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By Robert L. Hoss

The application of Muskat's differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948

By G. E. Pellissier, C. W. Mason

Tin has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphul.. The notorious "tin disease," which Cohenl has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white P tin to cubic gray a tin, has apparently encouraged the expectation that one or more additional polymorphic modifications might exist. The search for confirnmntion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but fur previous assumptions. The ball apparently was started rolling iii 1880 by Trechmann,2 who reported a new modification of tin (7 tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be 7 tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller. Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,~ by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) ant1 stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencers in 1921 examined the above evidence critically; lie lound similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on :L second lot of crystals, not described crystallographically.)

Jan 1, 1939

By G. E. Pellissier, C. W. Mason

Tin has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphul.. The notorious "tin disease," which Cohenl has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white P tin to cubic gray a tin, has apparently encouraged the expectation that one or more additional polymorphic modifications might exist. The search for confirnmntion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but fur previous assumptions. The ball apparently was started rolling iii 1880 by Trechmann,2 who reported a new modification of tin (7 tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be 7 tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller. Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,~ by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) ant1 stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencers in 1921 examined the above evidence critically; lie lound similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on :L second lot of crystals, not described crystallographically.)

Jan 1, 1939

By Charles W. Merrill

Obsolescence in the mineral world is virtually nonexistent if the term is taken to mean that a mineral commodity, once established in commerce and industry, subsequently has fallen into disuse. We are living in an age of minerals. Each generation puts an increasing array of mineral-based commodities, in larger quantities, to more uses than ever before. Bastnasite, a museum mineral and a collector's item a few years ago, is now produced in quantity at Mountain Pass, Calif. Uranium, a minor byproduct of vanadium mining in the Rocky Mountain plateau area before World War 11, has grown to be a leading mineral product in several western States. And finally the total quantity and value of minerals both in the United States and in the World establish new records almost yearly. Surely the mineral industry as a whole is not obsolescent in our economy. Nevertheless, there are particular uses for particular minerals that are obsolescent and some applications have been supplanted entirely. Tin does not occupy the prominent place in foil manufacture that it once did, and the schoolboy's slate left most classrooms before the oldest of us were born.

Jan 9, 1964

By J. B. Fletcher

The Miami mine first started operations in 1910. For convenience, the history of the orebody can be divided into the following categories (Fig. 1): 1) 1910 to 1925: 24.4 million tons of high grade ore, mined by top slicing, sublevel caving, etc. 2) 1926 to 1954: 102 million tons of low grade ore, mined by block caving.

Jan 1, 1961

By Arnulf Muan, Egil Aukrust

Activities of COO in the three solid solution series COO-MgO, COO-MnO, and COO-"FeO" have been determined at 1200°C by equilibrating oxide samples with a metal phase (cobalt or a Co-Fe alloy) in atmospheres of known oxygen activities. The systems COO-MgO and COO-MnO are ideal, within limits of experimental error, whereas the system COO-"FeO" shows a slight positive deviation from ideality at the temperature of this investigation. KNOWLEDGE of activities of oxide components in solid solutions is necessary for the calculation of the cation distribution among coexisting oxide phases in many important metallurgical, ceramic, and geochemical systems. Very few activity-composition curves are available for such systems at the present time. A start on the prodigious job of obtaining such data has been made by studies of solid solutions with simple sodium chloride type structure containing NiO or "FeO" as a component.1-3 The present paper describes similar studies for solid solutions with sodium chloride type structure containing COO as a component. For the systems COO-MgO and COO-MnO, the activity solid solution is determined by the equation Here po and are the oxygen activities of the gas phase in equilibrium with the phase assemblages metallic cobalt plus oxide solid solution, and metallic cobalt plus pure COO, respectively. In the system CoO-"Fe07', the metal phase is a Co-Fe alloy rather than pure cobalt. In this case the activity of COO in the oxide solid solution is calculated from the equation where a& is the activity of cobalt in the metal phase. Because the system Co-Fe is close to ideal4 and the metal phase appearing in the present work contains less iron than cobalt even at the lowest COO concentrations of the oxide phases used may be set equal to N . Hence, Eq. [2] becomes The value of Nc, can be estimated from the relative stabilities of the oxides COO (see below) and I) EXPERIMENTAL METHOD Two different but closely related procedures were used in the present investigation to determine the activity-composition curves. In one method, the oxide solid solutions were equilibrated against

