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By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P'. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett' proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman' found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy' suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By A. C. England, William F. Haney, Paul B. Crawford, Bobby L. Landrum

The creation of unsymmetrical vertical or horizontal fractures in a producing well will result in a unique distortion of the normal shut-in pressures existing at the four surrounding wells. An electrical model study has been made to show how the shut-in pressures at the wells surrounding the fractured producing well may he used to estimate the size and orientation of vertical or horizontal fractures. The pressure differences at the four surrounding wells are recorded during production from the fractured well. The resulting pressure dato are matched from a table of several hundred possible fracture combinations. The table refers to the figure showing the effective size and orientation of the commercially created fracture. INTRODUCTION The creation of commercial fractures about oil and gas wells has led to considerable speculation as to the size and shape of the fractures. It is important that the size and shape be known in certain instances, especially when pressure maintenance programs are to be initiated. It was shown that if knowledge of a vertical fracture could be found that such information may be utilized in planning a waterflooding or gas cycling program and that in some cases the fractures might be utilized very effectively.' Other work showed that it may be desirable to create "pancake" fractures in certain reservoirs but that they should exist in a desirable range.' If the fractures are too large, they should be plugged prior to initiating a pressure maintenance program. If an irregular shaped "pancake" fracture is created, it is desirable to know the orientation of this fracture because similar but unreported studies have shown that "pancake" fractures may or may not substantially affect the sweep efficiencies and performance of the flooding or cycling program. Consequently, it may be desirable in some instances to estimate the effective size and orientation of the fracture. ANALOG An electrical model was used in making this study. The electrical model consisted of a circular reservoir approximately 8 in. in diameter, 1 in. thick and was filled with a dilute salt solution. A copper band formed the periphery of the reservoir. A vertical fracture was simulated by a copper strip soldered to the wire well located in the center of the reservoir. Vertical copper strips of various lengths and orientation were soldered to the wire well to represent vertical fractures in the reservoir. In studies reported here on vertical fractures it was arbitrarily assumed that two fractures originated at the well and extended out into the reservoir. An electrical potential was imposed between the wire well and the periphery of the tank. Plots of the iso-potentials are shown in Figs. 1 through 9. This model provides the steady-state isopotentials existing in a uniform, homogeneous circular reservoir having a vertically fractured well at its center. The permeability of the fracture is much greater than the permeability of the matrix proper. The effects of gravity are neglected. In preparing Tables 1 and 2, four symmetrically located unfractured wells were assumed to exist around

Jan 1, 1956

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By Everett H. Graff, Ray H. Misener

THE Sol de Oro mine is in the province of Nazca, 487 km. southeast of Lima, and 60 km. inland from the coast at an elevation of 1200 m. above sea level. From Lima the mine may be reached in 8 hr. by automobile; 472 km. from Lima to Nazca over the paved Pan-American Highway and 15 km. from Nazca to the mine over a good graveled road. The trip from Lima can also be made in 2 hr. via the Faucett Air Lines which make two stops weekly at Nazca. The [Compania] Aurifera Nazca, owning and operating the Sol de Oro mine, was organized in Lima in 1930 by a group of prominent Peruvian mining men, including Ing. Carlos Alvarez Calderon, Dr. Alfredo Alvarez Calderón, Ing. Hector Boza, Ing. Jorge Félix Remy, Ing. Eulogio Femandini, Sr. Fernando Wiese, and Sr. Julio East. The nine claims in the Sol de Oro group owned by the company comprise an area of 52 square kilometers. Development of the property was not started until 1932 and only then under adverse conditions, owing to lack of transportation facilities. Mining machinery and other supplies could be taken as far as Ica by boat and railroad, but to transport them over the 180 km. of hot, sandy desert from Ica to the mine was a problem. There was no road in those days and only a few of the most venturesome truck drivers cared to contract the hauling. Another problem the company had to face was that of securing adequate labor. The Sol de Oro is in an agricultural region, and was forced to look to the near-by cotton plantations for men. Experienced men were imported from the "sierras," but they did not stay. The men are accustomed to high altitudes and cold climate and cannot easily acclimate themselves to the hot and arid coastal region. As a consequence the company has been forced to hire the inexperienced local laborers and train them for mining. The company has established three separate camps at the Sol de Oro property. Each is approximately one kilometer from the other and connected by auto road. The upper mine camp consists of living quarters for 300 workmen and their families, a general mine office, carpenter shop and timber-framing shed, compressor house, drill-sharpening and drill-repair shop, first-aid station, time office, school and store. At the central or "empleados" camp there is a 200-ton cyanide plant, general offices, warehouse, powerhouse, shops, laboratory, hospital, school, guest house, an 18-room hotel for the single staffmen, and 12 completely modern five-room cottages for the married staff employees. At the lower camp are living quarters for 200 workmen and their families, two general stores, a school and a small theater. Below this camp, along the river, are the company wells and pumping plant supplying water for mine, mill, and camp uses.

