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[PRESIDENT AND DIRECTOR * R. R. McNAUGHTON, '63, Trail, B. C., Canada PAST-PRESIDENT AND DIRECTOR * JOSEPH L. GILLSON, '62, Wilmington, Delaware PRESIDENT-ELECT AND DIRECTOR * LLOYD E. ELKINS, '64, Tulsa, Oklahoma VICE-PRESIDENTS AND DIRECTORS * JOHN S. BELL, '62, Houston, Texas * A. B. CUMMINS, '62, Bound Brook, New Jersey * WAYNE E. GLENN, '62, Houston, Texas * C. C. LONG, '62, Monaca, Pennsylvania * J. S. SMART, JR., '63, New York, New York * J. W. WOOMER, '62, Pittsburgh, Pennsylvania]

Jan 1, 1961

By William Cruger

OUTLINE SUMMARY A. Brief Description B. Characteristics 1. Can be highly cost effective 2. Restricted in usage 3. Political Controversy 4. Volume of Transactions 5. Users C. Mechanism 1. Five steps D. Investor issues 1. Application 2. Restricted usage 3. Discount 4. Formal or informal process 5. Restricted benefits 6. Recompense 7. Window of opportunity THE VARIOUS PROGRAMS1 A. Brazil B. Chile C. Venezuela D. Argentina E. Mexico USAGE IN THE MINING, METALLURGICAL, AND PETROLEUM INDUSTRIES

Jan 1, 1990

By J. M. Smith, D. Kunii, P. Adivarahan

Effective thermal conductivities were measured for seven samples of porous rocks through which gases or aqueous salt solution were flowing, parallel and countercurrent to the flow of heat. The results are analyzed in terms of the contributions of the solid and fluid phases to the total energy transfer. The solid contribution for the sandstone samples studied was found to be a Junction of the porosity and an effective thermal conductivity for the solid phase. The fluid contribution was a function of the Peclet number. Based upon the equations presented, the effective conductivity of the system can be estimated from the properties of the fluid, the flow conditions, and the porosity and pore-size distribution of the rock. INTRODUCTION Heat-transfer characteristics of porous media containing fluids are needed for the design and evaluation of thermal methods of petroleum production. The study reported here considers the problem of countercurrent flow of fluid and heat in sandstone rocks, and is a continuation of previous studies concerned with parallel and radial flow of energy and fluid in both rocks517 and beds of fine particles.6,10 In addition to these earlier works, Asaad,1 Kimura,4 Preston,8 Zierfuss and vlietll and waddams9 have reported effective conductivities for systems filled with stagnant fluids. There appears to be no published data on rocks through which fluids are flowing. The purpose of this study was to present such information and, particularly, to investigate the effects of properties of the rock and the flow rate on the results. The rock samples were naturally occurring sandstones from different locations and were similar to petroleum-bearing formations. The properties of the seven samples showing the range in porosities and permeabilities are given in Table 1. The mean pore sizes were calculated from mercury penetration data by averaging the radius with respect to pore volume. The details of this method and comparison with other procedures for estimating 7 are given elsewhere. Four fluids, nitrogen, carbon dioxide, helium and 10 weight per cent sodium-chloride solution were used with each sample. For Bartlesville sandstone, BA-5, runs were made at mean pressures from 15 to 250 psig using nitrogen. The other measurements were carried out at a mean pressure of 100 psig. The maximum temperature range eacountered was 70° to 300°F. The flow rate of fluid ranged from about 1.0 to 130 Ib/(hr)(sq ft), and this corresponded to a modified Reynolds-number range of 5 x 10-4 to 1.0. The variation in Prandtl number was 0.70 to 4.1. EXPERIMENTAL WORK The equipment consisted of apparatus to supply a constant flow of gas, or salt solution, at constant pressure to the bottom of a vertical test section, and metering and flow-regulation apparatus after the test section. The flow of salt solution was