Jan 1, 1963

By J. W. MacDonald

Review of equipment, performance, and shaft design plans including head-frames for sinking and forms for lining are given. Also included are comparative data for shafts of 11 x20 ft and 193/4 x 30 ft with 756 and 666-ft depths, respectively. Advantage from curtain wall installation with "slip forms" which warrant consideration for normal lining are outlined. A preliminary review is also made of "chemical grouting" to stop water inflow leakage with Halliburton equipment and service. Two coal mine shafts recently completed in Franklin County, Ill., afford experience and accomplishment to warrant review. These shafts provide access to a tract with a potential recovery of one hundred million tons. This work provided the initial sinking by other than a contractor's organization since 1918. Four additional shafts required during the interim were sunk under contract arrangement with others. Supervisory contact and inspection afforded experience to govern planning and conduct of the recent work. TEST DRILLING Core test holes were drilled within each of the two shaft locations. Four additional cable tool holes were drilled on a radius of 700 ft from the shaft bottom to determine the coal seam elevations and govern the underground layout plans for each shaft. A graphic log of the hoist shaft test drillhole is shown by Fig. 1. A very soft sandstone was found at a depth of 16 ft. Cored recovery of the sandstone proved much weaker than the overlying compacted sand secured with coring facilities for soil recovery. Gradation from the very soft sandstone to fairly hard material occurred with the next 14 ft, extending to a depth of 30 ft. The weak character within the upper portion entailed need of adequate protection when sinking as described later. A part of the sandstone provided sufficient porosity and permeability to warrant further investigation. Adjacent cable tool drilling for temporary water supply disclosed inflow was limited to 2 gpm with a depth of 40 ft. It was increased to 12 gpm during the next 50 ft of drilling and occasioned subsequent precaution when sinking. General arrangement of facilities for sinking the hoist shaft is shown by Fig. 2. An available steel frame building was used to accommodate the hoist, compressor, shop, and shower or change room. The stiff leg derrick with 90-ft length of boom permitted removal of forms from the wood shop to the storage area or delivery within the shaft. Reinforcing steel and other needs were similarly handled, in addition to headframe erection. The headframe was placed over one end of the shaft to enable passage of forms for lining through the adjacent half next to the stiff leg derrick. The steel headframe as shown by Fig. 3 was fabricated locally. Side anchored cables from the

Jan 1, 1961

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Battelle.-Green, G. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Bonnyman, J. Bowron, J. Bush, M. W. Crawford, G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geismer, H. S.

Jan 1, 1917

[NORTH AMERICA UNITED STATES ALABAMA Bessemer Coston, Otis D., Jr. Birmingham Cord, Richard M. Dismukes, Edward B. Pagel, Herbert E. Citronelle Mason, Seeber William Mize, Frank W. Perrin, Huey P. Fairhope Ruffles, William R., Ill Huntsville Waggoner, J. B. Mobile Hankins, James D. Petroutson, Peter C. Montgomery Crenwelge, Joe Ed Tuscaloosa Mason, William L. University Jones, Walter B. *Ricnards, Edward F.]

Jan 1, 1961

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

[Pumps: oil-well: plunger: essential parts, G26, 130; 74, 828 improved type, 74, 846 leakage, 74, 837 operating cycle, 74, 833 Uren design, G26, 145 sucker-rod failures, G26, 136 sucker-rod stress, 74, 835 sucker rods, 74, 830, 832 tubing, 74, 833 tubing difficulties, G25, 138; 74, 836 Olivite, 73, 337 valve and seats, 74, 832 Punching: Monel metal, 78, 86 nickel, 78, 86 Punjab. See Indian Empire. PUPIN, M. L biography, M26, 113 John Fritz medalist, 1931, M81, 499 recipient of Washington Award, M28, 155 PURDY, R.: Discussions: on Relative Efficiencies of Domestic Fuels in Relation to Their Costs and Their Advantages 108, 353 on Uses on Coal in the Ceramic Industry, 108,389,398]

