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By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By Strathmore R. B. Cooke

On the basis of experiments con- ducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a ceutral tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for re- agent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and

Jan 1, 1949

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By John C. McDonald

CONTROLLED cold work is used between solution heat treatment and precipitation heat treatment for producing certain tempers of the commercial aluminum base alloy 2219 (designation of the Aluminum Association, U.S.A.) which contains 6.3 pet Cu as the major ingredient responsible for the age hardening. The complete composition limits for this alloy are listed in Table I. The alloy has been described in detail,' and the control of the heat treatment has also been published.2 Beneficial effects of such cold work in other alloys have also been pointed out.3'4 NO data have been published on the effects of varying amounts of cold work under fixed aging conditions. In connection with an investigation of the possibility of providing the desired cold work by explosively generated shock waves, it became desirable to investigate the effect of variable cold work, and to compare the re -sults with those obtained from explosives. The general principles of explosive hardening are well-described in the literature.' All material used was guaranteed by the supplier

Jan 1, 1968

By Rollyn P. Jacobson

The town of Pacific, in Jefferson County, Mo., is 27 miles west of St. Louis. Since the area lies entirely on the flood plain of a cut-off meander of the Meramac River, it was considered a likely environment for accumulation of commercial quantities of sand and gravel. Excellent transportation facilities are afforded by two major railways to St. Louis, and ample water supply for washing and separation is assured by the proximity of the river. As a large washing and separation plant was planned, the property was evaluated in detail to justify the high initial expenditure. An intensive testing program using both geophysical and drilling methods was designed and carried out. The prospect was surveyed topographically and a 200-ft grid staked on which electrical resistivity depth profiles were observed at 130 points. The Wenner 4-electrode configuration and earth resistivity apparatus* were used. In all but a few cases, the electrode spacing, A, was increased in increments of 1% ft to a spread of 30 ft and in increments of 3 ft thereafter.

Jan 2, 1955

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By Rudolph G. Wuerker

MUCH descriptive matter has appeared on the subject of suspension roof supports, or roof bolting, as it is more commonly called. The widespread introduction of roof bolting into coal mines and metal mines is truly phenomenal. Mine operators were quick to recognize the advantages of supporting wide openings without hindrance to machine maneuverability and ventilation. Although suspension roof support has long been installed at St. Joseph Lead Co. mines in southeast Missouri,'" its application to coal mining presented new problems, such as proper anchorage and bearing for the bolts, bolt diameter, and spacing of bolts. After continuous testing and experimenting at the mines, standard roof-bolting materials were determined.'!' The study reported in this paper is not concerned with such details as bolt diameter, which may be considered already solved in practice. In the tests discussed here, small models patterned on actual bolts were found to function in the same way and as satisfactorily as their prototypes. The aim of these tests was rather to investigate the influence of roof-bolting systems on the stress distribution around mine openings and to study the fracture patterns obtained in actual testing. Little was found about this in the literature, as testing of suspension roof methods and quantitative measurements are only now coming to the fore. Several suggestions and actual measurements have been made to evaluate critically the functioning of roof bolting systems, single roof bolts, and parts thereof. Outstanding among them is Bucky's outline of structural model tests.'" Since none of the suggested testing equipment was available, however, for the experiments discussed below, a different approach was chosen. The response of a mine roof under stress has often been compared to that of a beam. The slow coming down and bending through of beam or plate-like banks of shale, sandstone, or top coal is a familiar occurrence, extensively cited in the literature." It was felt that testing of roof-bolt systems installed in a concrete beam which was loaded in bending would be a fair approximation of the behavior of a mine roof underground. Another school of thought considers the roof behavior over an underground opening in connection with the stress distribution all around a circular or rectangular opening. This is more accurate, and leads to the concept of a dome-shaped zone of material destroyed under tensile stress. This is likewise a common sight in unsupported roadways where the continuous fall of roof results in what has been called the natural outline of roof fracture. This theory could not be tested and is treated separately in Appendix B. It is important to note that according to both assumptions the immediate roof fails in tension; the use of a beam in these tests, therefore, should give information valid for either of the two theories. With the testing equipment at hand it was possible to load concrete beams 6xlx0.5 ft under two-point loading, giving an equal bending moment over the center part in which the model bolts were installed. A comparison was made of the ultimate loads needed to break plain beams and beams in which roof bolts were installed. Arrangements were made with: 1—plain beams; 2—bolts with plate washers, some with holes drilled at 90" angles and others with holes drilled at 45" angles; 3—bolts with channel irons underneath; 4—bolts in holes filled afterward with cement; and 5—bolts anchored in a stronger stratum. The foregoing arrangement is made in order of increasing strength, as assumed from the theory of reinforced concrete. Likewise, laminated beams with wooden model bolts and with combinations of the foregoing set-ups were tested. All in all, 21 experiments were made out of the much greater number of combinations possible. There were, too, some trial tests. Enough observations from this limited number were made to interpret the behavior of mine roof, supported by various types of suspension bolts, at fracture. In present-day concepts, which have been proved by mathematical derivations and stress analyses, any opening driven underground will change the distribution and magnitude of the stresses existing around it. It does not matter whether the stresses become visible, as in rocks whose strength is less than the forces acting upon them, or whether they are invisible, as in the gangways lacking evidence of rock pressure. In this latter case the rocks can withstand changes in stress-distribution. To consider the mine roof as a beam, there are, with transversal loading, tensile stresses in the lower fiber and compressive stresses in the upper layers above the neutral axis of the beam. Beams of brittle material such as rock and concrete fail exactly as shown in Fig. 1. Nearly all model beams showed the same fracture pattern as that of a tension crack. The influence of support, by roof bolting or conventional

