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By Kazutami Imai

Effects of heavy metal ions on the growth and the activities of iron and sulfur oxidation of Thiobacillus ferrooxidans were investigated. Mercuric, silver, and stannous ions inhibited both of the growth and the iron- oxidizing enzyme system of the bacterium. On the other hand, uranyl ion inhibited the growth, but it gave almost no effect on the iron-oxidizing enzyme system. The inhibitory effect of uranyl sulfate on the growth of the bacterium is intensified on lowering the cultivating ' temperature from 28 ºC to 7 ºC. In the concentration of 10-3M, cadmium and copper ions inhibited colloidal sulfur-oxidizing activity of the cells 69 and 52 %, respectively, though they did not inhibit the iron-oxidizing activity at all in the concentration. On the contrary, stannous chloride did not givr any effect on the sulfur-oxidizing activity of the cells, though it inhibited the iron-oxidizing activity 55 % in the concentration of 10-3M. Several differences were observed among the cytochrome systems of cell-free extracts of the cells grown on iron and on sulfur.

Jan 1, 1976

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By N. D. Shutler

This paper describes a numerical mathematical model of the steamflood process that depends on fewer restrictive assumptions than models previously reported. The solution, however, is obtained economically. Example calculations are presented that, on comparison with experimental results, tend to validate the model. Results that expose certain process mechanics are discussed. The model describes the simultaneous flow of three phases — oil, water and gas — in one dimension. It includes the effects of three-phase relative permeabilities, capillary pressure, and temperature- and pressure - dependent fluid properties. Interphase mass transfer of water-steam is allowed, but the oil is assumed nonvolatile and the hydrocarbon gas insoluble in the liquid phases. The model allows heat convection in one dimension and two-dimensional heat conduction in a vertical cross-section spanning the oil sand and adjacent strata. The hydrocarbon-steam gas composition is tracked, but the effect of gas composition on water-steam phase behavior is neglected. The model is solved numerically in three separate stages. The three-phase mass balances are solved simultaneously using Newtonian iteration on nonlinearities occurring in the accumulation terms. The energy balance is solved separately by noniterative application of the alternating-direction implicit procedure. Separate solution of the composition balance is accomplished by straightforward solution of the finite difference equations. The method of effecting nonsimultaneous, stable solution of the mass and energy balances is the key to the success of the model. INTRODUCTION Mathematical tools as well as laboratory and field experiments are necessary to help us understand the complex steamflood process. A mathematical model can expose process mechanics and show the relative importance of process variables, but this ability is often limited by restrictive assumptions. Most known models of steam processes,l-5 with the exception of the model of Gottfried,6 are "simplified" in that they involve analytic approximations and require many restrictive assumptions. The primary utility of these methods lies in the routine use as an aid in engineering design. By contrast, the comprehensive model presented here is numerical and requires far fewer restrictive assumptions. It finds its primary utility as a research tool. It serves as an aid in understanding the nature of the process, in interpreting laboratory experiments and in evaluating and developing simpler mathematical models for engineering design. The major reason why previously presented models have been confined to the "simplified" class is evidenced by the one published exception. In 1965, Gottfried6 presented a numerical model for the combustion process of which the steam process is a subset. The result is a comprehensive tool (though it neglects capillarity and two-dimensional heat conduction) that is troubled with convergence problems and that requires 2 to 3 hours of IBM 7094 time to complete a calculation. Though our present model does not simulate combustion, it does consider capillarity and two-dimensional heat conduction and it overcomes the convergence and computer-time problems. MATHEMATICAL DESCRIPTION OF STEAMFLOODING FLUID FLOW The equations employed to describe three-phase fluid flow are of a familiar form. Darcy's. law provides expressions for the velocities of the three phases (oil, water and gas), which, when combined with oil, water and gas mass balances, give the partial differential equations governing flow of the

Jan 1, 1970

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10'6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By Josef Intrater

