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By E. C. Burke, W. R. Hibbard

Plastic deformation in magnesium single crystals was studied by tensile tests at room temperature utilizing an improved preparation and testing technique. Consistent critical resolved shear stress values for basal slip were obtained. The advent of pyramidal slip at room temperature was rationalized upon the basis of grip constraints. A bend-twinning hypothesis was advanced as an explanation of mechanical twinning which occurs as a complex stress-relief mechanism. INVESTIGATIONS of the plastic deformation of magnesium have been limited to the determination of the fundamental kinetics which may be summarized as follows: 1—Twinning on the {102).l 2— Slip on the (001) plane in the [loo] direction at room temperature.' 3—Slip on the {101) or {102) plane in the [loo] direction above 225°C." 4—Critical resolved shear stresses for basal slip in tension at room temperature of 83 g per sq mm with a variation from 57 to 127 g per sq mm." Bakarian' studied the compression of thin wafers of magnesium single crystals and classified the components of the deformation mechanisms as follows: 1—The Basal field: (001) at an angle of less than 20" to the compression surface. Fracture along {101} or slip on (001) followed by {101} fracture. 2—The prism field: (001) at an angle greater than 60" to the compression surface. Twinning on the {102) generally occurring during the early stages of loading, basal slip in the areas of original orientation and (001) slip within twins. 3—The central field: (001) at angles greater than 20" but less than 60" to the compression surface. Slip on the (001). 4—The critical resolved shearing stress for {101} slip above 225°C was 400 g per sq mm. Observations of mechanical twins in hexagonal close-packed metals have been summarized by numerous investigatorsb-' emphasizing a lateral or rotational atomic adjustment, in addition to the pure twinning shear, and the importance of reorienting the basal plane to a position more favorable for continued slip, rather than the resulting small dimensional changes. Criterion for the operative twinning planes has not been clearly established. Schmid and Boas hurmised that an energy condition related to the atom movements is the determining factor. MillerQ bserved that twinning stresses in zinc crystals decreased as the amount of prior deformation increased. Preparation of Specimens Magnesium single crystals % in. in diam x 8 in. long were grown from the melt under an argon atmosphere in a gradient furnace similar to that described by Jillson." Magnesium containing 0.018

Jan 1, 1953

By T. M. Chatard, Cabell Whitehead

The Republic mine, situated forty miles from Marcus, a station on the Spokane Falls and Northern Railroad, in the northeastern part of the State of Washington, was located in 1896, but no development-work was dolie until the spring of 1897. While much of the ore mined since then has been rich enough for shipment to smelters, a method of locally treating the lower-grade ores soon became a matter of prime importance, because only about 40 per cent. of the values could be recovered by plain amalgamation, even with ores assaying 4 to 5 ounces of gold per ton. Experiments with cyanidation, in various ways, led to the adoption of the Pelatan-Clerici process and the erection on this system of a 10-ton experimental plant, which was later increased to a capacity of 35 tons per day. The extractions by this process showed much improvement over previous work, especially when the ore was crushed to

Jan 1, 1901

By William A. Johnson

IT was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomogeneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot he obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yields information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most important types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in a gold-lead

