cars of the low type were in the southern fields and all of the high type were in northern West Virginia. At that time several units were in the process of delivery. The data in this paper were collected in the field by Mr. Schroder in connection with graduate work on mechanical loading of coal in West Virginia by mobile loaders. In the course of his field work he visited five mines in the state that were using shuttle cars. All of these mines were in high-volatile coal beds of strong structure. The more pertinent data obtained at the mines visited are given in Table I. The maximum distance of shuttle-car haul is the distance between the transfer station and the farthermost place. Tonnage per loading unit per foot of bed thickness is to some degree a measure of relative efficiency, especially if the different operations are working the same bed or have somewhat similar conditions. The thin-bed operation is well up in the higher bracket of the afore-mentioned column, which is as

Jan 1, 1942

By J. L. Schroder, D. L. McElroy

Although the earliest use of rubber-tired haulage was in Illinois in 1936, the first unit of this type of equipment used in West Virginia was shipped into the state in 1938. All units placed in West Virginia mines have been of the shuttle-car type. The Katherine Coal Mining Co., at Lumberport, W. Va., was the second company in the United States to install shuttle cars and the Gay Coal and Coke Co., at Mt. Gay, W. Va., was the first company in the country to install the thin-bed type of shuttle car. On Oct. 8, 1940, nine companies in the state were using 41 shuttle cars, of which 10 cars at three mines were of the thin-bed type. All shuttle cars of the low type were in the southern fields and all of the high type were in northern West Virginia. At that time several units were in the process of delivery. The data in this paper were collected in the field by Mr. Schroder in connection with graduate work on mechanical loading of coal in West Virginia by mobile loaders. In the course of his field work he visited five mines in the state that were using shuttle cars. All of these mines were in high-volatile coal beds of strong structure. The more pertinent data obtained at the mines visited are given in Table I. The maximum distance of shuttle-car haul is the distance between the transfer station and the farthermost place. Tonnage per loading unit per foot of bed thickness is to some degree a measure of relative efficiency, especially if the different operations are working the same bed or have somewhat similar conditions. The thin-bed operation is well up in the higher bracket of the afore-mentioned column, which is as

Jan 1, 1942

By J. D. Braun, C. W. Powell

Diffusion between gold and indium at two temperatures below the melting point of indium (155.4oC) was investigated. The major, component of the diffusion zone was determined to be AuIn2; the other, intermediate phases in the system occur in much narrower layers In order of decreasing layer width these are: Au9In4, AuIn, Au4In. Inter diffusion coefficients of the four intermediate phases and the terminal solid solutions lie in the range of 2.4 x 10-l3 to 1.8 x 10-11 sq cm per sec. WHEN two metals which do not form a continuous series of solid solutions interdiffuse, each phase in equilibrium at the diffusion temperature should appear as a separate layer in the diffusion zone. In the Au-In system, diffusion plays a significant part in many commercial applications, particularly where indium alloys are used as solders for electrical contacts with very fine gold wire, for estab- lishing electrical contact to thin metallic films, and for mounting metal-coated piezoelectric crystals. A knowledge of the number, extent, and type of phases which form at diffusion temperatures below the melting point of indium, 155.4oC,1 and the diffusion constants for the system would be useful for these practical applications. Of more basic significance, additional information on polyphase diffusion in a system not previously investigated would be gained. The phase relationships in the Au-In system were determined primarily by Kubaschewski and Weibke1 and are based on thermal, microscopic, and X-ray analysis, Fig. 1. There are five intermediate phases in the system having approximate compositions corresponding to the formulas: Au4ln (ß)—80.0 at. pet Au; Au3In (?)— 75.0 at. pet Au; Au9In4 (d)—69.2 at. pet Au; AuIn—50.0 at. pet Au; AuIn2—33.3 at. pet Au. Solid solubility of indium in gold at 700°C is reported as 12.64 at. pet and at 406°C as 10.36 at. pet. No solid solubility of gold in indium is reported.

