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By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.' As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.' The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

By Donald Cummings

CERTAIN dusts are dangerous when inhaled, but most hazardous of all dusts are quartz or other forms of pure crystalline silica. The inhalation of dusts containing silica in combination with other elements gives rise to changes in the lung which differ from those produced by pure silica. As a generality, silicates are less dangerous than pure crystalline silica and vary greatly among themselves in harmfulness. Repeated analyses have shown that approximately 70 per cent of the total number of particles involved in any dust-producing operation are below 1 to 2 microns in diameter. (A micron is. approximately 1/25,000 in.) Similar studies of dusts recovered from silicotic lungs post mortem have demonstrated essentially the same size frequency distribu-tion, except that the upper limit of size retained in the air sacs is approxi-mately 10 microns. Experiments carried on by Gardner and the author have further demonstrated that greater changes were produced by a fixed weight of very fine quartz particles (2 to 3 microns and smaller) than by the same weight of slightly larger particles (8 to 10 microns). Any attempt to control a dust hazard should therefore be directed toward the removal from the working atmosphere of particles less than 10 microns in size, and particularly those below 3 microns. All industrial hygienists agree on this matter, but there remains considerable dispute as to the lower limit of particle size capable of causing injury. It has been gen-erally conceded, however, that particles of harmful dusts smaller than ¼ to ½ micron are not essentially concerned in the development of pulmonary fibrosis. This opinion is partly substantiated by the existence of large numbers of these small particles in practically all atmospheres that are, not associated with any known hazard. Such particles are so small that they have very little mass, fail to settle even in quiet air, and probably are not easily retained in the lung. Until further research proves that they are involved in the dangers provoked by the inhalation of certain dusts, engineers will generally agree that it is better to dis-regard them.

Jan 1, 1935

By John J. Howard

WE are approaching the depletion of our principal source of iron ore-the Great Lakes deposits, which have provided 85% of the nation's requirements for the past fifty years. This situation presents a threat to our standard of living and our position as a world power. Fortunately, in the Great Lakes region there are still tremendous quantities of potential iron ore in the form of the low iron, high silica rock called taconite. The economical extraction of iron from taconite will insure our future steel supply if no new deposits available to the United States even in time of war are discovered. In the new process presented here, the iron is reduced directly by a simple method and then separated from the silica. The product is "feed," not to the blast furnace, but to the steel plant. This process requires very much less plant, less physical and chemical treatment, and less fuel and auxiliary materials than the conventional ore concentration-blast furnace method. In my opinion, this new, fundamentally different approach offers a better hope for the solution of the iron ore problem.

Jan 5, 1950

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By A. T. Aldred, K. M. Myles

The vapor pressure of chromium over solid V-Cr alloys has been measured by the torsion-effusion method in the temperature range 1450" to 1650°K. The chemical activities as well as the free energies, entropies, and enthalpies of formation of the alloys have hem computed from the vapor-pressure data. The activities of both chromium and vanadium exhibit fairly small negative deviations from Raoult's law over the entire composition range. The values of the excess entropies and the enthalpies of formation found at 1550°K are considered in terms of the changes in the clzaracteristic properties of vanadium and chromium that occur upon alloying. RECENT interest in the theory and properties of transition-metal alloys has shown the need for relevant thermodynamic data. The present investigation of the V-Cr system was undertaken as part of a more general study of thermodynamic properties of transition-metal alloys. The system was chosen because of the reported complete solid solubility of the components at all temperatures1 and because the difference in magnitude of the vapor pressures of vanadium and chromium allowed a simple effusion technique to be used. The torsion-effusion method was employed to minimize compositional changes in the alloys during the experiments. EXPERIMENTAL Equipment. The torsion-effusion apparatus, shown diagrammatic ally in Fig. 1, consists of a torsion system suspended inside a vertical vacuum chamber whose lower end is surrounded by a high-temperature vacuum furnace. An auxiliary optical lever and screen are used to determine the angle of rotation of the effusion cell. The torsion fiber is an annealed, high-purity, tungsten wire usually between 0.003 and 0.007 cm in diameter and about 43 cm long. The wire supports a concave mirror and a rigid tantalum connector tube. The effusion cell is fastened to the lower end of the connector tube by a dovetailed yoke and har- ness arrangement. The cells, which are 1.27 cm in diameter and 4.4 cm long, were made by electron-beam welding tantalum endcaps onto a 0.025-cm-wall tantalum tube. The two orifices, formed by drilling, have similar areas ranging from 0.011 to 0.031 sq cm. The noninductive sheath-type furnace consists of a single-phase tantalum heating element 6.35 cm in diameter, 15 cm high, and 0.013 cm thick; the element is completely surrounded by radiation shields in an evacuated chamber. The power system includes a 17-kva self-saturating saturable core reactor with an integral magnetic amplifier and a water-cooled, 15-kva, step-down power transformer with a multitap secondary. Temperatures are controlled to within ±1/2o at 1600°K by means of a unit that includes a reference voltage source, a dc electronic null detector, a current-adjusting proportional band relay, and the self - saturating reactor. At 1650°K the temperature variation within the cell, vertically and horizontally, is 3/4oK. Unwanted motions of the torsion system are damped by the movement of an aluminum vane, which is mounted on the connector tube, between the poles of an electromagnet. When not in use the magnet is withdrawn and rotated 90 deg to prevent its interaction with the rotation of the system. Measurements. The vapor pressure, p, is re-

