Search Documents

By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By O. B. Bucklen, J. P. Matoney, P. G. Meikle, R. L. Terry

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also holds true for loading and storage facilities. Where once a 1 million st per yr (910,000 mt/yr) mine was rare, 3-5 million st per yr (2,730,000-4,550,000 mt/yr) mines are not uncommon today in the bituminous industry. This great increase in production, made possible through mechanization, requires greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend to- ward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw-coal storage and blending facilities. The development of the unit train with its attendant economics has contributed more than any other factor to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has added to the need for faster and larger loading facilities. In this climate of rapidly changing technology, any written ac-

Jan 1, 1979

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By Harry Seltz

SEVERAL investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeser1 has made measurements of "average heat capacities" of iron carbide between 1026° and 85° K., using a water calorimeter. His computed true specific heat at 78.1° K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0° K. The cementite used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes" has measured the specific heat of iron carbide, from 102° to 323° K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100° K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3C, S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley' has reviewed these measurements and calculations, and selects those of Roth4 and Naeser5 as worthy of most consideration. Roth has given ?H = 5400 cal. ± 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (ß) he finds OH = 5600 cal. Kelley accepts the rounded figure ?H = 5500 as the heat of formation at 298.1° K., but this value is quite uncertain.

Jan 1, 1939

By K. R. Evans

The deformation mechanisms occurring in polycrys-talline, commercially pure titanium and a Ti-8 pct A1 alloy have been investigated and compared to earlier results by Levine on high-purity titanium single crystals and by Conrad on commercially pure titanium. In accord with Levine, two consecutive deformation mechanisms are observed to exist below 500°K with the transition temperature between mechanisms, Tc, strongly dependent upon interstitial composition. T, is found to be 210°. 375° -430°, and 450°K for alloys A large number of investigations have been conducted to determine the rate-controlling mechanisms of plastic deformation occurring in fcc and bcc metals. Very few investigations of a similar nature have been conducted for hexagonal metals. In fact, until very recently, magnesium is the only hexagonal metal which has been systematically investigated for determination of the rate-controlling deformation mechanisms.1"3 From these investigations, it was concluded that basal slip below 420°K occurs by the intersection of forest dislocations,1'3 while for prismatic slip the Peierls mechanism is rate-controlling at low temperatures with interstitial compositions of 0.024, 0.42, 0.61, and 1.13 at. pct expressed in terns of oxygen equivalents. The low-temperature mechanism is found to be an impurity obstacle mechanism in contrast to Levine's earlier conclusion of the Peierls barrier. Measurement of the activation parameters for deformation and estimation of the force-distance profile of the obstacles show their retarding force to be effective over longer distances from the obstacle as the interstitial composition increases. and thermally activated cross slip at higher temperatures. 2 The potential technological importance of titanium alloys has prompted recent studies of the deformation and fracture characteristics of titanium and its alloys. 4-8 Levine' systematically investigated the low-temperature deformation behavior of high purity titanium single crystals oriented for either basal or prismatic slip. It was concluded that the Peierls mechanism was rate-controlling at temperatures below 210°K, while above this temperature an undefined mechanism was rate-controlling. Conrad 7,8 concluded from an analysis of the composition dependence of the critical shear stress at 0°K and measurement of the activation parameters that the low-temperature deformation of titanium is controlled by an impurity

Jan 1, 1969

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1'4'5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,' basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,'' modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.' These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.' All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By Dr. O’Neil Thomas J., Donald W. Gentry

