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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 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 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. 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

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 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

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

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 G. S. Cole, G. F. Bolling

ThIS note accompanies a study of grain structure changes in metal ingots produced by the alteration of fluid motion.1 Although the Prandtl Number of aqueous solutions is much higher than that for metals, it is quite instructive to see the simulation of freezing, as pointed out by Jackson and coworkers.2-4 Accordingly we have observed the effects of natural thermal convection, the changes induced by a steady-state rotation in one direction, and the changes under oscillation.' Temperature measurements were made under duplicate conditions whenever the visual observations appeared interesting. A solution of 15 pct NH4C1 in water was chosen. In each case the solution was preheated to 90°C in a 4-in.-diam Pyrex beaker filled to a level of about 5-in. depth and covered to prevent convective air cooling. The beaker was then placed in a container of iced brine, suitably arranged on a rotating table for movement about its cylindrical axis. Upon immersion in the brine under static conditions, fluid flow was observed near the wall of the beaker before the onset of crystallization, which generally commenced only after the temperature fell to 51.5"C. The region of flow extended about 1 mm from the wall and could not be observed elsewhere. The measured radial temperature increased sharply within 1 cm from the wall and thus over a distance considerably greater than that observed for the flow. However, we note that this difference of approximately one order of magnitude between hydrodynamic and thermal boundary layers should be expected for aqueous solutions, in contrast to metallic liquids. Beyond this layer the temperature was isothermal at a given height and in general nearly 10°C warmer than at the wall. The overall visual observation was therefore supported quite well by temperature measurement. There was also a vertical temperature gradient of nearly 2°C per cm throughout the liquid increasing from the colder bottom; this of course could not be observed visually. Eventually crystals precipitated from solution. (It

Jan 1, 1968

By E. J. Whittenberger

OVER the past two decades, the Cr-Ni stainless steels, popularly termed 18-8 steels, have been used in ever increasing amounts in the aircraft, automotive, chemical, transportation, and building industries.' The contribution of nickel to these steels is associated with its strong austenite forming tendencies which assure good hot and cold forming characteristics, and with its beneficial influence upon corrosion resistance, especially in oxidizing acids. The adjustment of the chromium and nickel contents has been used advantageously in controlling the rollability and the response of the mechanical properties of these steels to cold reduction. With the advent of the jet age and the government stockpiling of nickel, considerable emphasis has been placed upon the development of satisfactory low nickel or nickel-free substitute austenitic stainless steels, especially for nonmilitary applications.2 Fer-ritic 17 pct Cr (AISI Type 430) stainless steel has been effectively substituted for the austenitic grades in applications with mildly corrosive exposure. However, the limited formability and ferromagnetic behavior of this grade do not permit its satisfactory use for many applications. To achieve better formability in a nenmagnetic steel and conserve nickel, a number of low nickel substitute austenitic grades of stainless steel have been developed in recent years. In most of these steels, manganese and nitrogen have been substituted for a portion of the nickel content, for example, 17 pct Cr-4 pct Ni-6 pct Mn (AISI Type 201), 18 pct Cr-5 pct Ni-8 pct Mn (AISI Type 202), and 16 pct Cr-1 pct Ni-17 pct Mn, all of which contain approximately 0.15 pct N.1 The precipitation of ferrite when large ingots of these Cr-Ni-Mn-N steels are heated to temperatures high enough for conversion to slabs on conventional universal slabbing mills has seriously affected the hot workability of these steels. This has been especially true in the case of the 16 pct Cr-1 pct Ni-17 pct Mn (sometimes referred to as 15 pct Cr-1 pct Ni-15 pct Mn) composition." Because it is possible that little, if any, nickel will be available for nonmilitary stainless steel applications in the event of a national emergency, a need has existed for a nickel-free austenitic stainless steel containing hot and cold forming characteristics similar to 18-8 steels and corrosion resistance at least comparable to the 17 pct Cr ferritic steel. The aforementioned deleterious effect of ferrite upon the hot working characteristics of the 16 pct Cr-1 pct Ni-17 pct Mn, steel indicates the importance of establishing the austenite-austenite plus ferrite phase boundaries as the first step in the development of nickel-free or low nickel substitute steels. This paper presents the data collected in an elevated temperature constitutional study of the Cr-Ni-Mn-N system at the South Works of the United States Steel Corp. Experimental Procedure The 300 compositions used in the investigation were melted in a 26 Ib induction furnace and cast in 3 14 in. diam by 18 in tall hot-tcpped ingot mo1ds.