A dilatometric determination of the a + ß region temperature limits was performed on vacuum melted Zircaloy-2. The temperature of transformation for a-a+ß and a+ß — ß on heating and cooling as a function of rate of heating and heat treating history was studied. The limits were found to be 815° to 830°C to 975° to 995°C on heating and from 960° to 930°C to 785° to 770°C on cooling. A 5° to 15°C increase was observed for a- a + ß with increased rate of heating and a 20° to 30°C decrease for ß - a + ß with increased rate of cooling. 1 HE transformation temperature for pure zirconium has been determined by many investigators1-5 using metallography, electrical resistivity measurements, and dilatometry. The effect of the rate of cooling on the transformation temperature of zirconium has been studied by Hayes and Kaufmann6 and Duwez,7 and the effect of alloying elements by pfei18 and McGeary.13 Since the development of Zircaloy-2, the limits of the a + ß region for that alloy have been also determined. The first reported temperature for the a — a + a transformation in Zircaloy-2 was 900°C and for a + ß - ß 1000C Subsequent studies by Picklesimer and damson" indicated the beginning of the transformation at 810°C, and the metallographic study by the Technology Group of the Special Materials Section at the Westinghouse Bettis plant1' suggested that 820°to 830°C is the temperature of transformation. The dilatometric investigation by the latter group yielded 830°C for the beginning of the transformation. Thomas and Forscher12 set the beginning of the transformation at 900 °C on heating and the end of the transformation at 870°C on cooling. The above investigators stated in their paper that the dilatometric curve exhibits features caused by a eutectoid reac-

Jan 1, 1962

By D. Weinstein

Yieldilzg in annealed arc-cast molybdenunz in torsion was studied as a function of strain rate and tem-perature. The temperature dependence of the yield point for different strain rates was used to calculate a heat of activation for the yield point. The heat of activation was not a constant but was approximately a linear function of the stress at yield. It is proposed that the rate effect in yielding is determined in part by a site place-change of C (or other interstitial atom) in the metal. THE low-temperature embrittlement phenomenon in metals and alloys has been known to exist for a long time. Although a transition from ductile to brit-tle behavior has been observed in some close-packed hexagonal metals1 and a face-centered cubic alloy, the most common class of metals exhibiting this be-havior has a body-centered cubic lattice structure. For example, a ductile to brittle transition has been observed in iron,3 molybdenum,4 chromium,5 colum-bium,6 and tungsten.7 In the present investigation, molybdenum specimens were tested in torsion over a wide range of temperatures at three widely separated strain rates, and the temperature for onset of embrittlement was determined. Characteristic of body-centered cubic metals and closely associated with plastic deformation is the appearance of a sharp upper and lower yield point. Theoretical explanation of the yield point in iron and low-carbon steel is due to Cottrell,8 who attributes the phenomenon to the pinning of dislocations by the formation of impurity atmospheres around the dislocations. These atmospheres tend to lock the dislocations and make them more difficult to move. The stress required to move a dislocation and thereby cause plastic deformation is greatly increased, and thus an upper yield point is observed. In addition, theoretical analysis,9 as well as experimental observations, show that the upper yield point is strongly a function of temperature. The upper yield point is observed to decrease with an increase in testing temperature, and above a certain temperature (-700° K in iron) it no longer appears. This is consistent with the concept that thermal vibrations will help free a dislocation from its atmosphere, so that the external stress required to free a dislocation from its pinning atmosphere decreases with increasing temperature. Furthermore, with increasing temperature the equilibrium concentration of impurity atoms around a dislocation decreases exponentially with the result that the dislocation is less firmly pinned. In Cottrell's theory of yield point a static model is visualized in which the pinning atmospheres, particularly interstitial atoms, are immobile, and the dislocations are anchored to stationary positions in the lattice. However, experiments1,7 show the upper yield point to be time-dependent or a function of the rate of straining, a high strain rate causing a high upper yield point. Present theory does not adequately account for the rate dependence of the yield point, and the exact function of the interstitial atom is not under stood. Nevertheless, observation of the temperature dependence and rate dependence strongly suggests that the upper yield point phenomenon is due to the interaction between dislocations and pinning atoms, and that a diffusion mechanism is important in determining the yield point.