By W. M. Corse

I bring this investigation to your attention to emphasize the needless waste attendent upon the use of tin plate with an unnecessarily heavy tin coating. With our present knowledge, we are unable commercially to produce coatings as light as the lower weights used in this test. If, however, future research should develop means to this end, the resultant product would meet all practical requirements, and a very considerable saving in pig tin would result. DISCUSSION G. H. Clamer.-—The National Canners' Association is studying the action of fruit juices, etc., on solders. Of course these tests will take quite a long time, and we hope by that time the war will be over and there will be no need for conserving tin for war purposes. Germany for a great many years has prohibited the use of more than 37 per cent. of lead in alloys used in contact with food products. The eutectic composition is 37 per cent. of lead and 63 per cent. of tin; alloys containing more than that percentage of lead have some free lead. J. W. Richards,' South Bethlehem, Pa.—A great deal of conservation can result from the packing of dry foods in cartons and in fiber packages instead of using sheet tin. Many of the boxes used for packing things other than food are frequently made of sheet tin because it prints and lithographs well; these could be made of sheet iron coated with copper or some other substitute metal which prints equally well. The Aluminum Bronze Industry W. M. CORSE,† Mansfield, Ohio.—The conservation of tin, in view of the shipping situation, is one of great importance. Several methods of conservation can be employed: 1. Reduction of the amount of tin in an alloy or compound. 2. Substitution of an entirely different metal or compound for tin. 3. A combination of the first and second methods. The second method is the one that I wish to discuss. Metallic aluminum, has been known for a long time, and its use in copper alloys was discovered about 1855 by Lord Percy. The high cost of production of metallic aluminum retarded its commercial development, and it was not until the discovery of the electrochemical processes for its production that it came to be known as a common metal. I have been particularly interested, for the past few years, in working with the alloy known as aluminum bronze, which is usually composed of approximately 90 parts of copper and 10 parts of aluminum, by weight.

Jan 1, 1919

By C. E. Beecher

The application of gas or air under pressure to obtain more oil from a sand which has been practically exhausted by ordinary production methods has been practiced to a limited extent for many years. Until recently such methods were confined to the Eastern fields, principally those of Ohio and West Virginia, where in many cases the production obtained after applying pressure for a few years was nearly equal to the total production prior to that time which had been obtained by the usual production methods. As early as 1917, J. 0. LewisL called attention to this method of increasing the recovery of oil and cited the phenomenal results obtained by H. E. Smith, I. L. Dunn and 0. C. Dunn, who pioneered the application of air or gas pressure recovery methods. With this information available it would appear that other oil-producing sections of the country have been extremely slow to realize the advantages of repressuring. However, after a few successful projects in the Mid-Continent area, the oil producers appreciated t' e value of this method for obtaining further and profitable production from their practically exhausted leases and are now making extensive use of it. In general, it has been the practice to apply pressure to the sands when production has declined to a small yield per well. The purpose of this paper is to discuss some of the advantages which may be expected from returning gas under pressure to the oil sands during the early stages of development, before the rock pressure has been dissipated and the gas exhausted, and to stimulate discussion of this subject on which comparatively little actual field data are available. The Function of Gas Gas associated with or dissolved in the oil is the source of energy causing movement of the oil to the well. When this energy is dissipated production ceases. The exception to this general statement is found in fields where hydrostatic water pressure may supply energy after the gas