Jan 1, 1964

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper .to, discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in. brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: 1-gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2-liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3-glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4-crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that carried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant, contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.1 At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1-aqueous solution, a much more expansible liquid, and a gas; 2-aqueous solution, salt crystals, and a gas; and 3-the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20° and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.2-6 Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid. carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.7,8 Hartley (1876, 1877),9,10 Hawes (1881),11 Wright (1881),12 Johnsen (1920),13 and Holden (1925)14

Jan 1, 1952

By William B. Plank

IN this paper are presented the results of a complete statistical survey of the enrolment, courses and degrees, and the employment situation of recent graduates in all of the 46 institutions in the United States, including Alaska, and four of the six schools in Canada that grant degrees in mineral technology. The data were collected by the writer by means of a questionnaire in December, 1933, to which all the institutions, except one, replied. Included also are data of a similar study made by the writer in May, 1933, for the S. P. E. E. summer session of mining and metallurgical teachers at the University of Wisconsin and published in the Journal of Engineering Education for December. 1933. Some of the data of a paper of the writer's entitled, "The Trend of Mineral Engineering Student Enrolment in the United States," read at the A. I. M. E. meeting on Feb. 16. 1931, are given for comparison. Acknowledgment is made to all the administrative officers of the institutions who took the time from their busy lives to supply the in- formation asked for. Their fine cooperation has alone made possible these two surveys with a completeness of detail never before attempted

Jan 1, 1934

By T. M. Geffen, F. F. Craig

Laboratory model flow tests have been made to simulate field conditions of partial pressure rnaintenance by dispersed gas drive on rocks having sandstone-type porosity. In this production method there is a significant saturation gradient between injection and production wells. A means of calculating relative permeability characteristics. from partial pressure rnaintenance flow tests has been developed. This method takes into account the saturation gradient. These kg/ko characteristics are identical to those for solution and external gas drives. This method of calculation, which has been proved experimentally, has limitations; however, it is valid for cases likely to be encountered in field prediction of partial pressure maintenance performance. The production performance of a hypothetical reservoir has been calculated for several different injection programs, involving both full and partial pressure maintenance. Results indicate that the maxinum oil recovery by these gas injection programs is obtained by full pressure mainte- nance at the original bubble point. Correspondingly lower oil recoveries are obtained by postponing gas injection and/or by reducing the degree of pressure maintenance. INTRODUCTION Dispersed gas injection is an important method of recovering additional oil beyond that obtainable by pressure depletion alone. The injected gas acts as a source of additional energy to displace oil from the rock formation as well as to retard oil shrinkage in the reservoir. In practice, gas injection is usually started after the reservoir pressure has fallen below the original bubble point. For various reasons sufficient gas is generally not injected to completely maintain the pressure in the reservoir. So, injecting gas at a declining reservoir pressure results in a combined external and solution gas drive. These two oil displacement processes are characterized by different gross saturation distributions in the reservoir. The external gas drive, like all frontal drive processes, inherently results in an oil saturation which increases from the injection wells to the producing wells. In the solution gas drive there is essentially a uniform oil saturation throughout the reservoir, provided the field is being depleted uniformly. It has been customary to predict oil recovery performance under partial pressure maintenance by a method which does not take into account the saturation gradient1. It has been shown2 that neglecting the presence of a saturation gradient can cause considerable error. It is the purpose of this paper to develop and present an improved method of predicting partial pressure maintenance performance of reservoirs including, where necessary. the effects of well arrangement. From the laboratory standpoint, this problem involves the measurement of the basic flow behavior (relative permeability characteristics) under partial pressure maintenance conditions. Recent research- as shown that for rocks having sandstone-type porosity, the relative permeability characteristics are identical for solution gas drive and complete pressure maintenance external gas drives. Since both solution and external drives have the same basic flow behavior, it was speculated that partial pressure maintenance, being a combination of the two, would also