Jan 1, 1942

By R. A. Cunningham, A. S. Murray

If a dense fluid such as mud or water is used for circulation, the formation drilled is influenced by a hydrostatic pressure. This pressure depends on hole depth arid drilling fluid density. Laboratory tests indicute that drilling rates in many forri~ations are decreased with increased pressure,—in some cases as much as 90 per cent. A comparison between laboratory and field tests indicates that drilling fluid head affects drilling rates in the field approximately the, same as in the laboratory. Drillirrg rates of many formations are increased by reducing drilling fluid head. INTRODUCTION For many years it has been noted that field and laboratory drilling rate tests did not agree even when the formations tested were the same. For instance, tests of some shales by the Hughes Tool Co. laboratory indicated drilling rates approximately 20 to 30 ft/hour, whereas in the ground this shale would drill only 3 to 5 ft/hour. A possible reason for this discrepancy is the effect of the high pressure which the drilling fluid exerts against the formation at the bottom of the hole. Consider a small element of rock (Fig. II that is to be removed by a rock bit. If the hole is filled with mud or water. the upper surface of the rock element is subjected to a pressure which depends on hole depth and fluid density. The mass of earth around this rock element presses against the circumferential surface and the lower surface. Because of the probability of shearing stresses between the rock element and the surrounding rock, this element is not under true hydrostatic stress. However, as a first approximation for test purposes the rock element was assumed to he under hydrostatic stress. The effect of hydrostatic pressure on some physical properties of rock has been studied.1,2,3 These tests show that the "differential" compres-sive stress:': necessary to cause rup- ture in rock cylinders is greater when tested under high hydrostatic pressure than when tested under atmospheric conditions. These tests were made with pressures greater than 20,000 psi which is in excess of those normally encountered in oil well drilling. Similar tests were made by the Bureau of Reclamation' using pressures equivalent to those encountered in oil well drilling. Again the "differential" compressive stress necessary to produce failure increased with increasing hydrostatic pressure. These tests indicated that drilling rates would probably decrease. Correlation between these tests and drilling tests was not practical. The purpose of this work is to study the effect of mud column pressure on drilling rate, assuming that the material drilled is in a state of hydrostatic strcss. This problem was initially investigated in the laboratory using variable bit loads and confining pressure;. Confirmation of laboratory results was obtained in the field from a series of carefully controlled drilling tests. Because of the necessity of testing many different types of formations. only results from representative formations will be presented here.

Jan 1, 1956

By Bernard K. Asdell

Georgia, a state seldom considered to be an important mineral producer, has one surprising feature-it is the nation's largest producer of kaolin. Kaolin is a highly important raw material in the paper, rubber, ceramic whiteware, paint and chemical industries. In 1965, more than 2.7 million tons of kaolin were produced in this state, a 150,000-ton increase over the preceding year, and production continues to climb. Strictly defined, the term "kaolin" applies to a group of hydrous aluminum silicates in which kaolinite is the predominant mineral. Kaolinite is inherently white, non-abrasive, chemically inert, and of a very fine particle size, ranging from sub-micron to 40-microns equivalent spherical diameter. An electron-micrograph of kaolinite is shown in Fig. 1. The particles finer than about 2 microns are thin, elongated plates, hexagonal in outline. The larger particles, coarser than 2 microns, are predominantly vermicular in outline with a foliated structure. Table I shows a typical chemical analysis of commercial, wet-processed kaolin compared to pure kaolinite.

Jan 11, 1967

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employ¬ment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members. SEC. 3. Honorary Members: Each candidate for Honorary Membership must be recommended by at least ten Members and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of the Directors present; provided, how¬ever, that the number of Honorary Members shall at no time exceed twenty. Such election shall automatically act as a transfer of such member from any other class of membership to which he may belong. SEC. 4. -Senior Members: The Directors may in their discretion place on the Honor Roll of Senior Members and transfer from any other class of membership other than Honorary Membership the name of any Member or Associate who has reached the age of seventy years and who has paid dues for thirty years, and for good reasons in special cases may vary the age or number of years. SEC. 5. Junior Members: A person to be eligible for election to the class of Junior Member must be qualified through education or experience to hold a subordinate position in engineering, mining, metallurgical, geological or chemical work. He shall be not more than 33 years of age at the time of election. SEC. 6. Associates: A person eligible for election or transfer into the class of Associate shall be one, who, in the opinion of the Committee on Admissions and the Board of Directors, is suitable for such election or transfer by reason of his interest in or connection with mining, geology, metallurgy, or chemistry. SEC. 7. Rocky Mountain Members: Membership in a special class of life member¬ships without annual or other dues and without right to receive the printed literature distributed to other members or the right and privilege of wearing the official badge of technical members, is given to all members of the Rocky Mountain Club at the time of consolidation. These special Rocky Mountain memberships shall be claimable by any member of the Rocky Mountain Club, not already a member of the Institute, availing himself of the privilege within ninety days after mailing of notice to him, by the Secretary of the Institute. SEC. 8. Junior Foreign Afliate: Upon appropriate action by the Board of Direc¬tors and with its approval, members in good standing of any technical society having its headquarters outside of the United States of America, Canada, or Mexico,

