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By Donald P. Richards, John F. Abel

Geotechnical site investigation for new mine shafts can reduce the level of design uncertainty for shaft linings. The parameters which determine the lining strength required include rock strength and hydrologic properties, the in situ stress conditions, and the concrete strength. These parameters are applied to analytical methods of shaft lining design using the plastic and clastic assumptions of rock response to determine the required lining thickness to maintain the stability of the shaft excavation.

Jan 1, 1982

By John F. Blandy

IT is not my intention in this article to consider this subject in the light of the geographer or geologist, but rather in that of the mining engineer, and to endeavor to show the necessity and value to him of studying the minor details of the field or district in which he may be engaged. I t has been said by a distinguished geologist that "the natural boundaries of the geographer are rarely described by right lines. Whenever they occur, however, the geologist may look for something remarkable." And again : " Physiognomy is no idle or doubtful science in connection with geology. The physiognomy of a country indicates almost invariably its geological character." Our country furnishes examples enough of the truth of these remarks, and in no part of it is it so beautifully illustrated as in our own State, which has been so ably described by Prof. Lesley in his admirable little work on the "Topography of Coal." As the great mountain lines become guides to the geologist in determining and mapping out the geography of the formations, so do the minor details of topography become guides to the mining engineer in conducting his explorations, discovering of dislocations, and determining the character of the deposits which are the object of his search. I t is therefore requisite that he should, whilst making his surveys, pay the strictest attention to every variation of the landscape and surface of the ground. Until he has mapped out every feature he may be unable to read the geological changes which may have

Australian research scientists at the University of Melbourne's Institute of Materials Research have discovered two methods of extracting metals from raw ore, using brown coal. The discoveries could lead to extensive new markets for the brown coal producers of Australia (boasting the world's largest brown coal deposits in the Latrobe Valley region of Victoria), the United States and West Germany. Research on the extraction processes began at the University's Department of Metallurgy in mid-1969 under the direction of Geoffrey Cullen, manager of the Materials Research Institute. In June of this year. Cullen announced that both metal extraction processes, using brown coal, had proven successful.

Jan 1, 1971

By E. R. Parker, T. H. Hazlett

An understanding of the mechanism of creep of metals requires an accurate knowledge of shape of the time-deformation curve. An expression is developed which accurately expresses the creep curve for a number of structurally stable metals and alloys. VAST strides have been made in the development of high temperature creep resistant alloys; however, no sound understanding of the physical mechanism of creep exists to date. Consequently, creep resistant alloys are still developed by "cut and try" methods formerly so successful but now yielding returns at a continuously diminishing rate. It is apparent to all workers in the field that if the mechanism of creep were understood, much fruitless labor could be avoided. The dirth of fundamental knowledge has not discouraged the theorists. Speculation has flourished and numerous theories of creep have been proposed. A critical review of these theories reveals that, even though there are some general areas of agreement between the majority of the workers, there are many basic questions yet to be resolved.' It is generally conceded that theoretical speculation is far in advance of experimental evidence. The shortage of reliable creep data greatly hinders more rapid progress in this field. It is essential that the effects of different stresses and temperatures on the creep characteristics of metals be quantitatively determined. Once this has been accomplished, it will then be possible to evaluate the effects of alloying additions and, it is hoped, to provide a firm basis of facts for theoretical treatment of the creep phenomenon. The work reported herein was undertaken to determine the effects of such variables as stress, temperature, alloying, and structure on the creep characteristics of some metals. Material and Equipment Nickel was selected as the base material for the current investigation and an experimental program was initiated to determine the effects of temperature and stress on the creep characteristics of this material. Since a large quantity of high purity nickel was required for the proposed program and such material was not commercially available, it was decided to refine, cast, and prepare the required metal in our own laboratory. The resulting nickel test bars had the following composition, given in percentage by weight: Fe, 0.030 (1); Si, 0.003 (2); Ca, 0.001 (1); Mg, 0.020 (2); and S, 0.002 (2); to make total impurities of 0.056. The nickel (balance by difference) is 99.944 pct. The details of the purification process are described elsewhere.' This

Jan 1, 1954

By William L. Fink, H. R. Freche

The constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunckl analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoA16 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer13 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644' C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550" C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum-rich alloys prepared from electrolytically refined a1uminum.l Preparation of Alloys.—The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys. Chemical Analysis.—An analysis sample from each melt was chill-cast in the form of a plate 3/16 in. thick. In all cases the casting temperature was well above the liquidus. Cobalt was determined electrolytically in all alloys containing more than 0.05 per cent cobalt and by the nitroso-

Jan 1, 1932

By M. B. Yung

The Fu Chuan district lies near the eastern boundary of Kwang Si province in Southern China and is connected with the coast by the West river and its branches.