Jan 1, 1929

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

By E. E. Malouf

With the continued development of low-grade porphyry copper deposits by open pit mining, substantial amounts of copper-bearing strip material have been accumulated in waste dumps adjacent to the many large mines. Since the end of World War II, the production of copper from leaching these copper-bearing wastes increased from approximately 4% of the total copper production to 10% by the early 1960's. Projected increases will probably raise this figure to 20 to 30% by the early 1970's. Furthermore, a gradual recognition of the economic feasibility of leaching mined-out areas is evident and will undoubtedly contribute additional production. Waste dumps in canyons and gulches on the periphery of open pit mines, mine stopes, caved areas, and abandoned open pits often contain substantial quantities of leachable rock ranging in concentration from 0.1 to 0.4% copper. Recent developments in the leaching of copper, mainly the recognition of bacterial oxidation of sulfide minerals combined with better under- standing of the control of the salt content of the leach solutions, both by adjusting the pH and/or by hydrolysis, are resulting in a greatly expanded recovery of copper from these hitherto uneconomic mine rejects. 11.5-1. Mechanism of Leaching. Leaching processes for the extraction of metal values from mine ore or waste may be classified for convenience as either chemical leaching or bacterial leaching. Chemical leaching is considered to be the extraction of soluble salts by metathesis in acidic, basic, or neutral water solutions. The reactions involved may be evaluated by chemical thermodynamics. Bacterial leaching, although a chemical process, is dependent on biological catalysis and this is generally a much more complex process. This justifies its separate treatment in the application to leaching. Acid ferric sulfate solutions are commonly employed in the mining industry to leach valuable metals from metal sulfide ores. The leaching mechanism is a reduction-oxidation reaction in which minerals are oxidized at the expense of ferric sulfate. Such chemical leaching is profitable when

Jan 1, 1968

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By William R. Webster

An investigation has been made of 500 samples of universal and sheared plates of basic Bessemer and basic open-hearth steel manufactured by the Pottstown Iron Company, the carbon-limits being 0.07 to 0.18 per cent. Through the courtesy of Mr. W. H. Morris, President, I am able to lag before the Institute the results of these tests. The samples tested were all taken from the finished material, and the chemical determinations were made on drillings from the broken test-pieces, which were sent to the chemist without giving him the heat-numbers. The results are such as to encourage me to keep on with the work, and, if possible, to have it carried out on other steels. It is kith this view that I now offer my tables in their incomplete form. My first table mas constructed by grouping the tests according to chemical analysis in various. ways, and making a rough tabulated statement, from which the ultimate strengths were worked out and carefully compared with the actual results of the tension-tests. From data thus obtained, one table after another was worked out, and by this method of "cutting and trying" I finally arrived at the results which I now present in Table I. (p. 771). I do not claim absolute accuracy, but my approximations have proved to be so close that the figures are practical data for current use at the works. The indications are that a pure iron, without carbon, phosphorus, manganese, or silicon, if it could be obtained, would give 38,000 pounds ultimate strength. This is assumed as a base, and to it is added the effect of each of the above elements, as explained below. The upper part of Table I. gives the ultimate strength due to carbon and phosphorus, and is the same for both basic Bessemer and basic open-hearth steels. The lower part gives the increase in ultimate strength due to manganese. By adding this to the amount obtained from the upper part, we have the ultimate strength of basic Bessemer

Jan 1, 1893

By H. F. Silver

Although the literature indicated that a hydrogen-ated coal bitumen might be used as a substitute for petroleum asphalt and road tar, no work could be found in which the material was actually used or evaluated as a road binder.' Therefore, a study was initiated to investigate the production and properties of a road binder made by hydrogenating coal in the presence of a solvent at elevated temperatures and pressures. HYDROGENATlON PROCEDURE Four different samples of sub-bituminous Wyoming coals and three samples of coals from other states, ranking from lignite to a low-volatile bituminous coal,

Jan 1, 1969

E. O'C. Acker '86 Truman H. Aldrich '78 Anson W. Allen '87 John H. Allen '84 W. Lawrence. Austin '82 W. S. Ayres '73 David Baker '86 John Henry Banks '83 Wm. de L. Benedict '83 Robert Bentley '84 Andrew A. Blair '75 Walter M. Brudie '72 Frederick Burbidge '87 H. H. Burden '83 Charles Butters '83 R. C. Canby '82 Arthur C. Carson '84