Money is like an arm or leg-use it or lose it." -Henry Ford INTRODUCTION If it were not for the existence of interest, the analysis of investment opportunities would be greatly simplified. In the absence of interest, investors would be indifferent as to when cash outlays are made or cash benefits are received. It would, in fact, be irrelevant whether the outlays preceded or followed inflows as long as both amounts are known with certainty. Of course, it does make a considerable difference whether, for example, a firm receives $1 million now or five years from now. The reason is that money does, indeed, have a value which is a function of time. Interest is how this time value is measured. Interest is generally defined as money paid for the use of borrowed money. In other words, interest is the rental charge for using an asset over some specific time period. The rate of interest is the ratio of the interest chargeable at the end of a specific period of time to the money owed, or borrowed, at the beginning of that period. In order to understand why interest exists, it is necessary to take the lender's viewpoint. The lender can justify charging interest for several reasons: 1) Risk: The lender is faced with the possibility that the borrower will be unable to repay the loan. 2) Inflation: Money repaid in the future will be in units of lower value due to inflation. 3) Transactions Cost: There will be expense incurred in preparing the loan agreement, recording payments, collecting the loan, and other administrative tasks. 4) Opportunity Cost: By committing limited funds to one borrower, a lender is unable to take advantage of other available opportunities. 5) Postponement of Pleasure: By lending money, an individual (or organization) is postponing the pleasure which that money could purchase. Each of these is a valid reason for a lender demanding interest from a borrower. The level of interest is, like the price of other assets, determined by supply and demand. Nonetheless, from time to time various analysts have taken a then current average interest rate and broken it down into the components described previously.

Jan 1, 1984

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.

By Thomas T. Read

MINING, which is at least twenty centuries old, was at first, and long, wholly a practical art. Little more than two centuries have elapsed since the inception of the idea that general education and a knowledge of natural science would be of advantage to those engaged in the mining industry. Though schools of mining began to develop in Europe early in the eighteenth century the concept of educational preparation for technical conduct of the industry was slow in winning general acceptance in the industry itself. John Hays Hammond, in his autobiography,1 recalls that when he sought employment with a mining company after he had graduated from Yale and Freiberg he had to assure its executive, before being even considered for employment, that he did not consider that he had learned anything about mining. This was as late as 1880. Existence in the industry of a prejudice against education of the academic type is perhaps an explanation why inadequate provision has been made by the mining industry for the continuing education of technical employees after they enter employment, although engineering education prior to engaging in industry has now won general acceptance. I am familiar with the existence of "loop" courses for engineering graduates in metallurgical plants, of schemes for giving mining graduates "practical experience," and of the interest in vocational courses for workmen which sprang up in the period of labor shortage during and immediately following World War I (but which quickly died when the depression of 1921 again made experienced workmen available in sufficient supply), having been chairman of a committee appointed by the Mineral Industry Education Division to make a survey of existing provisions for post-employment training for engineers in our industry. The results of that survey, reported elsewhere, clearly indicate that it is inadequate as to amount; the aim of this paper is to present evidence for belief that it is also inadequate in quality. To avoid becoming too involved, no reference will be made here to post-employment vocational training for workmen, which is a subject differing so much from post-employment education for engineers as to require separate treatment. Neither will postgraduate education for metallurgical engineers be discussed, because a distinction must then be made between training for research work and for plant operation, whereas mining engineers engage almost exclusively in operations. Since the situation in the coal-mining industry has been discussed at several recent meetings, that also will be passed over, and what follows should be taken as a discussion applying exclusively to the metal-mining industry. PROFESSIONAL DEVELOPMENT In the operations field (both in mining and metallurgy) the work to which a beginner is assigned is seldom closely related to previous academic education. The contrast is almost as great as between