Jan 1, 1954

By Edward Steidle

TWO years ago the Committee on Latin American Education Relations, Mineral Industries Education Division, started a study of mineral industries education in the Latin Americas. Information was obtainable only with great difficulty. Some information was available piecemeal but no complete resume had ever been assembled. Initial assistance was gained from the United States Office of Education and the Pan American Union. This, and first-hand knowledge of the writer, provided a list of colleges and universities which were believed to offer work lead. ing to a degree in one or more branches of the mineral industries. Detailed information could be obtained only by direct contact with each university through air mail service. Questionnaire letters were sent to officials of 34 colleges and universities. Twenty-one gracious replies were received. Fourteen of the colleges and universities concerned offer curricula in mining, five in metallurgy, three in petroleum, seven in geology, one in geographical engineering, one in topographical engineering, and one in geophysics. Two institutions offer advanced training in petroleum engineering. No institution offers any courses under the caption of ceramics or fuel technology.

Jan 1, 1945

By NEWTON B. KNOX

THE war has forced the principal industrial nations of the' world into the strait jacket of a closely controlled economy; taxes have been heaped upon all enterprises in order to maintain the armed forces and to deprive the people of the ability to bid for goods now unavailable. These restrictions, controls, and taxes are unlikely to disappear entirely after the war has been won, for debts will remain to be paid with a long period of difficult readjustment. Although the new economy will doubtless offer plentiful opportunities for the advantageous use of capital, no investor can ignore the favorable conditions offered by industry in Latin America, where taxes are relatively low and the restrictions on free enterprise comparatively mild. In mining in South America, the great international corporations have

Jan 1, 1944

By P. R. Kalischer

IN the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more components that tend to form very stable oxides Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken If, however, it s required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible Since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets All of the pertinent properties of the magnets could be accurately and delicately measured by density measurements and magnetic tests of sufficient scope to give a complete demagnetization curve From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties NATURE AND REMOVAL OF SURFACE BARRIERS The early work of the present investigation was based upon published processes In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 per cent Fe, 50 per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200ºC or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics However, this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen Both the iron and nickel powders sintered

Jan 1, 1941

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By B. D. Saklatwalla

FOR the proper understanding of the inclusion of certain elements in this review it seems necessary to state the meaning of "rare metals." Certain elements occur in deposits limited in extent or concentration, so that the extraction of the element in relation to market conditions becomes uneconomical. Others may occur in extensive and rich deposits but the reduction of the metal may be difficult and costly. Both these conditions effect the same result, namely, make the metal rare and costly. As an example of the first kind may be mentioned radium and of the second, calcium.