Jan 1, 1937

By L. C. Glenn

In the preparation of this paper the writer has drawn freely upon the writings of Orton, Munn, Shaw, Mather, Miller, Hoeing, St. Clair, Jillson, and others, as well as upon his own personal knowledge of the fields of both states. It is to be regretted that certain data gathered by him and his assistants last fall are not available for publication. Oil in Tennessee A few wells drilled for brine for salt making in Tennessee between 1820 and 1840 obtained oil, but no definite search was made for oil until just after the close of the Civil War. Active drilling was then begun in Overton and counties southwest of it on the eastern half of the Highland Rim. A number of strikes were made at shallow depths in the basal part of the Mississippian but the wells were soon exhausted and abandoned. Drilling was revived, about 1892, when the Spurrier district in Pickett County was developed and was followed by the Riverton district in the same county in 1896. A pipe line was laid from the Wayne County, Ky., fields and about 60,000 bbl. of oil were run before a very heavy slump in the production, a failure to find an extension of the field, and excessive local taxation caused the removal of the pipe line in 1906. There was then no production in Tennessee until the discovery, in 1915, of oil near Oneida, Scott Co., at about 950 ft. (289 m.) in fissures in the Newman or St. Louis limestone. This field, however, soon failed and was abandoned. In 1916, oil was found at Glen Mary, Scott Co., in the Newman limestone at a depth of 1232 ft. (375 m.) A number of wells have since been drilled there, some of which were dry while others, close by, were produccrs. The largest one yielded, at first, about 340 bbl. per day and produced for several months, when it suddenly went dry. Several of the first wells began at 6 or 8 bbl. per day and are still maintaining that output. Production is from a fissured part of the limestone and varies greatly in accordance with the size and extent of the ramification of the

Jan 1, 1921

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

By J. L. Thompson

There are two basic forms of the LPG-slug process: the gas driven and the water driven. The pressure required for miscibility between gas and LPG prohibits the use of the gas-driven LPG process in shallow reservoirs. The water-driven LPG slug process normally exhibits good sweep efficiency. However, displacement of the LPG by water is poor. An improvement in this process appears possible by injecting a slug of carbon dioxide between the LPG slug and the water drive. Laboratory experiments were conducted in homogeneous linear systems to determine the effect of pressure on the various displacement zones. In the carbon dioxide-LPG displacement zone, the effect of pressure on the displacement efficiency is negligible above the miscibility pressure. However, the displacement efficiency decreases linearly with decreasing pressure below the miscibility pressure. With water displacing carbon dioxide, it was found that the recovery of carbon dioxide after water breakthrough can be predicted from its solubility in water. A displacement test was conducted with LPG and carbon dioxide slugs large enough to avoid interference between the oil-LPG, LPG - carbon dioxide and carbon dioxide - water displacement zones. Under these conditions, essentially complete oil and LPG recovery was obtained. However, a substantial amount of carbon dioxide was left in the core at water breakthrough. INTRODUCTION It has been shown in homogeneous linear systems that essentially complete oil recovery can be obtained by displacement with a miscible fluid such as LPG. Economic considerations dictate that the valuable LPG also be recovered. Methods proposed for recovering the LPG include (1) displacement with natural gas at a pressure high enough to make the two fluids miscible1 (the disadvantage of this method is that the required pressure of about 1,500 psi is too high for shallow reservoirs) and (2) displacement of the LPG with water2 (principal disadvantage is that a large amount of LPG remains in the formation because of poor displacement efficiency). This paper treats an improvement in the water-driven LPG slug process3,4 where carbon dioxide is injected between the LPG and water. Carbon dioxide is completely or at least partially miscible with propane and soluble in water; thus, displacement efficiency is improved at both ends of the carbon dioxide slug. To minimize effects of other variables, all experiments were conducted in linear core systems. GENERAL PROCESS DESCRIPTION The displacements of propane by carbon dioxide and carbon dioxide by water are considered separately, assuming enough of each is injected to prevent mutual interference. Displacement descriptions are confined only to the part of the pore volume containing mobile fluids unless otherwise specified. The schematic representation is given in Fig. 1. Starting at the producing well, a zone containing only oil is followed by a zone containing a single-phase mixture of propane and oil. The concentration of propane increases in the direction of the injection well and ultimately grades to pure propane. Then follows a zone containing a mixture of propane and carbon dioxide in continuously varying proportions until 100 percent carbon dioxide is reached. In this zone, the concentration of carbon dioxide in the immobile water phase also varies from zero to full saturation. Whether the displacement of propane by carbon dioxide is of complete or partial miscibility depends on pressure and temperature (Fig. 2). If the horizontal line representing the prevailing pressure intercepts the boundary curves of the phase envelopes for the prevailing temperature (i.e., if the pressure is lower than the critical