Jan 1, 1941

By E. Robert Ruhlman

The term potash refers to potassium oxide (K2O), a compound not found in nature or produced by man but used as a basis for comparison of all potassium compounds and now is applied generally to various compounds of potassium used by agriculture and industry. Potassium, the last of the three major plant foods to be used in appreciable quantities by agriculture, was originally produced only from organic materials for chemical uses. The first recorded identification of a mineral source of potassium was in 1797; but, until the discovery in 1839 of the large deposits of soluble potassium salts in Germany and their development in 1860-61, nearly all potassium compounds continued to come from organic sources. With the importance of potash to plant life discovered in 1840 by von Liebig and the production of potash in Germany after 1861, agriculture soon became the major consumer of potash. In 1958 agriculture accounted for about 95 pct of the total potash consumption; the chemical industry used the remaining 5 pct. Mineralogy and Geology Potassium, an important constituent of the earth's crust, occurs in many forms in numerous rocks and minerals, including water solutions, but is not found in its native state. Twenty-five of the more important potash minerals are listed in Table 1. The properties of the five potash minerals most common in Permian salt formations follow: Sylvite is isometric; has a hardness of 2, a specific gravity of 1.98, vitreous luster, and cubic cleavage; and ranges in color from clear to brick red. In taste it is similar to halite but has a sharper taste and a cooling effect on the tongue. It is very plastic under pressure. Langbeinite is isometric; has a hardness of 4, a specific gravity of 2.82, vitreous luster, conchoidal fracture, and no cleavage; and ranges in color from clear to gray. It is taste- [ ] less, somewhat granular, and slowly soluble in water. Polyhalite is triclinic; has a hardness of 3, a specific gravity of 2.77, and dull luster; and

Jan 1, 1960

The first mention of the mining and use of coal in the Pittsburgh district refers to the mine under Duquesne Heights that furnished coal for the garrison at the fort at Pittsburgh in 1760. Coal had been dug and used as fuel just outside of Brownsville, Fayette county, in 1759, but this was not a regular mine as the opening was in an outcropping. Maps of Ohio in 1770 showed "Cole Mines" at various points. The Penns purchased all the coal south of Kittanning in southwestern Pennsylvania from the Chiefs of the Six Nations for a reported price of $10,000. During the Revolution, coal from Herron Hill, Mincrsville, and Coal Hill, all within the present city limits, was used in Pittsburgh. There is today one custom pit opened in Coal Hill (Duquesne Heights). The first steam engine was set up in Pittsburgh in 1794 and used coal as fuel. The first mine in the Youghiogheny gas district was opened in 1796. In 1803, the first shipment of coal by water was made from Pittsburgh down the Ohio river and landed at Philadelphia, where it sold for approximately $9.50 per ton. The mines along the Monongahela were naturally the first to be opened. With the completion of locks and dams in 1844, permitting slack-water navigation, the industry began to thrive. The No. 8 field of Ohio and the Fairmont region of northern West Virginia were opened in the period 1840 to 1855. From that time on there has been a continuous development of the coal rcsources of this district, until at present productive capacity is enough to supply 30 per cent. of the country's needs of bituminous coal. The original method of working the Pittsburgh seam was to drive under cover at some easily accessible point on the outcrop with a single entry, usually 1½ yd. wide. Rooms or gangways were turned to the right and left from this entry and ventilation was usually poor and inade-

Jan 1, 1927

By E. L. Anderson, J. R. Long, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By T. Prof. Egleston

ALL industrial establishments whose operations depend upon chemical reactions use gases. In the simplest case the oxygen of the atmosphere, heated or not, as the case may be, is used, and in other cases, gases which are produced by a special apparatus of more or less complex composition. The manufacturer depends, for the success of his operations, entirely upon having these gases arrive at the right time, in the proper proportions, at the required temperature. It often requires but a slight variation in their composition to make a given process a success or a failure. In most cases the gas used is formed from fuel, and according as variations in its composition are produced by alterations in the manner of charging the grate, not only different, but often directly opposite, results are obtained. The great industrial question of the present time, and one upon which the prosperity of the world depends, is how to get the greatest amount of useful effect from fuel, whether the caloric is used directly or is transformed into horse-power. In almost all industrial pursuits this translates itself into the question of how to construct a fireplace and its adjuncts in such a way that the heat of the flame and of the products of combustion shall be made to produce a maximum effect. Unfortunately, until very recently, except by comparison, there was no means of ascertaining whether the loss of useful effect was 80, 40, or 20 per cent. of the total amount of fuel employed. It seems now strange that there should have been furnaces so constructed as to produce 20 per cent. of carbonic acid in the fireplace, but this has been proved by analysis to have been true. It does seem incredible that, notwithstanding the immense number and variety of furnaces used for different processes, and the great difference in kind, quality, and quantity of fuels consumed, there should formerly have been used for them all, the same stereotyped fireplace, varied only in its dimensions of height, length, and breadth. It is true that, with a good fireman, excellent effects may be, and have been, produced, but the manufacture is here, as in many other cases, dependent on the intelligence of the workman, a very uncertain reliance for capital to rest upon. The workman, unless he receives a prime for fuel saved, or is fined for excessive use of it, may be said