Jan 1, 1962

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By J. E. Pavlick, A. G. Guy

The total creep of tin alloys containing antimony in solid solution was observed to decrease with increase in antimony content. However, near the solubility limit an anomalous maximum in deformation was. found, in agreement with similiar observations by Bochvar. IT has long been recognized that alloys may deform more rapidly under stress if there is a tendency for a phase change or other structural change to occur simultaneously. However, the phenomena involved are complex and in some instances the opposite effect, strengthening, may result.' This area of research has not attracted much interest in the western world, and although Russian investigators have studied it for the past 15 years their work has not received due attention here. Recently diametrically opposing views on one aspect of this problem have been espoused by two Russian investigators, Kornilov and Bochvar. The question is this: in certain binary alloys tested in creep at the temperature where the solute is at the limit of solid solubility, does the incipient formation of the second phase strengthen or weaken the alloy? Korni-lov's arguments in favor of strengthening were presented at the 1954 Symposium at the National Physical Laboratory, =Creep and Fracture of Metals at High Temperatures.The most recent statement of Boch-var's theory of weakening is in Oding's new book on creep and rupture.3 Although Bochvar agrees that strengthening occurs in some alloy systems, he argues that in certain alloys an anomalous weakening is observed. However, the extensive work of Korni-lov's group on creep properties of alloy systems has not revealed any anomaly of this type, but instead has tended to refute Bochvar's theory. This clear-cut controversy offered a good opportunity for a simple experiment to resolve the problem. The experiment and its results supporting Bochvar are the subject of this paper. However, it will be helpful first to sketch the present status of the larger question of the effect of a phase change or other structural change on plastic deformation. PREVIOUS WORK One of the first researches in this area was by Pfei1,37 who investigated the creep resistance of an 80 Ni-20 Cr alloy containing varying amounts of titanium. He found that the resistance to creep increased rapidly as the solid solubility limit in the alloy at 775'c was approached and slightly exceeded. With further addition of titanium the creep resistance decreased, presumably because of precipitation effects. Bochvar's first work in this field was a study in 1945 of "superplasticity" in zinc alloys containing 15 to 25 pct Al.4 He found that alloys quenched from about 400 had anomalously low hardness when tested below this temperature. The following year, in a paper on the dependence of mechanical properties on the composition and structure of alloys,5 he extended some observations of Kurnakov to predict that at high temperatures of testing the hardness values for solid-solution alloys might be lower than those for the component metals. He also pointed out the influence of changes in solidus temperature in affecting curves of hardness vs composition, and he

Jan 1, 1962

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By S. Mellgren, W. Opie

AN equilibrium state of importance in the process of electrolytically depositing titanium from fused chloride electrolytes is that which exists between titanium metal, titanium dichloride, and titanium trichloride. This can be expressed by the reaction titanium concentration of the solution, temperature, and the proportion of strontium chloride and sodium chloride in the solution. Procedure The general procedure used consisted of the following steps: 1) Development of an analytical method for determining Ti+2 and total titanium. 2) Preparation of batches of fused salt solutions containing various amounts of total titanium, Ti+2 and Ti+3 3) Blending of the prepared batches and excess titanium metal in Vycor tubes and allowing the solutions to come to equilibrium. By blending, solutions with different total titanium content could be prepared and equilibrium could be approached from the high Ti+2 and low Ti+2 sides. 4) Studying the effect of titanium concentration, temperature, and the mole ratio of the solvent chlorides, SrC1, and NaC1, upon the equilibrium.