Jan 1, 1915

By P. R. Sperry

Aluminum alloy 3S was examined to determine the relationship between the applicable phase diagram and the microstructures produced under conditions tending toward non-equilibrium as well as equilibrium. The only phases present in the alloy were aluminum, (Mn,Fe)A16, aAI(Mn,Fe)Si, and silicon. It was found that the alloy behaved essentially as though it belonged to the Al-Mn-Si system. The effects of various solidification rates and of various homogenization treatments were studied. Particular attention was given to a nonuniform precipitate distribution which reflected the solute distribution in the cast aluminum solid solution. Some possible explanations for the solute distribution based on characteristics of the Al-Mn-Si or AI-Mn systems were discussed. ALUMINUM alloy 3s (aluminum plus 1.25 pct Mn) is one of the oldest and the most widely used of the wrought aluminum alloys. In spite of this fact, there are some aspects of the metallography of 3s which have not been revealed or which have not been brought to the attention of the metallurgist working with the alloy. The purpose of this investigation was to demonstrate in general how some of the fundamentals of equilibrium phase diagrams may be applied to the study of an alloy and to show specifically the origin of certain metal-lographic features of aluminum alloy 3s. It is hoped that this information can serve as a basis for solving specific problems relating microstructure to such things as mechanical properties, recrystallization, grain growth, and surface finish. Literature Survey Considering that alloy 3s contains only one alloying addition, manganese, it seems reasonable that it would have characteristics pertaining to the A1-Mn system. However, those characteristics might well be altered by the impurities in the commercial alloy, especially iron and silicon. Therefore, not only the simple binary but also more complex systems had to be reviewed. One characteristic of the A1-Mn system worthy of mention is its sluggishness, which leads to conflicting solubility data1,'2 and makes it relatively easy to supersaturate the solid solution and shift the eutectic composition during rapid solidification.3'4 Another characteristic is the strong influence which small amounts of impurities, especially iron, exert in lowering the solid solubility of manganese. Undissolved manganese is ordinarily present in an intermetallic phase, MnAl,, having an orthorhombic crystal structure. A metastable precipitating phase designated as "G" has been reported but small amounts of iron and silicon suppress this phase entirely." Raynor has established that MnA1, can dissolve a considerable amount of iron by a substitution of iron for manganese atoms up to 50 atomic pct.'" Consequently, in the Al-Mn-Fe liquidus diagram, the eutectic valley separating the primary aluminum and (Mn,Fe)Al, fields is fairly close to a constant Mn + Fe content." This is an important consideration in regulating the composition of 3s and also other aluminum alloys with high manganese additions."

Jan 1, 1956

By M. C. Udy, P. C. Rosenthal

THE use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace, The present study presents the results of a systematic survey of. the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels, Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. EXPERIMENTAL WORK Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. [ ] Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions . was prepared with boron additions in amounts of 0.0015, 0.003, and o,006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two com¬mercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120, Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel scrap were used for melting stock. Deoxidation was carried out in the furnace with o.10 per cent aluminum. The aluminum addition was

Jan 1, 1946

By Sidney L. Wise, Walter Strache

While the installation of mine bulkheads to retain water under high pressure is by no means a rarity, the following points which arose in the designing and placing of two of these bulkheads may be of interest: The Hibernia magnetite mine, located about 40 miles west of New York, in the State of New Jersey, is partly fillcd with water. This mine is located on an ore lens, the outcrop of which is over a mile long. The ore has been mined from this lens from the surface to a depth of more than 1,500 ft. It was held desirable to separate the old workings from the new, and to allow the former to fill to the 850-ft. level. Two weak places existed between the new and old workings below this Ievel: namely, a temporary bulkhead on the 10th level and a rock bulkhead of indeterminate thickness on the 16th level. When the matter of allowing the old workings to fill was investigated, the fact was developed that if these old workings were filled, the bulkhead on the 10th level would be subjected to a water pressure of about 50 lb. per square inch, and that 200 lb. per square inch would act on the 16th-level bulkhead. As the above-mentioned barriers were not deemed of sufficient strength to permit of these pressures, it became necessary to design and install new bulkheads. Design As the 16th-level bulkhead was required to withstand a pressure of 200 lb. per square inch, it presented some difficulties. A careful consideration of the various types of mine dams now in use led to the adoption of a design of the form of a truncated wedge. In this, the pressure side of the dam is of greater area than the hack, so that the resultant action is similar to driving the wedge. By cutting generous skewbacks in the walls, roof, and floor, this type in reality becomes an invisible arch. The wedge feature tends to compress the materials in the bulkhead, thereby adding to its imperviousness.