Jan 1, 1874

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By Harlan W. Nelson, James B. Purdy

A study of data obtained during laboratory tests to determine the suitability of bituminous coals for use in residential underfeed stokers of the clinkering type has led to the following general conclusions: 1. Performance data obtained during the test furnish useful and practical information upon which to judge the performance of stoker coals. 2. Conclusions derived from the results of evaluation tests are in general agreement with use experience of the coals in the field. The method is of practical use in this regard. 3. Few direct relationships were found between data furnished by the evaluation test and determinations by standard laboratory tests. This is particularly true with regard to coke formation and clinker formation, two of the most important factors in determining the degree of satisfaction to be obtained in applications of the small underfeed stoker. It has not been the intention in this paper to prescribe this evaluation test as the best method for the evaluation of coals for use in residential stokers. That there are other test methods having similar objectives serves to point out the necessity for full-scale laboratory tests. At the present time, a standard test procedure for the evaluation of coals for use in residential stokers is not available. For the past several years a joint committee, appointed from the membership of the Residential Stoker Committee of Bitulninous Coal Research, Inc., and from the Engineer- ing and Research Committee of The Stoker Manufacturers Association, has been working to develop a standard procedure for testing and evaluating bituminous stoker coals. This procedure has been completed to the extent that it has been drawn up in tentative form. It is now planned to install the equipment in several laboratories and to run check tests, using portions of identical lots of coal, to determine the degree of reproducibility offered by the method. Completion of this standard test procedure should greatly facilitate the evaluation of coals for use in residential stokers. Acknowledgments The cooperation of coal operators sponsoring the coal evaluation tests, in granting permission to use data and results from their tests, is gratefully acknowledged. Acknowledgment is also made to Carroll F. Hardy, Chief Engineer, Appalachian Coals, Inc., for his interest and timely suggestions on the preparation of this paper. Special thanks are due to Ralph Sherman, Assistant Director, Battelle Memorial Institute, who was largely responsible for development of the evaluation procedure, for helpful suggestions and advice. References I. H. A. Sherman: The Evaluation of Coal for Use in Domestic Stokers. Univ. of Ill., Eng. Experiment Station, Circular No. 39 (1939). 2. . Q. Shotts: The Relation of Free- swelling Indexes to Other Characteristics of Some Alabama Domestic Stoker Coals. TP 2314, Coal Tech., (Feb. 1948); Trans. AIME (1948) 177, 502. 3. . J. Helfinstine and C. C. Boley: Correlation of Domestic Stoker Combustion with Laboratory Tests and Types of Fuels 11. Combustion Tests and Preparation Studies of Representative Illinois Coals. Ill. State Geol. Survey, Re1. of Zntlestigations No. 120 (19467 ) p. 35. DISCUSSION E. R. Kaiser*—AS a former fuel engineer assigned to residential stokers at Battelle, the writer has read with considerable interest the paper by Messrs. I'urdy and Nelson. It is gratifying to note that earlier test techniques have been developed and that criteria found important in the years 1935 to 1938 are still important in judging the performance of stoker coals for residential heating. The authors have plotted a number of the primary coal data singly against performance data of the stoker in an effort to establish relationships. Unfortunately, wide scattering of points usually resulted, which did not illustrate what experience generally indicates to be the case. For example, Fig 3 indicates almost no trend in the percentage of released ash converted to clinker with change in ash-softening temperature. Other factors, such as fuel bed temperatures and zones of heat release must have influenced the results. In the present state of our knowledge, we cannot explain all of the reasons why suitable stoker coals perform satisfactorily, nor why one satisfactory coal may be better than another. It would therefore

Jan 1, 1950

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944