Jan 1, 1938

By C. W. Price, G. A. Wheeler

BERYLLIUM has always been a difficult material to prepare for metallographic examination. Severe surface deformation occurs during mechanical grinding and polishing, and a suitable bright-field etchant has not been developed. Certain electrolytic techniques produce satisfactory polishes, but these techniques have not yielded entirely consistent results. Furthermore, they have not provided satisfactory bright-field etches. The purpose of this paper is to describe an electrolytic polishing technique that can also provide an excellent bright-field etch. In addition to the bright-field etch, other advantages of this technique are excellent reproducibility, rapidity, and ease of polishing and etching. Experimental Technique. Specimen Preparation. Beryllium specimens may be either mounted or unmounted for the use of this technique, and the size of the specimens is not important. Specimens with surface areas up to 4 sq cm have been electrolytically polished and etched successfully with this technique. The most important requirement is to provide a good electrical contact to the specimens, preferably on the back of the specimens. When specimens are mounted, a hole is drilled through the back of the mount so that the specimen can be contacted with a probe. Conventional metallographic grinding techniques are used to prepare the specimens for electrolytic polishing. The specimens are ground on silicon carbide papers. Grinding through the usual series of papers down to the 600-grit paper is recommended to minimize the electropolishing time, although successful electrolytic polishes and etches have been obtained by grinding only through the coarser papers. A continuous flow of water is used during grinding to provide lubrication and to minimize contamination. Mechanical polishing is not required because high rates of material removal are achieved with the electrolytic polishing. Polishing. Most of the results reported in this paper were obtained with a "Disa-Electropol", manufactured by Struers Scientific Instruments of Copenhagen, Denmark. Satisfactory results have also been obtained with the conventional beaker technique of electrolytic polishing, however, the conditions applicable to both the Disa unit and the beaker technique will be described. Stainless-steel cathodes are used in both techniques. In the beaker technique, a flat cathode, with an area at least twice that of the specimen, is used, and the specimen is held parallel to the cathode. The distance between the specimen and the cathode affects the quality of the electropolish. This distance is set at about 7 mm in the Disa unit; the same distance produces the best results in the beaker technique. Specimen-cathode distances greater than about 20 mm produce considerable relief, while distances less than 7 mm cause high current densities that are difficult to control. An electrolyte of 2 pct HC1, 2 pct HNO3, and 2 pct HCIOl in ethylene glycol gives the most satisfactory results for both electrolytic polishing and etching. This electrolyte was developed by altering the composition of a similar electrolyte used for electrolytic lapping1 and adding HClOl to improve the etching characteristics of the electrolyte. Variations of from 0.25 pct to as much as 5 pct of each of the acids do not significantly affect the results, but the greatest amount of control and reproducibility can be obtained with the composition of 2 pct of each acid. Generally, lesser amounts of the acids produce lower polishing and etching rates, while greater amounts of acids cause high current densities that are difficult to control.