Jan 1, 1958

By I. E. Campbell, R. I. Jaffe

Oxygen, nitrogen, and hydrogen are known to be absorbed by titanium at elevated temperatures. Ehrlichl reports that about 30 at. pct oxygen can be dissolved in solid solution by alpha-titanium. Nitrogen also has a solid solubility in alpha-titanium, but there is no information as to its extent. The solid solubility of hydrogen in titanium also is high. Kirshfeld and Sieverts2 report 50 at. pct soluble, while Hägg3 reports about 33 at. pct hydrogen to be soluble in alpha-titanium. General statements are made in the literature that oxygen, nitrogen, and hydrogen embrittle titanium, but no quantitative measurements have been made of the effect of these gases on the mechanical properties of the metal. One reason for this is the lack of a source of titanium pure enough to be considered a suitable starting material. Iodide-refined titanium, made by thermal decomposition of titanium iodide vapor on an incandescent wire,4 contains small amounts of carbon, silicon, iron, and aluminum, but is very low in oxygen, nitrogen, and hydrogen content, and, therefore, was used in this work. A further reason for the lack of quantitative information on the effect of these gases, particularly oxygen, is the difficulty of carrying out accurate analytical determinations at the low concentrations of interest in this work. For this reason, the oxygen, nitrogen, and hydrogen were added in measured amounts as gases, and diffused into the titanium, to avoid the necessity of chemical analysis. The purpose of the work reported here was to isolate and measure the effects of oxygen, nitrogen, and hydrogen on titanium of the highest purity available at the time. The concentrations studied were 0.25, 0.5, and 1 at. pct in each case. Experimental Work One-half of a 24-in. hairpin of iodide-refined titanium was available for this work. The rod was approximately 0.25-in. in diam and had a 0.003-in.tung sten core. From chemical and spectro-graphic analyses, the purity of the sample was estimated to be between 99.80 and 99.95 wt pct. The chief impurities (aside from the tungsten core) were iron (0.04 pct), silicon (0.01-0.1 pct), aluminum (0.05 pct), carbon (0.03 pct). The tungsten core constituted 0.05 pct by weight of the sample. Although some alloying undoubtedly took place between the tungsten and the titanium during the deposition reaction, the core remained substantially intact in the deposited metal. The initial average hardness of the titanium as deposited was 105 Vickers (10-kg load). The maximum hardness was 116 Vickers and the minimum 91 Vickers. The metal was somewhat harder than that currently being obtained by the iodide process, that is, 75-90 Vickers. The rod was cold swaged to ¼-in. diam and then cold rolled in diamond shaped rolls to about 0.080-in. square, using reductions of 15 pct in area per pass. The 0.080-in.-square wire was cut into 6-in. lengths for the preparation of the alloys by the gaseous absorption and diffusion method. ADDITION OF OXYGEN, NITROGEN, AND HYDROGEN TO TITANIUM A modified Sieverts' absorption apparatus, shown in Fig 1, was used in

Jan 1, 1950

By J. W. Halley

THE effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. PUBLISHED WORK A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimm1 found no change in Olsen ductility, Rockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.15 per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.01 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.06 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0.50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. EXPERIMENTAL WORK Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1942

By J.W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By J. W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By K. D. Hester, A. W. Fletcher

A nickel-copper sulphide concentrate was treated in a pilot plant at Warren Spring Laboratory during 1961, by a hydrometallurgical roast-leach-solvent extraction process devised to cleanly separate the metal values and produce acid sulphate liquors containing the metals. It is shown that 86 pct of the nickel and 95 pct of the copper could be leached from the calcine, after a sulphatizing roast on finely ground flotation concentrate. Iron was removed from the leach liquor by limestone neutralization with a small loss of values. Copper and nickel were separated by solvent extraction with naphthenic acid in kerosene after partial neutralization of the iron-free liquors with ammonium hydroxide. Hydrogen sulphide and chlorine were used to remove zinc (and residual copper) and cobalt impurities respectively. The recovery of pure copper and pure nickel, by electrowinning, from the acidic solvent extract strip liquors finally produced, appears technically feasible. An economic analysis of production costs shows that small, geographically isolated, nickel-copper sulphide deposits cannot usually be worked profitably by established processes. The requirements for profitable operation on a comparatively small scale could possibly be met by a flotation-roast-leach process. Two difficulties, obtaining satisfactory extraction of nickel from a sulphide concentrate and separating the copper and nickel in solution, have prevented the previous use of this method. A solution to the first problem, dissolution of the nickel, was described in a recent paper by Thornhill.1 It was shown in this paper that copper and nickel in a flotation concentrate could be oxidized to water soluble sulphates by roasting in a fluidized bed with added salt cake. Workers at the Warren Spring Laboratory have shown that the separation of copper and nickel can be accomplished by solvent extraction using a relatively inexpensive carboxylic acid, naphthenic acid. Moreover, the mineral acid required to strip values from the loaded solvent could be produced, and the metals recovered, by electrowinning; thus the latter section of the process was regenerative. The removal of iron from the leach liquor and the elimination of impurities such as zinc and cobalt before nickel electrowinning would be necessary to complete the flowsheet. The process under investigation could therefore be summarized (Fig. 1) as follows: 1) Flotation to produce a bulk sulphide concentrate. 2) Fluidized bed roasting to sulphate the nickel and copper minerals. 3) Leaching of roaster calcine to extract soluble nickel and copper. 4) Precipitation of iron from the separated leach liquor by air oxidation after the adjustment of pH and temperature. 5) Recovery of copper from the iron-free Liquor by pH adjustment and liquid-liquid extraction. 6) Purification of the copper raffinate by removing zinc and residual copper as insoluble sulphides and cobalt as cobaltic hydroxide. 7) Recovery of nickel from the purified liquor by pH adjustment and liquid-liquid extraction. Laboratory and pilot plant studies detailed below, were carried out at the Warren Spring Laboratory, to test the feasibility of each one of the unit processes and to obtain preliminary plant design data. FLOTATION The ore was an altered basic rock containing concentrations of magmatic sulphides.