By AIME AIME

FEW men are as well known to metallurgists or steel men everywhere as this year's Chairman of the Iron and Steel Division. This is evident from the writer's experience some years ago while visiting Krupp's new open-hearth plant near Essen and the Skoda Works at Pilsen. The first question asked there was: "You know Dr. Herty?" Knowing Charlie Herty has advantages, not the least of which is (or was in 1933) a fine lunch with a plethora of good Rhine \vine at Essen and a super- plethora of Pilsener beer at Slioda.

Jan 1, 1941

By W. W. Schmittroth, A. Y. Bethune

The commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "super-purity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,' it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon were not desirable. The use of special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1949

By B. W. Levinger

THE system Ti-CI- has been studied by several investigators." ' Though titanium and chromium are completely miscible at high temperatures, an intermediate phase of the approximate atomic proportions TiCr, has been identified at various compositions between 60 and 68 wt pct Cr. The structure of this phase was established as the cubic C15 (MgCu2) type with 24 atoms per unit cell and a lattice parameter 6.929 kX.2 During a study of the ternary system, Ti-Mo-Cr,5 the existence of a high temperature modification of the TiCr, phase was discovered. In a series of alloys annealed at 1300°C and containing from 60 to 70 wt pct Cr and 5 pct Mo, a new phase was present which did not correspond to either ß solid solution or TiCr,. By trial, the new phase was identified to be of the hexagonal C14 (MgZn2) structure with 12 atoms per unit cell. Further work showed that the hexagonal structure was. in fact, also present in binary Ti-Cr alloys quenched from high temperatures. To make the identification more certain, the intensities of the various reflections were calculated assuming a composition TiCr2 and C14 structure. Table I lists reflection planes, interplanar distances, calculated intensities, and a comparison of these values with the lines of a binary Ti-Cr alloy (66 pct Cr) annealed for 20 min at 1385°C and water quenched. Since high angle lines were more diffuse, the correspondence between visually observed and calculated intensities was not as good at these angles. Lattice parameters were computed to be a = 4.922 kX, c = 7.945, c/a :- 1.614. The corresponding interatomic distances are: titanium to titanium distance, 3.00:, kx, chromium to chromium distance, 2.43, kX, titanium to chromium distance, 2.88,, kX. These compare to 3.00, 2.45, and 2.87 kX in the cubic phase, respectively.' The atomic positions in the C14 structure are as follows: Titanium 1/3, 2/3, Z; 1/3, 2/3, 1/2: 2/3, 1/3, i; 2/3, 1/3, (1/2-z); Chromium 0, 0, 0: 0, 0, 1/2; 2x, 2, 1/4; 232, x, %; X, 22, 1/4; X, 2x, 3/4; x. x, 1/4; x, x, 3/4; The values of x and z were calculated for the alloy mentioned and found as follows: z — 0.061, x = 0.165. The values assumed in the intensity calculations were those for an ideal close-packed lattice or z = 1/16, x = 1/6. Work in the Ti-Mo-Cr system indicates that y2 the hexagonal modification of TiCr2, is the stable phase above 1300°C, while y1 with the cubic structure is stable below 1000°C. X-ray examination of a number of alloys annealed at intermediate temperatures showed that the hexagonal and cubic phases can coexist. Alloys quenched from 1000°C and annealed at 1100" and 1200°C showed small amounts of y2 at the higher temperature. A considerable amount of y, seemed present, however, in cast alloys annealed at 1100°C. It further appears that there is a small but definite solubility range for both phases in the ternary system. Acknowledgment The results of this paper represent work carried out in conjunction with a project sponsored by Watertown Arsenal, Contract No. DA-11-022-ORD-272. References 'M. K. McQuillan: Journal Inst. Metals (1951) 79, p. 379. 2 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44, p. 495. W. J. Van Thyne,. H.. D. Kessler, and M. Hansen: Trans. ASM (1952) 44, p. 974. 1 F. B. Cuff, N. J. Grant, and C. F. Floe: Trans. AIME (1952) 194, p. 848; Journal of Metals (August 1952). Unpublished Research, Armour Research Foundation. "H. J. Wallbaum: Ztsch. Krist. 103, p. 391.