Jan 1, 1945

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By W. D. Steele, S. D. Brady

The Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains minable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon-galia Co. thence south and southwest across the state to Wayne Co. near Hunt-ington. The Pittsburgh coal is also minable in the Upper Potomac region but is now practically exhausted there. The total minable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13¼ billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio River as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern West Virginia District comprising Wetzel, Mon-ongalia, Marion, Preston, Harrison, Dodd-ridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 1880 (when the Monongahela River Railroad, now B. & 0. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgan-town and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Mononga-hela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of minable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. Economic Importance The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1949

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1&apos;2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult&apos;s law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors&apos; data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a&apos; solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a&apos; phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors&apos; contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors&apos; enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By G. R. Rubly, H. J. Steele

LOCATION AND HISTORY THE San Manuel property is in townships 8S and 9S, range 16E, Gila and Salt River Base and Meridan, State of Arizona. This area is in the Old Hat mining district, southern Pinal County, and is about 3;2 miles southwest of the town of Mammoth on the San Pedro River and one mile south of the Mammoth mine at Tiger, Arizona. The property consists of over 150 contiguous lode claims. The Old Hat district was prospected prior to the Civil War, but there was little or no production until 1881.1 The chief producers have been the Mammoth and Mohawk mines, now consolidated and operating as the St. Anthony Mining and Development Co., Ltd. Production to 1936 was $5,200,000, of which 83 pet was gold.2 Since 1940 the production has been chiefly lead and zinc, and some molybdenum and vanadium. There are a few small properties in the vicinity that have produced very minor tonnages of copper ore. In the San Manuel group there are claims which have been held continuously from 1906 to the present time, and at least two churn-drill holes were put down on or near the outcrop in 1917. No logs for these holes are available, but it is assumed that the grade of copper encountered was not sufficient to encourage further exploration. A small amount of ore has been shipped from open cuts on the San Manuel outcrop area, but there is no record of the tonnage or grade. It is estimated that not more than 5o tons were mined. These cuts, plus a few shallow shafts and some short adits indicate limited and unenthusiastic prospecting at San Manuel. In 1942, through the efforts of James M. Douglas, R. B. Giffin, Victor Erickson, and Henry W. Nichols, owners of the San Manuel group, the Reconstruction Finance Corporation and War Production Board authorized the United States Geological Survey to investigate the property, and by their recommendation, the United States Bureau of Mines was authorized to put down a limited number of churn-drill holes. The Bureau of Mines carried on drilling from November 1943 to February 1945. Seventeen holes were drilled, varying from 305 to 1990 ft in depth. The property was brought to the attention of Magma Copper Co. in June I944 and an option agreement was made with the owners. Subsequently, a group of claims lying north of the original group and held by the Apex Lead Vanadium Mining Corp., and a group to the east held by the Quarelli family, were optioned. A drilling program was laid out to conform to the Bureau of Mines pattern, and drilling started in December 1944. San Manuel Copper Corp. was incorporated September 1945, and has carried on the exploration program to the present time. GEOLOGY General The mineralized outcrop, chief copper mineral of which is chrysocolla, is a tri-