Jan 1, 1957

By William G. Kegel

Aside from having a usable product and good mining conditions, the greatest asset for a profitable coal mining organization is an effective mine maintenance program. The first step in acquiring this is the presence of good mechanics-men who have a desire to be mechanics and who want to know more about the design and control of the machines in their charge. The knowledge and ability to be found in a good mechanic is the result of ambition, curiosity, and determination. With these qualities as a start, the aspiring mechanic can launch his career if he begins learning all he can about mechanics, electricity, and hydraulics. The path is rough, but the goal is rewarding. Mining machinery probably absorbs as much or more abuse than any other heavy equipment in use today. And when one considers the conditions under which much of the repair work must be done, it can be seen that the mine operator needs the best of men and tools to perform the service. MOTORS AND POWER SUPPLY Mining machines, from their inception, have utilized the electric motor; and down through the years of mechanization, this power source has undergone many changes to better adapt it to the job. The first motors used were large, heavy-framed, open d-c motors (direct current), using a series or shunt winding. A motor having one or more field coils connected in series and themselves in series with the armature, is called a series motor (Fig. 1). The series motor had the advantage of quickly developing starting torque, and it was, and still is, the best motor for locomotive or shuttle car tramming service. The series motor, however, speeds up as the load is reduced and, if not properly controlled, can overspeed. The shunt motor, as its name implies, has one or more field coils in

Jan 1, 1973

By H. C. Goodrich

THE earliest record of copper production from the state of Utah comes from "The Resources of Utah," by. Mr. Fabian, in 1872, wherein it is stated that the. Mammoth mine of East Tintic was located in 1870 and that the ores yielded a large percentage of copper, silver and gold. It is also stated that shipments had been made to Swansea, England, which assayed between $200 and $300 per ton. The Mammoth-Copperopolis mine was located in, 1870 and sold the year following to an English syndicate. Some copper was shipped to. England and in 1873 there was constructed a 15-stamp mill and two copper smelting furnaces; these were operated a few months and before the end of the year were closed down and the property sold for debt. . This property -vas reorganized in 1879 and is at the present day a producer, though its principal product now is lead and silver. While a certain amount of copper has always been coming from the various lead-silver camps of Utah, the real history of copper in Utah should start with the discovery of the mines in Bingham Canyon, located about 25 miles to the southwest from Salt Lake City.

Jan 1, 1925

Occasionally it is interesting, and sometimes useful, to review the past for early references to our industry, and to learn of the trials and travail passed through before it arrived where it now is - and the results of such a review follow. Some time ago one of our modern playwrights and poets, Arthur Guiterman, turned to coal, with the following result : Afar in the Carboniferous time I grew in Paleozoical slime, A lepidodendron with boughs on my stem And lepidostrobusea grew out of them. My roots in the mud of the ages I spread And up to the heavens I vaunted my head, I throve in the heat of tropical sun, And now I am coal at two dollars a ton.