Jan 1, 1954

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By E. E. Gardner, P. A. Schumann

A description of a new four-point probe configuration which permits measurement of epitaxial layer resistivity is given. An analytic solution to the potential distribution due to a point current source on a multilayered structure is briefly described. Typical solutions for this probe configuration are presented. Probe spacing, layer thickness, substrate resistivity, and substrate thickness enter into the calculation. Correction factors for typical cases are given. A brief description of the construction of a probe which can achieve a small spacing of 15 is presented. The prohe is constructed so that all points are adjustable by micrometers and the probe spacing and configuration can be easily altered. Measurements of layer resistivity with the four-point probe are compared with those taken with the three-Point probe and diode-capacitance techniques. TWO techniques of obtaining profiles of N/N+ epitaxial structures are given. The reproducihility of the probe spacing and resistivity measurement is discussed. The effects upon the resistivity measurement of errors in the measurement of the lager thickness, substrate resistil)itv, and substrate thickness are presented. SINCE its introduction by valdes' in 1954, the four-point probe has been the most widely used tool for determining semiconductor resistivity. Its usefulness ranges from the evaluation of bulk semiconductor ingots to the characterization of impurity profiles in diffused structures. In general the four points, two current probes and two potential probes, are placed on one surface of the material being tested either in an in-line array or in a square array. Numerous correction factors1 8 have been worked out for these configurations which are dictated by the finite geometry of the sample being tested. One method of evaluating thin wafers has been proposed which has two probesg on each side of the wafer. Further modifications have added a fifth'' and a sixth" probe. One paper1' has discussed the accuracy of the four-point probe and the precautions necessary in its use. With the exception of the method where two points are placed on opposite sides of the wafer, the four-point probe is restricted to evaluation of wafers with a homogeneous resistivity or to the case where an isolating junction exists between the substrate and the layer (epitaxial or diffused) being evaluated. Due to the relative resistivities and thickness, the resistance of the epitaxial layer is much greater than that of the substrate, and consequently a majority of the current flows through the substrate. The potential distribution at relatively large distances from the current sources is determined by the substrate resistance, and hence the AV/I value is a measure of the substrate resistivity and not that of the epitaxial-layer resistivity. In the immediate vicinity of a current source the potential distribution is determined by the layer resistivity among other factors. Consequently, if the potential probe is placed very close to the current source, then with appropriate correction factors it is possible to determine the layer resistivity. This was the theoretical basis for using two closely spaced probes on opposite sides of an epitaxial wafer. However, due to mechanical problems, it is desirable to place the four probes on the same side of the wafer. This paper discusses the potential distribution in