Jan 1, 1964

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

THE story of Miami really is two stories. First, that of an excellent Porphyry Copper mine, ably managed as a business enterprise, and always among the leaders in technical progress. Concentrating its first ore in 1911, it had by 1925 paid dividends totaling $30,000,000 or $40 per share on stock that had cost the public $5 per share in March, 1908. The ore, containing 2.5 per cent copper at the start, had become progressively leaner but the recovery had tended to improve. Production costs had gone up during the World War and the early post-war period; and had come down again. In all these respects it had followed the norm. If the mine had been abandoned as exhausted and the company had been liquidated late in 1925 (a program that had been given earnest consideration in 1924), Miami would have gone down into history a first-rate mining venture; as an active and progressive participant in the great Porphyry achievement. But Miami was not liquidated in 1925; instead it started to write the record of its second and really amazing story. Near the old mine was a large body of low-grade ore containing, in place, less than 20 lb. of copper to the ton, and without, incident- ally, any considerable sweetening of gold and silver. Any method of underground mining that was cheap enough would certainly entail some dilution, so that ore as sent to the concentrator necessarily would average much less than 20 lb. As a matter of record, the average for 1929 was 16.6 lb., from which 11.726 lb. was recovered as concentrate. As already said, the exhaustion of the older orebody during 1925 was foreseen; but in 1924 the decision was reached to enlarge the concentrator and develop a new mine. An expenditure of $2,500,000 was entailed in this program. By October, 1925, the

Jan 1, 1933

By R. A. Deju, R. B. Bhappu

Further information on the surface characteristics of the silicate minerals was obtained by experimentally correlating the oxygen-silicon ratio of the silicates with their electrokinetic properties. Specifically, the behavior of the minerals in an electric field was investigated using zero point of charge as a parameter. A modified electrophoresis cell was used for the determination of electrophoretic mobilities. It was shown that there is an increase in the zero point of charge with increasing oxygen-silicon ratio in the silicates. Finally, a chemical interpretation was presented to describe the surface phenomena observed in the experiments. In recent years great interest in surface chemistry has produced a number of methods to study the surfaces of minerals and to observe the phenomena occurring at their interfaces. One such method is discussed in this paper. A rather complete review of the surface characteristics of the oxide minerals has been undertaken by parks,' but, a similar study has not been made for the silicate minerals. Two previous papers by the authors2'3 attempted to remedy this situation. In these papers it was demonstrated that the reaction between the silicate mineral particles and acidic water involves mainly an exchange of metal ions for hydrogen ions on the surface of the solid, leading to an increase in pH of the aqueous phase. Also, the degree of reaction was found to depend on the oxygen-silicon ratio of the silicate structure, being least for the quartz and greatest for the olivines. A hypothesis was then set forth explaining that upon the fracturing of a silicate mineral, the oxygen-metal bond (which is almost entirely ionic in character) will break more easily than the stronger oxygen-silicon bond. This results in the exposure of unsatisfied oxygen sites on one hand and active, exchangeable cations on the other. These active sites on the fractured surfaces are then available for reaction with the hydrogen ions in acidified aqueous solution. Thus, an increase in degree of adsorption of hydrogen ions occurs as the oxygen-silicon ratio increases due to the presence of a larger number of active sites on such minerals. A correlation between oxygen-silicon ratio and electrokinetic properties will be further pursued in this paper from both the theoretical and experimental points of view. Efforts will then be made to present a chemical interpretation of surface phenomena observed in the experiments. It is believed that this study may supply pertinent information on the behavior of silicate minerals in froth flotation systems. ELECTROKINETIC STUDIES Equipment: In a previous paper,2 Deju and Bhappu described a simple method for determing the zero point of charge using a potential across a cata-phoresis cell and observing particle movement by means of a Rayoscope* optical system. This setup is simple in design and operation and extremely reliable. With care, reproducible results within 1.5% accuracy may be obtained. A new setup has been developed, based partly on the design by Zeta-Meter Corp.4 and partly on previous cells used at the New Mexico Bureau of Mines. This new, modified cell is shown in Fig. 1. Although

Jan 1, 1967