Jan 1, 1968

By L. H. Wolfe, J. O. Thieme

The tensile and shear strengths of frozen soil and the compressive strengths of ice and frozen soil were measured These tests showed that the strength of ice and of frozen soil increased as the temperature was decreased. A method is presented for the measurement of thermal conductivity and specific heat of earth and ice. Using the parameters thermal conductivity, specific heat and density, the thermal diffusivity was calculated. Results of thermal property tests establish water as the major variable contributing to thermal property values. INTRODUCTION During the last few years, a considerable interest has developed in underground storage of cryogenic liquids such as liquid natural gas. Because of its economy and safety, underground storage is being used. Before underground caverns could be seriously considered, however, the strength and thermal characteristics of the soil had to be obtained. Methods are presented herein for measuring tensile, compressive and shear strengths, specific heats and thermal conductivities. The tests were performed on two soils at temperatures from ambient to -195C. Because it is difficult to find data in the literature that pertain to a particular soil, ice was used to evaluate some of the experimental procedures. Some of our ice data are compared to the published values. PHYSICAI, PROPERTIES SOIL SELECTION AND SAMPLE PREPARATIONS The physical and thermal tests were performed on recompacted samples of two typical soils that might be encountered in underground caverns: a gray, fire clay that had been pulverized and mixed with water into a pliable mud; and a brown, sandy silt that was dug from a dry river bank and subsequent1y mixed with tap water. The moisture content of the test specimens was 17 to 22 per cent (based on the wet weight of the soil). This amount of water nearly saturated the silt, but the clay was well below the saturation point. The soils are partially described by the sieve analyses (Fig. 1) which show the particle size distribution of the coarser than 44 micron portion of the soils. The curves also show that approximately 75 per cent of the clay and 20 per cent of the silt are finer than 44 microns. The particle size seems to affect some of the physical properties, and the finer than 44 micron portion is important in the thermal conductivity test. Physical specimens were cut with a bandsaw from frozen blocks of the soil. The specimens were then sanded and kept frozen until after they were tested. They were stored at the approximate test temperature for several hours. Then, to equilibrate the samples to the test temperature, they were stored at the temperature at least an hour before they were tested. TEST EQUIPMENT An Instron, which is a constant speed gear-driven instrument, applied force to the samples and drew stress-strain plots of the test. All of the samples were strained at 0.02 in./min. All of the physical tests were conducted in a temperature cabinet that controlled the temperature to 1C. TENSILE STRENGTH Briquette or "dog-bone" shaped tensile specimens were pulled with suitably shaped jaws. This shape of specimen, which is usually used for tensile tests of concrete, is satisfactory for testing frozen soils except that the samples tend to

Jan 1, 1965

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.

By C. L. Magee, H. W. Paxton

PREVIOUS workersl'% ave found that as-quenched ferrous martensites can be plastically deformed at low stresses. They have also found that the stress to obtain small strains can be significantly increased by aging at temperatures up to 150°C. This behavior has been interpreted in two ways: 1) that the deformation at low applied stress is due to internal stresses and thus the aging phenomenon is due to relaxation of the internal stresses;' 2) that the microdeformation arises through the motion of unpinned dislocations and the aging process is the diffusion of carbon to the dislocations to pin them.293 In a recent paper,4 we have shown that under certain conditions the dominant microdeformation mechanism of as-quenched Fe-31Ni marten-site-austenite aggregates is the transformation of retained austenite. Our results on resistance changes during deformation and temperature dependence of the deformation also established that, at temperatures above 300° K, the microdeformation was not due to this transformation. The purpose of this note is to report results of experiments which indicate that explanation 1 is appropriate for this deformation. All results presented here are from conditions where transformation does not make a measurable contribution to the microplastic deformation, in Fe-31Ni-0.002C, or in Fe-29Ni-0.02C-0.25Ti. The experimental techniques that were used for measurement of the plastic deformation are described4 and analyzed5 elsewhere. Fig. 1 shows the microplastic response of 100 pct austenite at 300" and 350° K. The microplastic response of an austenite-martensite aggregate is also given in Fig. 1 and it is seen that, after formation of martensite, the initial plastic deformation occurs at lower stresses. Thus, the softness is not entirely due to retained austenite—the quenched structure can be deformed at lower stresses despite the fact that the macroscopic strength is significantly higher. A result which allows a distinction to be drawn between the alternative explanations for this behavior is derived from aging experiments on the low-carbon alloy containing titanium. We have previously shown4 that the presence of titanium in this alloy reduced the free carbon to a sufficiently low level that thermal stabilization of the austenite-martensite transformation was not detected. Despite this, Fig. 2 shows that the microplastic response is decreased by aging treatments. A similar aging effect in Fe-ZONi, with some titanium, has previously been reported by . Thus, carbon is not necessary for the aging process and explanation 2 is at best incomplete. Since internal stress relief can occur independently of carbon (any temperature dependence of the flow stress can result in decreased internal