Jan 1, 1965

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

By G. K. Manning, M. C. Udy, L. W. Eastwood

Those who have examined beryllium and beryllium-rich alloys under the microscope have noted the results of the difficulties encountered when preparing these materials for examination. Hard constituents are readily chipped and pulled out of the matrix, and the soft ones are easily gouged out or embedded with abrasive or other material. The matrix is easily deformed, which makes it very difficult to remove the effects of scratches. Furthermore, the matrix and some of the constituents are also readily pitted during etching, which makes the structure difficult to develop. The metallographic techniques designed to avoid these difficulties are neither radically new nor necessarily the best possible procedures. They were developed at Battelle to fill immediate requirements as part of a study of the preparation and pouring of beryllium melts as described in a separate paper. A part of the research program on the causes of gas unsoundness in beryllium castings entailed a study of the effects of such gases or gas formers as oxygen or oxides, nitrogen or nitrides, and carbon or carbides. These gases or gas formers, if dissolved in the melt, might be an important factor in the study of unsoundness caused by gas evolution in beryllium. Because it was necessary to be able to distinguish these gases or gas formers, if present as alloy constituents, from metallic phases also present as alloy constituents, a series of alloys was prepared with additions of the various possible metallic and non-metallic constituent formers. It should be emphasized that the constituents referred to as gases or gas formers are important in the study of gases in beryllium only if they form a part of the alloy, that is, if they dissolve in the liquid or solid metal. During the first part of the development of metallographic techniques, the Massachusetts Institute of Technology, unpublished report (TC 3315, Nov., 1945) by Paul Gordon, describing various microconstituents in beryllium, was quite useful. Of particular interest in this report is the confirmation of one of the conclusions drawn from the present investigation, that is, that a distinct oxide phase apparently does not occur in beryllium. The Preparation of Metallographic Specimens GRINDING PROCEDURE The original specimen is either sawed or cut on an abrasive wheel to a convenient size. For best results, the surface to be polished should not be more than about 1/4 in. square, and it is convenient to mount the specimens in bakelite to facilitate handling. Two alternative grinding procedures have been developed. As one alternative, specimens are ground successively on 120-, 240-, and 400-grit, wet-or-dry metallographic discs. The abrasive discs are revolved at 1750 rpm on a conventional pedestal grinder. The coarsest disc (120 grit) is used either wet or dry, and in most instances, it can be eliminated from the procedure. Grinding on the two finer discs (240 and 400 grit) is accompanied by the application of kerosene. The technique consists of holding an oil can, containing kerosene, in one hand and the mounted specimen in the other hand. While the grinding is being done, several drops of kerosene are applied every few seconds close to the center of the disc. Carbon tetrachloride serves at least as well as kerosene as a lubricant; perhaps it is slightly better, but it volatilizes so readily that an additional health hazard is involved. Light oils and water are not satisfactory for the finer grinding operations. The second procedure is perhaps slightly slower than the first and requires a more careful technique, but it eliminates the use of kerosene. The specimen is first ground wet on a 240-grit disc, followed by dry grinding on a 400-grit disc. Finer grinding does not appear to be necessary with either of the two alternative procedures. The pressures used throughout either grinding operation must be extremely light, that is, barely sufficient to hold the specimen in contact with the disc; otherwise, flow and chipping are almost certain to occur. In both procedures, it is essential that the discs be sharp and that they be discarded as they show evidence of becoming dull or loaded. In general, not more than four or five specimens can be ground on a disc before the disc becomes dull enough to warrant discarding it.

Jan 1, 1950

By V. S. Rood

Typical System of Workings THE general system of workings at the Utah-Apex is similar to that found in many of the western metalliferous mines. There is a vertical three-compartment shaft extending to the surface, from which the various levels have been driven to the orebodies. The 1000-ft. (305-m.) level, about ¾ mile long, was driven as a haulage and drain adit. Geology The formation is a flat north-dipping series of alternating limestone and quartzite beds. Extensive north-south faulting and-fissuring have taken place, resulting in the formation of large replacement orebodies in the crushed zones in the limestone. The orebodies are irregular in shape and size, but follow closely the trend of the mineralizing fissures. The ore consists of galena, pyrite, sphalerite and small values in silver and gold. Large masses of non-commercial pyrite are frequently found in or adjacent' to the orebodies, and more or less pyrite is found for some distance in the walls of the orebodies. Lenticular bodies of a black pyritic shale also occur in the zones where extensive faulting has taken place.