Jan 1, 1964

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By E. S. Shaw

Utah continues as a very unimportant factor in oil and gas production. During the year 1933 there were no developments of noteworthy significance. There were no completions of either producers or dry holes during the year. The only commercial production in Utah has been from the five fields listed in Table 1 and mentioned briefly in the following paragraphs. Virgin Field.—Oil was first discovered in 1907 in a well drilled in sec. 13, T.41S., R.12W. Of the first 15 wells drilled, all but three were failures. In 1920 production from four wells from 550 to 600 ft. deep was about 20 bbl. per day. San Juan Field.—The majority of drilling in this area was done during the years 1908 to 1911. Probably the first commercial well in the field was that drilled in NW.$i sec. 6, T.42S1 R.l9E., in 1909. Farnham Dome.—The discovery well was drilled by the Utah Oil Refining Co. in April, 1923. A number of years later a second well was drilled by The Carbon Dioxice a mica1 Co., the present operator, which markets the gas in the manufacture of "dry ice" and allied products. The eslimated production, as indicated in Table 1, includes 500 million cubic feet estimated to have been lost while drilling the discovery well. Cisco Dome.—The discovery well was drilled by The Utah Oil Refining Co. in November, 1924. The Crystal Carbon Co. markets the gas in the manufacture of carbon black. Ashley Valley Dome.—The discovery well was drilled by the Utah Oil Refining Co. in April, 1925. The Uintah Gas Co. markets the gas in Vernal, Utah, for fuel. Woodside Structure.—In February, 1924, gas was discovered in a well drilled by Utah Oil Refining Co. in sec. 12, T.l9S., R.l3N., on the Woodside structure. This gas is reported to contain an appreciable amount of helium. It is being held as a helium reserve by the United States Government. Salt Valley Structure.—The test of the Utah Southern Oil Co. in sec. 31, T.23S., R.21E., on the Salt Valley structure has been shut down for some time at 6120 ft. This test has passed through more than 5000 ft.

Jan 1, 1934

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By Louise Barton Freeman, Iley B. Browning, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943

By Iley B. Browning, Louise Barton Freeman, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943

By W. A. Backofen, D. H. Avery, W. F. Hosford

Sheets of the magnesium alloys AZ31B, HK31A, and ZE10A in several different tempers were tested in tension and determinations were made of the ratio of width-to-thickness strain. A marked increase in the ratio with tensile straining and a dependence upon alloy and test direction are rationalized in terms of a balance between the amounts of basal and prism-plane slip. All such variations are related, in turn, to the prevailing crystallographic texture. Fracture appearance is explained on the basis of anisotropy in plastic flow, and implications for developing texture -hardening effects in these alloys are discussed. ThE crystallographic texture or preferred orientation of a given material is determined by details of processing history. Such texture is known to influence many aspects of material behavior, in particular both the yielding and strain-hardening characteristics which are of special interest in the present work. Traditionally, the resulting plastic anisotropy has not been regarded as especially desirable. Earing in drawn sheet is perhaps the most common example of an unwanted effect of texture. However, it has also been recognized that suitable textures may be usefully employed to improve drawability,1,2 as a specific example, and generally to control yielding resistance under combined-stress loading.374 Texture would seem to be a detail of structure not yet exploited to nearly the fullest extent. A convenient basis for characterizing anisotropy in plastic behavior is the ratio of width-to-thickness strains obtained in a tension test;5&apos;6 the parameter is frequently labeled "R" and its value is revealing with respect to the nature of the prevailing texture. R gives a useful measure of a material&apos;s "thinning resistance". For an isotropic material, R = 1. With R > 1 the increased through-thickness strength in a sheet means greater resistance to yielding under biaxial tension, or "texture hardening";3&apos;4 if R < 1 the result may be a "texture softening" under the same loading conditions.4 Most R data relate to steel sheets for deep-drawing applications. Values for steel and other materials of cubic structures are not often much greater than 1 and nearly constant with strain in testing.1,2,7,8 To explore the implications of plastic anisotropy further, it was felt that experiments with much more strongly textured materials would be useful, and this led to the choice of magnesium alloys. The "ideal" sheet texture for magnesium contains the (0001) plane in the rolling plane, which ought to lead to R values approaching infinity. However, departures from the ideal texture, the possibility of slip in non-close-packed directions, and deformation by twinning would all be expected to introduce some range of R. Accordingly, studies on these materials were undertaken. EXPERIMENTAL Alloys in sheet form, Table I, were selected to obtain a variation in crystallographic texture, in the expectation that this would be reflected in differences in plastic anisotropy. Pole figures constructed by the Schulz surface-reflection technique9 were provided with the experimental materials by the Dow Metal Products Co. Profiles of pole density along great circles through the rolling (0 deg) and transverse (90 deg) directions were prepared from the pole figures and are collected in Figs. 1 and 2; considerable departure from the "ideal" (0001) alignment in the rolling plane is evident, with the largest angular spread in both directions being found in the ZEl0 alloy. Results of tensile tests on full-thickness specimens of 6-in. gage length by 1/2-in. width are given in Fig. 3 as engineering stress-strain curves* in rolling and transverse directions. All tests but one were made at a constant drive rate of 0.02 in. per min, and the final values of percent elongation at fracture, over the initial 6-in. gage length, are noted at the ends of the curves; one test on ZE10A-

Jan 1, 1965

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952