Jan 1, 1936

By John B. Knaebel, Robert J. Grant

This paper outlines the trends in gold production since the discovery of America, in the world as a whole, and in the principal producing regions as well. World production climbed at an average rate of about 20,000,000 oz. per 5-year period until the record all-time output of 111,307,000 oz. in the period ending with 1915. Production fell off during the war period, but has been mounting since 1925, and will probably be nearly 100,000,000 oz. for the 5-year period ending in 1930. Total world production of gold from 1492 to the end of 1930, as closely as can be determined, is more than 1,061,000,000 fine ounces. More than one-half of this total, or about 575,000,000 oz., has been mined since 1900. In percentage of world production, the United States jumped from 4.8 per cent for the decade 1831-1840 to 44.5 per cent for the five years ending with 1855. This is the highest figure ever reached by this country, although, with the exception of the 10-year period ending 1865, it ranked first among the nationa from 1849 until the end of 1905. During the 5-year period ending with that year, the United States produced 24.7 per cent of the world's gold. The tremendous increase from South Africa following 1890 resulted in that country's becoming the largest contributor for the five years 1906-1910, a position it has held with increasing dominance ever since. Relegated to second place in the period 1906 to 1910, the United States produced nearly 20 per cent of the world's new gold until 1920. From 1921 to 1925 it averaged 13.6 per cent and since then it has continued to decline in relative importance, accounting for only 10.9 per cent in 1927. Final figures for 1930 may place Canada second among the gold producers of the world.

Jan 1, 1931

By W. A. Burns

Vertical flow is an important mechanism in many petroleum reservoirs. Yet no adequate method has heretofore been proposed for determining the in-situ vertical permeability in a reasonable length of time. Core measurements of vertical permeability do not necessarily represent effective in-situ values. Cores may be representative of only localized pockets of high or low permeability, and total reliance on cores might cause one to overlook the presence of vertical fractures altogether. Conventional single-well tests, interference tests, and pulse tests commonly are used to determine horizontal transmissibility, khh/u, but generally are not designed to measure vertical trans-missibility or other groups containing vertical permeability, ku. A new well test described here provides a measure of in-situ vertical permeability as well as the previously measurable horizontal permeability. This "vertical test" determines the vertical diffusivity, kv/gcu, and horizontal transmissibility, khd1/u (where dl is the length of injection or production perforations). The test is basically a short-term interference or pulse test normally lasting less than a day. Conventional down-hole equipment is used between two isolated sets of perforations in the same well, as shown in Fig. 1. A "layer-cake" description of a reservoir can be obtained by running two or more vertical tests in the same well, each over different vertical intervals. Each test can be analyzed for the effective vertical and horizontal properties of the interval tested. In addition, a vertical well test can determine the effective- ness of a shale barrier or tight zone by testing across it. Field use to date of vertical testing has confirmed its utility in reservoir description. Mathematical Basis Interpretation of vertical tests for ku and kh is based on comparison of measured pressure response with computer-generated response. Pressure behavior during a vertical test in a homogeneous, anisotropic, infinite-acting reservoir (infinite in radial extent and bounded in both directions vertically) is given by the diffusion equation for slightly compressible fluids with negligible gravity effects.l A schematic diagram of the problem is presented in Fig. 2, and an analytic solution, based on the image

Jan 1, 1970

By A. J. Terrones

THE classical papers on contact metasomatic deposits by Lindgren on the Clifton-Morenci district,' by Barrell on Marysville, Mont.,' and by Gold-schmitt on the Oslo district, Norway,' laid the foundation for understanding of the importance of separating the metamorphic process from the subsequent metasomatic stage. Knopf' made a big step forward by recognizing that sulfide ore minerals are invariably younger than silicates and by further stressing the importance of structural control" in ore finding. Some years later Harrison Schmitt" fought the idea that contact metasomatic deposits are erratic, irregular, bunchy, economically marginal, and of small size, concluding that these descriptions have little factual basis. He emphasized the importance of detail mapping and careful geological study as fundamental requirements for a better understanding of these deposits. This article presents a comparative description of the structural features at the Magistral, Antamina, Morococha, Vilca, Ferrobamba, Katanga (Quibio), Tintaya, and Huarca contact deposits (Fig. 1). Further, it will describe how these structural features controlled the emplacement of the intrusives, their shape, distribution of metamorphic and metasomatic halos, and sulfide deposition in post-skarn structural channelways. Finally, the modifications introduced by a superimposed hydrothermal stage recognized at some localities will be discussed. Primary exploration and careful sampling of recognized structural targets were instrumental in outlining the copper ore potential at the Antamina and Tintaya districts, thus proving the benefits and reward of careful geological examinations in this type of deposit. The Magistral District: This district lies in the Province of Pallasca, Department of Ancash, in northern Peru, at 8o 16' S and 77" 47' W. High to medium grade copper orebodies in garnetite, bordering a quartz monzonite stock, are exposed at the bottom of a glaciated valley in the western slope of the Andes at 4250 m (14,000 ft)* elevation.