Jan 6, 1918

By J. Lohrenz, R. J. Francis, G. C. Clark

Compositional material balance methods have been extended to solution gas-gas cap-water drive reservoirs. Partial or complete pressure maintenance as well as reservoir repressuring by gas and/or water injection may be considered. Increrments of reservoir withdrawals and injections equivalent to a given time increment are used as the basic iterative step to allow the extension. An example field study shows how the reservoir volumes. extent of the water drive, and relative permeability ratio function may be estimated. Knowing these, the methods can be used to predict reservoir behavior. INTRODUCTION The compositional material balance is similar to conventional material balances in many aspects. The assumption of a pressure-homogenous reservoir with no transients is common to all conventional material balances1-1 although numerical methods are different. The compositional material balance also contains this assumption. Inclusion of phase equilibria directly in reservoir calculations is the key difference and improvement in the compositional material balance. A continuous account of the compositions of the reservoir fluids and effluents is determined. Calculations of fluid phases and properties can be based on these compositions. Excepting fluid phases and properties determined in this manner, the compositional material balance uses procedures exactly analogous to conventional methods. Brinkman and Weinaug5 and Jacoby and Berry6 have given compositional material balances for simple solution gas drive reservoirs; subsequently Jacoby and Berry' extended their procedure to include pressure maintenance by gas injection at constant reservoir pressure. This paper extends compositional material balance techniques to a more general combination drive reservoir with various types of pressure maintenance operations. The procedure for this extended compositional material balance and an example of its field application are presented. PROCEDURE The numerical calculations of this compositional mate- rial balance are performed on a high-speed digital computer. The most comprehensive case the present compositional material balance program can handle is a solution gas-gas cap-water drive reservoir with (1) water production, (2) water influx, (3) separate or commingled production from the oil and gas zones, (4) any surface processing arrangement including LPG and gasoline production, and (5) gas injection into the gas and/or oil zones." This description of the procedure applies to this most comprehensive case. Appropriate deletions in the procedure can be made for more simple mechanisms. ASSUMPTIONS In common with conventional material balances, the compositional material balance makes the following assumptions: (1) the total reservoir is at a uniform pressure at a given time; (2) the volumetric ratio of gas to liquid withdrawal at reservoir conditions is directly proportional to their mobilities; and (3) instead of assuming a pressure-dependent total gas-oil equilibrium, the cornpbsitional material balance makes a sianificantly different and more rigorous assumption as follows. Thermodynamic equilibrium exists for each component in the liquid-gas mixtures in the reservoir and in surface processing. These three assumptions are fundamental in the compositional material balance procedure. Other assumptions involve arbitrary simplifications of the reservoir mechanisms. This compositional material balance uses the following simplifying assumptions: (1) no bulk mixing occurs between the gas and oil zone; (2) total mixing occurs between any injected gas and the contents of the injection zone; (3) no in situ hydrocarbon liquid is produced from the gas zone; (4) no reservoir gas is retained behind any net bottom-water influx; (5) the residual saturation of hydrocarbon liquid at reservoir conditions behind any net bottom-water influx is constant; and (6) fluids retained behind any net bottom-water influx exert no further influence on the reservoir. These six assumptions are not fundamental. Modifications of the present procedure can be made for different assumptions of the reservoir mechanisms. THE TIME INCREMENT Previous compositional material balances have used a pressure increment for simple solution gas drive reservoirs"" and an increment of injected gas for pressure maintenance.' These increments are suitable for these simple cases. They are, however, inadequate for reservoirs with time dependent drive mechanisms including water drive. A time increment removes this inadequacy and is