Jan 1, 1947

By Ferit Gurses

Extensive coal and lignite deposits exist in Turkey. Bituminous coal is the nation&apos;s principal mineral resource; important not only as fuel for the industrial development of the country, but also as a means of obtaining foreign exchange. Of the electrical power generated during 1939, 82.8 per cent was derived from coal.&apos; It is anticipated that the lignite deposits will be one of the major sources of power for the electrification of the country. Bituminous Coal The locations of the four principal bituminous-coal2 basins are indicated on Fig. 1. The Eregli-Zonguldak basin lies on the Black Sea northwest of Ankara; the Canakkale basin lies near the junction of the Dardannelles; the Trakya basin is in European Turkey northwest of the Bosphorus and the Erzurum basin lies far to the east. The Eregli-Zonguldak basin is the most important of the four. This coal basin was discovered in 1829 but did not arouse interest until 1848; up to 1865, its annual production had not exceeded 50,000 metric tons. In 1865, during the Sultanate, working of coal mines was started by the Navy department, and the annual production was 61,145 metric tons. In 1908, the Minister of Commerce and Agriculture was authorized to develop the whole coal basin. Production reached 264,397 metric tons in 1910, and during 1915-1922, preceding the revolution, the total produc- tion of the basin was&apos; 2,676,043, or an average of 334,000 metric tons annually. The period of national revolution that followed was marked by a steady increase in coal production in Turkey, although world production decreased, because of the crisis of 1929-1932, about 52 per cent. ARea and Geology of the Coal Basin The geology of the Eregli-Zonguldak area is not yet completely known. The basin begins -at Gungazi, to the west of Eregli, and extends to Sogutozu, a distance of about 106 miles. The coal beds, however, appear only in places and the overlying Cretaceous strata hide them elsewhere. This area includes the most important centers, such as Kandilli, Alacaagzi, Teflenli, Kozlu, Gelik (see Fig. 2). The geological sequence of the district is correlated with the Cretaceous of the Balkans; which is, in turn, a prolongation of the Alpine zone. Geological surveys made by G. Ralli, R. Zeiller and P. Arni3 show that the Eregli-Zonguldak formations fall into three natural divisions. Series a, The Alacaagzi in the district of that name (Fig. 2), is of the Culm stage. The strata strike generally east-west and dip about 30" south. This series appears also around Kandilli and Camli, with a steeper angle of dip, but the deposits there lack regularity. The Alacaagzi stage appears also farther east, to the south of Kozlu and Gelik. The Alacaagzi series contains 15 seams of an average thickness of 2 ft. of good coal. Series b, the Kozlu, best represented in Zonguldak, Kilimli, Catalagzi, and between

Jan 1, 1944

By W. D. Steele, S. D. Brady

THE Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains mineable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon¬galia Co. thence south and southwest across the state to Wayne Co. near Huntington. The Pittsburgh coal is also mineable in the Upper Potomac region but is now practically exhausted there. The total mineable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13% billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio river as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern. West Virginia District comprising Wetzel, Monongalia, Marion, Preston, Harrison, Doddridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 188o (when the Monongahela River Railroad, now B. & O. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgantown and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Monongahela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of mineable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. ECONOMIC IMPORTANCE The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1948

By John W. Crutchfield, Emil F. Bowers

This paper presents the initial results of a pressure maintenance by water return project in the Lower Pawelek reservoir of the Falls City Field, Karnes County, Southwest Texas. Production is from the Lower Wilcox section at an average depth of 6,030 ft on the downthrown side of a "down to the coast" fault. Of particular interest is that the reservoir oil is high gravity and low viscosity but far undersaturated with gas at the original reservoir pressure and temperature. The early pressure and production history indicated only a partial or limited water drive, and this fact, coupled with the characteristics of the reservoir fluid and artificial lifting problem.. made advisable the water injection program to maintain reservoir pressure. The paper includes a description of the reservoir and reservoir fluids, the pressure and production history, a description of the water injection facilities, and the results of reservoir calculations involving Hurst&apos;s unsteady state flow and the material balance equations for calculation of water influx and prediction of the pressure-production relationship at various rates of withdrawal. The reservoir calculations and initial field results indicate that reservoir pressures in excess of 85 per cent of original pressure can be maintained by control of water injection even at very high rates of production. INTRODUCTION The purpose of this paper is to report the initial results of a pressure maintenance by water return program in the Lower Pawelek reservoir, Falls City Field, Karnes County. Texas, and to calculate an empirical relationship between pressure and production in this limited or partial water drive reservoir. Location The Falls City Field (Fig. 1) is located two miles north of the town of Falls City in Karnes County, Texas, and is approximately 50 miles south-southeast of San Antonio on U. S. Highway 181. Discovery and Development The initial block of leases was taken after a surface geological survey identified a major east-west fault and closure on the south or downthrown section. The discovery well, Southern Minerals Corporation&apos;s Joe F. Bartosch 1; was completed at 4,650 ft in the Lower Bartosch sand in December, 1944. Drilling was continuous until December, 1946, and resulted in the discovery of 12 oil reservoirs between 4,600 and 6,050 ft in the Middle and Lower Wilcox formations. These are shown on the cross-section (Fig. 2). As of the current date there are 64 oil wells completed as follows: Southern Gulfshore Magnolia Minerals Oil Petroleum Reservoir Corp. Co. Corp. Total Upper Bartosch 0 0 0 0 Lower Bartosch 16 0 0 16 Shulze 7 0 1 8 Upper Faires 2 0 0 2 Lower Faires 4 0 0 4 Upper Moczygemba 0 0 0 0 Lower Moczygemha 2 0 0 2 Olinick 2 0 0 2 Upper Martinez 0 0 0 0 Lower Martinez 5 0 0 5 Upper Pawelek 0 0 1 Lower Pawelek 27 1 3 31 Total 65 2 4 71

Jan 1, 1950