Jan 1, 1935

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By C. P. PERIN, DONALD BELCHER

T HE production of pure iron by electrolyzing solutions of its salts has been the object of scientific curiosity and research for about 80 years; and in the last two decades a realization of the unusual physical and chemical qualities of electrolytic iron has turned the attention of chemists and metallurgists toward a commercial application of this accumulated knowledge. Thus Burgess and Hambuechen in America, . Cowper-Coles in England, and Fischer in Germany- devised methods, more or less successful, for the electrolytic refining of iron, but none of these processes has yet attained large-scale operation. During the war some interesting ,work was done in France and England on building up worn or defective machine parts by electrodeposition of iron. It remained for the Société "Le Fern in France to carry on the process commercially. For six years Les Fonderies et Forges. de Sainte-Maire et Gravigny and the works of Bouchayer & Viallet at Grenoble have manufactured pure-iron boiler tubes in competition with established practice. The French process originated in the researches of Anthelme Boucher in 1910, and was, not put into operation until several years of experimentation had passed.

Jan 1, 1921

By D. B. Jugle, J. B. Darby, O. J. Kleppa

A systematic study has been made of the kinetics of solution under steady state, dynamic conditions of titanium, vanadium, chromium, iron, cobalt, and nickel in liquid aluminum. It was found that the temperature dependence of the solution rate obeyed an Arrhenius-type rate equation, and that at a given temperature the rate of solution of the various solutes correlates quantitatively with the equilibrium solubility of the solute in liquid aluminum. These results are consistent with a mechanism where the rate-controlling step is the diffusion of solute atoms through a liquid boundary layer. THE present study was initially started in order to explore the feasibility of liquid-metal solution calorimetry for transition metals and alloys. Previous work1 in this field employing liquid tin as a solvent at temperatures in the 500' to 600' range had indicated that the rates of solution of most transition metals in tin are very low. Under such conditions effective solution calorimetry is difficult. The objective of the present investigation was two-fold: a) To obtain, as far as possible, quantitative data on the rates of solution of a series of transition elements in liquid aluminum. b) To explore whether liquid aluminum might be a suitable solvent for liquid-metal calorimetry. In the course of this work a comprehensive set of data was obtained on the steady state rates of solution of transition metals in a common liquid-metal solvent. The results are consistent with the boundary layer model, which assumes that the rate-controlling step consists of diffusion of solute atoms through a viscous liquid layer. EXPERIMENTAL PROCEDURE A vacuum-tight stainless steel vessel was surrounded by a resistance furnace, as shown in Fig. 1. In all experiments the temperature of the liquid solvent was controlled to 2.5' by means of a Micromax controller. A high-vacuum manifold connected to the vessel maintained a vacuum of 1 x 105 mm of Hg or better. The vacuum vessel was equipped with a charging section isolated from the working chamber by a vacuum-tight gate valve. This arrangement allowed the specimen holder to be removed or inserted into the apparatus without removal of the liquid metal bath. The specimen holder was suspended from a closed end stainless steel tube, which also served as the thermocouple protection tube. The portion of the tube that was below the solvent level was surrounded by an alumina protection tube to isolate it from the liquid metal bath. The stainless steel tube was connected through a rotary vacuum seal and a gear train to a fractional horsepower motor. For most experiments the tube was rotated at a constant

Jan 1, 1963

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By Arthur Boynton

IN THE preparation of this paper the writer has been influenced by the fact that descriptions of various means of cleaning blast-furnace gas have been published and that further descriptive treatment of the subject will probably be less interesting than a statement of conclusions with regard to preferable methods which have been reached by him as a result, of experience and observation in this country and also as a result of somewhat detailed investigation of the subject made toward the end of the year 1927 on the Continent of Europe and particularly in. Germany. Owing to various circumstances, including a cost of fuel that is extremely high in relation to the wages of labor, the German iron and steel industry has accumulated experience in gas washing which is as yet in part lacking in the United States of America. The paper begins with a statement regarding the economics of the use of blast-furnace gas, then considers the principle's and practices employed in its purification. USES OF BLAST-FURNACE GAS For many reasons having to do with the utilization of coke-oven and blast-furnace gases in steel manufacture and with the use of hot metal, the blast furnace is now usually a part of a steel-producing unit, which also includes coke plant and rolling mill. Therefore both blast-furnace and coke-oven gas are usually applicable to any of the iron and steel-making processes, including the generation of power, and their allocation in any given works should be considered as a single problem. The uses to which blast-furnace gas, either alone or mixed with coke-oven gas may be put, include the following: Regenerative Heating of Air for the Blast Furnace.-This is the oldest and metallurgically the most important of all uses. It is universally performed with unmixed blast-furnace gas and under proper conditions should require not over 23.5 per cent. of the total gas generated for a blast temperature of 1350° F. For Steam-raising Purposes.-This is almost universally done with unmixed blast-furnace gas. From the standpoint of quantity used, it is at the present time the most important application in American steel-works practice.