By Orville R. Lyons

THE continuous vacuum filter, whether it be a vertical or horizontal disk, inside or outside drum, when properly applied is a very effective device for dewatering fine solids. Because of the number of variables that affect its performance, however, it is not possible to obtain consistently maximum moisture reduction in an operating plant. This paper presents a method for determining the average cake moisture and the variations in cake moisture to be anticipated when dewatering fine solids by continuous vacuum filters under normal operating conditions. Previous investigators1,2 have found that certain factors influence filter performance, drum or disk diameter, speed of rotation, percentage of immersion, and the percentage of solids in the feed influence capacity. Blinding of the filter cloth reduces effective vacuum, produces a wetter cake, and may decrease capacity. Reduced vacuum or improper adjustment between vacuum and blowing portions of the cycle will produce a wetter cake and also may decrease capacity. Widely fluctuating feed tonnages will adversely affect cake moisture and capacity. Flocculation, when properly applied, increases capacity and reduces cake moisture. Without flocculation, the slimes are the first particles sucked to the filter medium, which becomes partially blinded in consequence. With flocculation, the flocs act as coarse particles and the filter medium is not blinded. Overflocculated pulps, although filtering well, may yield wet cakes. Average Particle Size and Cake Moisture A method for predetermining the surface moisture content of coal filter cakes was published in 1949; but this method could not be applied to coals deficient in —200 mesh material or to fine mineral concentrates. Test data obtained for geared-weight types of vibrating screens4 and for centrifuges5 used to de-water coal provided definite correlations between the average particle size of a dewatered cake and the surface moisture content of the cake. It was thought that this same method of correlation should be applicable to filters, whether dewatering fine coal or fine mineral concentrates. To develop a correlation or correlations between average size of cake and cake moisture, the author collected data for filtration operations from as many sources as possible. In a considerable number of instances the information was provided by plant preparation engineers,"-" a few of the tests were on a laboratory scale: and the remainder of the data was obtained from published articles.10-17 Table I contains size-consist and miscellaneous data for coal filter cakes, and Table II contains the same data for mineral concentrate filter cakes. Fig. 1 shows the relationships existing between the average particle size of the cake and cake moisture (surface moisture for coal and total moisture for minerals) when dewatering fine solids by a variety of makes and types of filters. Average particle size is calculated by averaging the linear openings of the various pairs of screens used in the screening test, weighted in accordance with the percentages of material in the various fractions.

Jan 1, 1952

By David B. Reger

The discovery of prolific oil wells in old territory hitherto regarded as doubtful, if not worthless, and the rapid extension of a gas pool opened late in 1938 were the most interesting petroleum features in West Virginia during 1939. Oil activity in general was slow because of crude prices that were still fairly low at the end of the year, although substantially increased above those in January. Fewer oil wells were completed, but the average results were better than in 1938. Fewer gas wells, also, were completed, with greatly lessened average initial production. Many old oil and gas wells were abandoned, so that the total number of active wells has not changed appreciably. The account of operations, as gathered from trade journals and other sources, shows that 561 new wells were drilled, resulting in 101 new oil wells with 2261 bbl. of daily initial production; 366 new gas wells with 602,400,000 cu. ft. of daily open flow; and 94 dry holes. Besides these new wells, 61 old wells were drilled to deeper sands, with 12 bbl. and 13,328,000 cn. ft. of added production. On the new wells the oil average was 22.38 bbl. per well per day; and the gas average was 1,645,900 cu. ft. per well per day; the ratio of dry holes to completions was 16.76 per cent. From an exploratory standpoint one partly discredited oil area was revived by good new production, and another small oil pool may have been opened. Some of the results in gas exploration will require more drilling for true appraisal. It is certain, though, that one very considerable gas field in the sands of Mississippian age has been proved; and there is a probability of six new pools in the Middle Devonian shale. In the Oriskany sand (L. Dev.) the Elk-Poca pool has been extended considerably farther northwest into Jackson County; and farther north in Jackson County two widely separated wells, which may be pool openers, have been successfully completed. On the other hand, several important wildcats in various counties have been dry. Stratigraphically lower, some additional wells have been completed in the Newburg sand (Sil.) and one small producer has been completed in the Clinton sand (Sil.), the importance of which can scarcely be overestimated, because no Clinton production has previously been found in the state, although at least seven wells have been drilled through the sand.

Jan 1, 1940