Jan 1, 1969

By AIME AIME

OPPORTUNITY may not be knocking but it, at least, is waiting for you, your family and your friends in that amazing republic south of the Rio Grande. For the first time we are able to publish the official itinerary for the forth-coming Mexico City meeting of 1936. As shown on Page 351, the deluxe special train leaves St. Louis on Thursday. Nov. 5 at 5:30 p.m., returning to St. Louis on Nov. 18 at 8:15 a. m. The schedule provides seven days and six nights in Mexico City with numerous excursions to nearby towns and resorts. The oldest surviving city in' North America is Mexico City, dating back at least to the twelfth century. It was the Aztec capital when Cortez arrived in 1519. The famous cathedral still standing was built on a foundation of sculptured Indian images and the remains of a great Aztec temple. Today it is a city of romance.

Jan 1, 1936

Two separate but closely related projects now under construction on the St. Lawrence River- the Seaway and the St. Lawrence Power Project- are providing the impetus for what may become one of the most significant economic expansions in the Northeast. By 1959, or even earlier, electric power will be flowing from the largest single hydroelectric installation east of the Rockies. Simultaneously there will come into existence a great new commercial waterway which will provide cheap transportation from the farm and industrial heartlands of the U. S. and Canada to the markets and resources of the world. When the Seaway is completed, vessels with five to ten times the capacity of those now using the Canadian canal system will be able to move from the Atlantic Ocean to Lake Superior.

Nov 1, 1955

By S. Gilbert, G. R. Bailey

A further evaluation of the bomb-sampling method for determining the oxygen content of liquid steel is presented. The results of this study and their close agreement with the results of an earlier evaluation confirm the conclusion that the bomb-sampling method is valid for obtaining representative samples for the determination of the oxygen content of a liquid steel bath. WHAT constitutes the most desirable procedure for obtaining a sample suitable for determining the oxygen content of a liquid steel bath has been a controversial subject for several years. In 1952 Huff, Bailey, and Richards' described a modification of the bomb-sampling technique originated by McCutcheon and Rautio.' In both the modified and original techniques, a small cast-iron or steel mold containing aluminum wire and appropriately covered is inserted into the furnace, coated with slag, and then plunged into the metal bath. Upon entering the metal, the cover melts and a sample of the steel bath enters the mold. The data presented by Huff, Bailey, and Richards' indicated that reproducible samples could be obtained by their method. Furthermore, the oxygen analyses from samples obtained by their method agreed better with those from controlled laboratory experiments than did analyses from samples obtained by methods previously suggested for sampling large liquid-metal baths. Most techniques, other than bomb-sampling, require that a sample of liquid steel be removed from the furnace in a well slagged spoon and poured into an iron mold containing aluminum or into a massive copper mold for rapid chilling. Pouring in this manner requires that the sample pass through the air. The controversy, then, is somewhat as follows: Proponents of the spoon-sampling method and similar dip-and-pour methods feel that the introduction of a cold steel mold into a molten steel bath may result in a localized boiling condition that may deplete the steel of oxygen to a significant degree in the area where the bomb is introduced. Conceivably this boil could cause results that are, on the average, too low and nonrepresentative of the bath composition. On the other hand, samples that are spooned and then poured through the air may also be nonrepresentative because of oxidation by the atmosphere. The restrictions imposed in sampling with a spoon are much more stringent than those imposed when sampling with the bomb-type mold within the furnace. The spoon sample must be taken in a well slagged spoon, a requirement that depends on the condition of the slag in the furnace. Also, the samples must be poured as quickly as possible, without shaking the spoon and without allowing slag to enter the mold. The necessity of fulfill-

Jan 1, 1955

By W. T. Isbell

IN the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 14000 to 1500°F and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace was expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. EQUIPMENT AND ITS USES Dezincing Machine.-The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig I). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.-The treating cham¬ber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1947