Jan 1, 1958

By C. D. Hunter, I. B. Browning, N. W. Shiarella

During the year 1936 improvement in the oil industry in Kentucky continued at about the same rate as shown by that of the year 1935 over the year 1934. The development of several new pools in western Kentucky and the increase in the application of repressuring methods to the old fields of eastern and to a lesser extent of western Kentucky increased the total production to 5,481,227 bbl., as compared to 5,175,054 produced in 1935. The principle sources of this increased production are the Livermore field and the new Bates Knob field in McLean County, in western Kentucky, and the result of repressuring operations in the " Corniferous" pools of Lee, Powell, Wolfe, Morgan and Estill Counties and the "Weir" sand (of Mississippian age) fields of Magoffin, Lawrence and Johnson Counties in northeastern Kentucky. The last named fields have a producing sand especially adaptable to these methods. Drilling No new fields were opened in eastern Kentucky during the year. All new drilling was codned to pressure wells and new oil wells to complete patterns around the intake wells. Owing to the relatively low "initial" or flush production of the wells in this section—even though the ultimate recovery per acre is as large—higher prices for crude will have to prevail before extensive search for new fields is begun; as in northwestern Kentucky, where active exploratory work has been carried on as in the several preceding years, resulting in numerous new and prolific, although comparatively small fields. In this section approximately 500 new oil wells drilled in the Owensboro field, embracing several pools in Ohio, Hancock, Daviess, McLean, Henderson, Webster and Nuhlenberg Counties in the northwestern part of the state. The total oil production for this field during 1936 exceeded by many thousand barrels the 2,821,722 bbl. produced in 1935. In these fields the producing sands range from the middle Missis-

Jan 1, 1937

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann's twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a '(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.' By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2'3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By Paul L. Russell

7.5-1. introduction. The possible engineering uses of nuclear explosives were recognized with the first nuclear detonation. Subsequent experiments have demonstrated the ability of nuclear explosives to move very large volumes of rock and earth efficiently and at costs below conventional earth-moving methods. The ability to package a quantity of energy equivalent to a few million tons of conventional explosive in a container approximately 20 ft long and 36 in. in diameter enables easy emplacement and thus provides the potential for excavation on scales heretofore impossible. Space does not permit detailed discussion of the many experiments with conventional high explosives and with nuclear explosives that were performed in developing the information presented here. A bibliography is included for those wishing detailed information. Material from those sources and from personal experience has been used freely. 7.5-2. Nuclear Explosives. An explosion, in general, results from the very rapid release of a large quantity of energy within a limited space. This is equally true for both conventional and nuclear explosions, although the energy is produced in quite different ways. In the case of a conventional explosive, this energy arises from chemical reactions. In a nuclear explosion, the energy is produced as a result of the formation of different atomic nuclei by the redistribution of the protons and neutrons within the interacting nuclei. Nuclear energy is of a much higher order of magnitude than chemical energy when equal masses are considered, and the release of this energy is a thousand times more rapid than the fastest chemical detonations. Explosions may be produced by fission or fusion reactions. FISSION. When a free (or unattached) neutron enters the nucleus of a fissionable atom, it can cause the nucleus to split into two smaller parts. This fission process is accompanied by the release of a large quantity of energy. The complete fission of 1 lb of uranium can produce as much energy as an explosion of 9,000 tons of TNT.