Jan 1, 1928

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By N. Brown, M. Herman

IT has been pointed out by Cottrell' and Fisher that long-range order would produce superdis-locations, consisting of two partial dislocations separated by an out-of-phase region. The mutual repulsion of the partial dislocations is balanced by the surface tension of the out-of-phase domain boundary joining the dislocations (Fig. 1). The calculation of the equilibrium spacing of the dislocations has yet to be made. The argument uses the Bragg and Williams theory of long-range order." The metal under consideration is the A-B, body-centered type, such as ß brass. The slip system is taken to be [Ill], (110). Since nearest-neighbor interactions are considered, only the atoms position in the two (110) planes adjoining the slip plane have to be labeled. Corner sites are called a and a' in the top and bottom (110) planes, respectively. Similarly ß and ß are the body-centered sites. Thus, a and ß and 0 and a sites are nearest neighbors. Assume that the bottom plane moves and the top plane is fixed during slip; the atoms in a and ß sites exchange sites but atoms in a and ß sites remain fixed. Fraction of A atoms in a sites, for example, is given by fa and fa. for the un-slipped and slipped condition, respectively. Similarly number of A atoms in the a sites is given by n, and n'a for the unslipped and slipped condition, respectively. As the dislocation moves into the ordered region the change in number of A-A bonds is given by

Jan 1, 1957

By R. Kossowsky

BRIDGMAN has listed five possible transitions in bismuth at 25°C which were observed as volume changes. He was unable however to detect the last three transitions by electrical-resistivity changes. Kennedy and LaMori have verified the pressures at the Bi 1-11 and Bi 11-111 transitions. They suggested however that the 125-kbar transition previously reported by Bundy3 actually corresponds to the 90,000 kg per sq cm transition observed by Bridgman.1 Jura4 reported a well-defined drop in resistivity at 92 kbar obtained by a four-lead method. The Bi 111-IV and Bi IV-V transitions have not been reported in any of the above-mentioned references.'-' Bundy3 observed a small dent in the low-temperature boundary of the Bi Vll region which is consistent with the presence of a 111-IV boundary. Zeitlin and Bray-man5 were the only ones to report small but well-defined drops in resistance of bismuth at 44.0 and 63.8 kbar, corresponding to Bridgman's 111-IV and IV-V transitions, respectively. High-purity (99.99 pct) 0.020-in.-diam 0.5-in.-long bismuth wire was used to calibrate the Uniram tetra-hedral high-pressure apparatus used in the present work. The bismuth phase changes at 25°C were correlated with changes in electrical resistance as a function of pressure. The output of a sensitive bridge constructed of carbon resistors and kept at a constant temperature of ±°C during the measurements was fed to the Y axis of a MoseleyX-Y recorder and the X axis was used for time scans. Specimens were pressurized using a hydraulic press with maximum capacity of 200,000 lb. Load was applied in increments of 2000 lb and held for about 3 min. The resistance was recorded at the end of this time period. Good contact was established below 20,000 lb. Typical recorder charts are reproduced in Figs. 1 and 2 which show that resistance fluctuations were practically nil during each time scan. Well-defined discontinuities in resistance were observed at 58,000 and 82,000 lb, Fig. 1. Two small but definite "blips" are noticed at 92,000 and 122,000 lb, Fig. 2. At 156,000 lb another drop is observed which

Jan 1, 1967