Jan 1, 1959

E. O?C. Acker Jinzoc Adachi Truman H. Aldrich Walter H. Aldridge Anson W. Allen John H. Allen William R. Appleby W. Lawrence Austin W. S. Ayres David Baker John Henry Banks Henry C. Banon Alonzo F. Bardwell Wm de L. Benedict Robert Bentley Andrew A Blair Walter M. Brodie Elwin F. Brown Fredrick Burbidge H.H. Burden Charles Butters

Jan 1, 1941

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By H. DeWitt Smith, W. H. Sirdevan

The mine operated by the United Verde Copper Co. is situated near Jerome, Ariz., on the eastern flank of the Black Hills, at an elevation of approximately 5500 ft. (1676 m.) above sea level. The mine and the town of Jerome are located on a steep hillside, which slopes rapidly to the valley of the Verde River. The smelter town of Clarkdale is situated in the Verde valley 4.1 mi. (6.5 km.) distant in an air line from Jerome, and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel & Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 mi. long and has a compensated 4 per cent. grade. At Clarkdale, it connects with the Verde Valley branch of the Santa Fe R. R. The narrow-gage (36-in.) line of the United Verde & Pacific Ry. was, until 1919, Jerome's only rail connection with a main trunk line. This road connects with a branch line of the Santa Fe system at Jerome Junction, after traversing 26 mi. of mountainous country. From the time of its location, in 1876, until its purchase by Senator W. A. Clark, of Montana, in 1889, the United Verde mine was worked on a small scale and shipments of high-grade gold-silver ore were made from the surface workings. Until 1894, when the narrow-gage railroad to Jerome Junction was completed, all supplies for the mine and smelter

Jan 1, 1922

By M. G., Corson

1. In addition to the alloys of copper with iron previously found by Hanson and Ford to show an increase in the concentration of the alpha range with increase in temperature the following binary and ternary systems have been found by the author to exhibit: the same feature: (a) Copper-chromium. (b) Copper-cobalt. (c) Copper-silicon. (d) Copper-nickel-silicon and its pseudo-binary section Cu-Ni2Si (formula of compound definitely established). (e) Copper-cobalt-silicon and its pseudo-binary section Cu-Co2Si (formula of compound established with some probability but not as definitely as for Ni2Si). (f) Copper-chromium-silicon; formation of a compound definitely established (compare Figs. 1 and 2). The formula of this compound may be either Cr2Si or Cr3Si. (g) Copper-iron-silicon; presence of a phase containing both iron and silicon established in an indirect way only. No definite microconstituents observed. 2. RANGES OF SOLID SOLUBILITY (percentage at various tempera¬tures). (a) For copper-chromium: 0.8 at 1000° C.; 0.5 at 900° C.; 0.25 at 800° C.; 0.05 to 0.1 at 500° C. (b) For copper-cobalt: 3.4 at 1000'C.; 2.4 at 900'C.; 1.7 at 800'C.; 0.9 at 600°C.; 0.35 at room temperature. (c) For copper-silicon (Fig. 3) : 6.8 ± 0.1. per cent. at 800° C.; 3 per cent. at 400° C. and probably below 2 per cent. at room temperature if sufficiently long annealed. (d) For copper-cobalt silicide: 3.3 at 1000° C.; 2.4 at 900° C.; 1.6 at 800° C.; 0.7 at 600° C.; 0.3 at 300° C. (e) For copper-nickel silicide (Fig. 4): 8.2 at 1000° C.; 5.5 at 900° C.; 3.6 at 800° C.; 1.6 at 600° C.; 0.7 at 300° C.

Jan 1, 1927

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors' value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors' excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors' interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic'" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.'"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot's23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors' reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952