Jan 1, 1968

By D. F. Kaufman, E. D. Levine, L. R. Aronin

The deformation of' impure beryllium crystals by basal glide at room temperature invariably tevminates by basal cleavage after a few percent strain. It is generally accepted that .fracture of this type is caused by the splitting of low) -angle boundaries, or bend planes, by obstacles that restrict the motion of the bed planes in the deforming crystal. The details of such a process have been developed by Stroh, who showed that the high tensile stress norrnal to the basal plane in the region where the bend plane is split results in the propagation of a basal cleavage crack, provided there is no available dejorvrlatzon mode having a shear component normal to the basal plane It has been postulated that puvification of beryllium might lead to increased basal ductility by the vemoval of barviers to bend plane motion and possibly by the activation of nonbasal defor~rlation systems. Large increases in the amount of basal glide that can he sustained prior to fracture have been observed in crystals purified by zone refining. In each case, eventudal fracture was by sharp basal cleavage, suggesting that the split bend plane model still applies to tile fracture of beryllium of rensonably high purity. In the present work, calculations are made to show to what extent basal duetilits can be increased by purification while the split bend plane .fracture process remains applicable. Experimentally observed ductilities are generally somewhat lower than those predicted by calculation because of premature failure due to defects introd~cced during specimen preparation and testing. SEVERAL investigators1-4 have studied the deformation characteristics of beryllium single crystals of commercial purity, and have related the strong anisotropy of plastic deformation in single crystals to the problem of brittleness in polycrystalline beryllium. For most orientations, the principal deformation mode is basal slip, which, at temperatures between 300" and 900°K, begins at a critical resolved shear stress of approximately 1500 g per sq mm and terminates after 3 to 6 pet glide strain by cleavage on the basal plane in the neighborhood of (1120) bend planes that are formed during the deformation. This type of fracture, which is also observed in zinc at low temperatures, has been interpreted by stroh5 to be caused by the splitting of bend planes by obstacles to their motion. In the Stroh model, a (11.20) dislocation wall, or bend plane, moving along the slip direction under the action of the applied stress, encounters obstacles which cause part of the bend plane to be held up, the other part continuing to move. Stress concentrations are built up in the region where the bend plane is split, with a high tensile component normal to the basal plane, resulting in a microcrack at the end of the split wall. Because no deformation mode having a shear component at an angle to the basal plane is available to relieve the stress at the crack tip, the crack can propagate under a sufficiently high applied stress. The Stroh criterion for crack propagation is given by

Jan 1, 1964

By John McGhee, Jack Newcombe, M. J. Rzasa

A series of water floods was made on laboratory prepared unconsoli-dated sand columns to study the effects on oil recovery of the solid-water-oil contact angle, the oil-water interfacial tension, flood rate, and oil viscosity. A procedure was developed for treating silica sand with silicone polymer to produce surfaces of varying degrees of wettability as evaluated by measuring the contact angle on a flat silica plate that had been simultaneously treated with the sand. Fluid interfacial tensions were changed by the use of surface active agents in the flood water. Water-wet, oil-wet, and intermediate wettability systems were studied at high and at low values of interfacial tension, at several flood rates, and with oils of different viscosities. For both oil-wet and water-wet systems and a low viscosity oil, recoveries were functions of the oil-water interfacial tension; also, increase in flood rate resulted in increased oil recoveries. High interfacial tension floods were more efi- cient than low interfacial tension floods on water-wet systems, while low interfacial tension floods were more eficient on oil-wet systems. Intermediate or neutral wettability systems were less sensitive to rate of flood advance and interfacial tension than either oil-wet or water-wet systems. The eflects of surface forces on oil recovery for high viscosity oils were not so well defined as for low viscosity oils. INTRODUCTION Reservoir rock surfaces vary in their wettability1, some being water-wet while others are apparently oil-wet. The factor of wettability enters into reservoir performance in both primary and secondary recovery, and into laboratory measurements of capillary pressure, connate water saturation, and relative permeabilities.' In theory, the degree of wettability is measured by the contact angle for the system solid-water-oil. A water-wet system is defined as one in which the advancing water contact angle is less than 90". An oil-wet system is one in which the advancing water contact angle is greater than 90°.3 The surface forces in a solid-water-oil system are related by the Young-Dupree equation as follows4: These surface forces are commonly expressed as the difference in adhesion tension, or the product of the water-oil interfacial tension and the contact angle. If the contact angle is less than 90°, the adhesion tension difference is positive and oil displacement by water from a solid surface will be spontaneous and favored by a high oil-water interfacial tension. If the angle is greater than 90" the displacement will not be spontaneous but will require less energy the lower the oil-water interfacial tension. The contact angle and interfacial tension also appear in the capillary pressure equation5: PC = 2ocosejr .... (2) The quantity cos was used by Rapoport and Leas6 s a factor in the generalized form of their "sealing coefficient." Warren and Cal-houn' presented the results of cos on oil recovery in oil-wet systems and correlated their data using a "scaling coefficient" suggested by Jones-Parra and Calhoun.8 The "sealing coefficients" were advanced to help correlate the effects of the variables influencing oil recovery by