Jan 1, 1939

Gentlemen.-It is pleasant to be able to report that the year just closed has been a prosperous and successful one for the Institute. As is shown by the reports of the Treasurer and the Finance Committee, the business affairs of this organization are in excellent condition. With property valued at more than three-quarters of a million dollars, and with considerable sums in various funds and endowments, it is possible to spend on each member of whatever class $22.65 each year, more than the maxi- mum amount of dues received from any one, and substantially twice the average amount, $10.94, received from all. To do this has required close management and a strict regard for our limitations. In 1926, when the Budget was made up, the estimated expenditures for the work which it was felt the Institute must do exceeded the estimated receipts by some $14,000. At the close of the year, despite a number of unexpected decreases in receipts, it had proved possible to accomplish substantially all the work laid out and close the books with the usual transfer of initiation fees to the General Reserve, and still only reduce the cash balance $2,074.54. This was made possible by the hearty and loyal cooperation of the whole staff of employees and the extremely large amount of gratuitous service rendered by the officers, the members of the Divisions and technical Committees, and the membership generally. Even so it was impossible, because of limitations of funds, to undertake many things it is highly desirable for the Institute to do, and it was necessary to refuse the publication of important papers and committee studies, because of the lack of funds. PUBLICATIONS In an analysis of the income and expenses of the Institute published in the February issue of our Journal, MINING AND METALLURGY, it was pointed out that the largest item of expenditure is, as it should -be, for publications. Printing, binding, and distributing the various technical papers sent to the members cost in 1926 more than all the money received from dues, including the portion allocated as subscription to the magazine. Within the. year, the following volumes were printed and, with the exception of the second volume of TRANSACTIONS, which was mailed in January, were distributed : TRANSACTIONS, Volume 73, 1241 pages, covering papers on non-ferrous metallurgy, milling and concentration, non-metallic minerals, iron and steel, and the Institute of Metals Division papers read at the

Jan 1, 1928

By Blandford C. Burgess

Mica is an orchid among minerals. It is formed in pegmatites, one of the most bizarre of igneous formations, and is exceeded by few other minerals in the perfection it may attain as to size, color, and cleavage. First used for window glazing, as an ornament and article of trade, it has become one of the most essential insulators of electricity, heat, and shock. Most internal combustion engines use mica condensers or capacitors and such machines of war as planes, tanks, and submarines are immobile without it. The original manuscript of this guide was written in April 1943 at the peak of war emergency. It was not used be- cause shortly thereafter a decision was made to buy on a one price basis eliminating differentials for both quality and size. This is now presented with the thought that from the standpoint of preparedness we can only consider an- other war imminent and every effort should he made to set up in usable form the experience gained during the Second World War. Colonial Mica Corp. was set up by Metals Reserve Co. as a wholly owned government agency to encourage production of domestic mica and to purchase it. It soon became the exclusive buying agency for such mica. The writer as Southern Manager called on all the private agencies buying mica to assist in formulating buying policies, methods, and prices.

Jan 1, 1949

By T. A. Read, H. K. Birnbaum

Deformation of AuCd alloys having the 8 (orthorhombic) and (3" (tetragonal) structures occurs by the stress induced motion of twin boutdaries. A restoring force acts on displaced twin boutdaries as a result of internal energy increases in the volume through which the boundaries are displaced. The phenomonology of the twin boundary motion is described and a mechanism for twin boundary motion and the restoring force is proposed. A time-dependent stabilization behavior of the twin boundaries, which is observed after the twins are formed by the diffusionless phase transformations, is described. THE AuCd 8 phase (ordered bcc structure) exhibits a transformation to a phase having an orthorhombic structure, 8' (space group D'), for compositions in the vicinity of 47.5 at. pct Cd and to a phase having a tetragonal structure, 8" (point group 4/m, m,m), for compositions in the vicinity 50.0 at. pct Cd. Both transformations are diffusionless, occur on cooling at 60" and 30OC, respectively, and are crystallo-graphically reversible.' They are accompanied by an inhomogeneous deformation which was observed to be twinning in the low-temperature phase. 3'4 The transformations may occur by a "single interface" or by "multiple interfaces."5'6 In the "single interface" transformation, the twinned product phase consisted of two twin orientations as shown in Fig. 1. In the multiple interface transformation the product phase contained "domains" each of which contained two twin orientations, Fig. 2. Deformation of specimens containing transformation twins was achieved by motion of the twin boundaries. Releasing the applied stress resulted in the displaced twin boundaries returning towards their initial positions. This "pseudo-elastic" behavior of the boundaries varied with time after the formation of the twin boundaries by the transformation.

Jan 1, 1961

By Thomas L. Kesler

Essentially all of the barite produced in Georgia has come from the Cartersville district in the northwest part of the state. The earliest recorded shipment of ore, 60 tons, was made in 1894.1 With the exception of the four-year period 1931 to 1934, the separate yearly output has been recorded and published since 1915, whereas the total yearly output of the United States has been published since 1880. The separately recorded production of Georgia (Cartersville) through 1947 is 2,232,544 short tons valued at $14,900,746,2 but unpublished data on the period 1931 to 1934, plus the estimated unrecorded output prior to 1915, make the actual total about 2,400,000 short tons. This is about 21 pct of the total production of the United States, which, through 1947, is 11,328,440 short tons valued at $71,683,386.2

Jan 1, 1949

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962