Jan 1, 1956

By R. S. Hoch, Roy A. Bobo

Maintenance of desirable plastic flow properties of weighted drilling muds may be greatly simplified by use of centrifugal classification to control the drilled solids content. The new application of a decanting type centrifuge to separate and reject the low density solids from the weighting material results in a drilling mud of greatly improved quality with lower values of yield and rigidity. Its practicality and economy has been proven in field operation. The degree of separation of light and heavy solids is not limited by the machine, but by the particle size distribution of the solids in the mud. Removal of the low density component of drilling mud that makes chemical treatment necessary permits a marked reduction in chemicals. The main uses of the centrifugal process are the treatment of muds while drilling, the reclaiming of discorded muds, cleaning up of workover muds, and the reduction in lime content of mud for completion. INTRODUCTION Drilling mud in any circulatory system is made viscous and difficult to pump by gradual accumulation of drilled solids which pass through the shale shaker and are continually reground. In a weighted mud containing a large proportion of barite by volume, the amount of drilled solids that may be tolerated is greatly reduced. Much effort has been expended to control by chemical treatment the effects of such solids. Though chemical treatment is quite effective, the time eventually comes at deeper depths after enough drilled solids have entered the system when a portion of the mud must be discarded and replaced with water and more weighting material. Once begun, this process is generally continued at frequent intervals with resultant high maintenance costs. At the termination of drilling, mud highly contaminated with light solids and spent chemicals is poorly suited for completion operations.' It is likewise limited in utility for other drilling operations. This investigation was conducted for the primary purpose of determining an acceptable mechanical means of removing the lightweight solids from weighted drilling muds in order to maintain viscosity at a minimum. A decanting type of centrifuge was selected from the various possible methods of mechanical separation. The centrifugal process has been employed in this country for this purpose in central mud reclamation systems in California in earlier years. It also was used for treatment of weighted muds on the Gulf Coast.' In more recent years only sporadic attempts have been made to employ it in the field on weighted muds. DISCUSSION OF PROCESS Selection of Apparatus Two factors favor mechanical procedure for the separation and removal of drilled solids or clays from the mud circulatory system. First, the greater specific gravity, 4.1 to 4.3, of the barite would promote more rapid settling than the clays whose specific gravity range is from 2.5 to 2.7. Second, the relative coarseness of the barite particles also facilitate faster settling of this phase. A decanting type of centrifuge was preferred for this process over other possible methods for these reasons: 1. Requires no costly additives or excess dilution. 2. Centrifugal force affords greatly accelerated separation as compared to gravity.

Jan 1, 1955

By W. R. Opie, O. W. Mole

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.' The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.' Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.

Jan 1, 1961