Jan 1, 1915

By Enid C. Plante

This paper deals with the flotation of the mineral fluorite (calcium fluoride) and of two associated gangue minerals, calcite and quartz. The aim of the investigation was to produce "acid-grade" fluorite, which must contain less than one per cent of silica. Several reagents are used successfully in practice for floating fluorite from its ores. Oleic acid is the most widely used collector, usually at temperatures above 60°C, with sodium silicate as a dispersant for quartz and quebracho or tannin to depress calcite. Sulphides (e.g., galena) are often removed first by xanthate flotation. Many investigators23 report results in which more than 80 pct of the fluorite is recovered in a concentrate assaying 96 pct or more of fluorite and less than I pct of silica. This investigation was undertaken with the intention of floating the gangue, which is the minor constituent of the ore, from the fluorite. Hence emphasis was first placed on the cationic compounds that float quartz. No satisfactory separations were obtained in this way, and other reagents were investigated to discover whether these were more effective than oleic acid in floating fluorite from quartz in the usual way. The first part of the paper describes experiments with several long-chain collectors available commercially. Most of this work has been by captive-bubble and cylinder flotation tests, with some batch tests in a flotation machine. The second part describes the use of sodium cetyl sulphate as a collector for fluorite and includes laboratory tests and extension of the work to batch tests in the flotation machine. A method for determining the adsorption of sodium cetyl sulphate on fluorite has been developed and is described. Theory of Collection by Paraffin-chain Salts It may be assumed that these compounds are adsorbed at the mineral surface in one or more of three ways outlined by Kolthoff:12 1. Exchange adsorption between lattice ions in the mineral surface and collector ions in solution. Closely related is adsorption by the collecting mechanism postulated by Taggart,17 in which there is metathesis between the collector and the mineral cation or anion. 2. Exchange .adsorption between adsorbed gegen ions (p. 67, ref. 19) and collector ions in solution. 3. Adsorption of nonelectrolytes (polar-nonpolar) without displacement of adsorbed ions. With cationic collectors, inorganic cations in the solution (e.g., hydrogen ion) compete with the collector ions and therefore act as depressants, while inorganic anions have the same effect with anionic collectors. From this follows the general conclusion that ions of the same charge as

Jan 1, 1949

By Eric R. Jette

In order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned. Heterogeneous Reactions The thermodynamic side of metallurgical reactions has received much attention in the past; the mechanisms, relatively, very little. The main reason for our present lack of information on the mechanisms of these reactions lies in the fact that every one of importance is a heterogenkous reaction; i. e., the substances involved in the reaction exist in more than one phase, while, if we neglect the large amount of work which has been

Jan 1, 1931

Lieut. Louis J. Brunel, now in France, was commissioned on July 27, 1917, as Second Lieutenant in the Engineers Reserve Corps, assigned to the 7th U. S. Engineers, Dec. 10, 1917, and has been with the American E. F. since Mar. 26, 1918. He was assigned to the staff of the General commanding the 5th Field Artillery Brigade, as Engineer Officer, on Aug. 6, 1918. E. Ross Housholder writes that "the record for pontoon bridge building was broken Sept. 25, 1918, by Section A, Co. 4, 5th Engineer Officers' Training School, at Camp Humphreys, Va., of which I am a member. The time was 15 min. 11 3/5 seconds. We then proceeded to break the record for dismantling in 9 min. 57 1/5 seconds. The length of the bridge section was 200 ft. The post band was sent out to meet us, and we feel proud of this record. I have met quite a few A. I. M. E.

Jan 11, 1918

By I. R. Kramer

A study was made of the effect of surface-active agents an copper, gold, and zinc single crystals as well as polycrystalline aluminum. The study on coppw showed that the maximum effect of the surface -active agent occurred at the same concentration of the solution as that at which the rate of solution of the copper soap was the greatest. Surface -active agents did not affect the creep behavior of gold or freshly polished zinc specimens. The creel-, rate of zinc specimens in a solution containing a surface-active agent zoas always lower than that of freshly polished specimens. In previous papers1'2 it was reported that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing dur- ing tensile deformation, it was found that the slopes of Stages I, 11, and In were decreased and the extent of Stages I and I1 were increased when the rate of metal removal was increased. The results of the investigation of surface-active agents showed that changes in the slopes and extents of Stages I and II occurred when single crystals of aluminum were deformed in tension in a bath containing solutions of paraffin oil and stearic acid. The amount of change was a function of the concentration of stearic acid and the maximum effect occurred at a concentration of 0.002 mole per liter. These results were interpreted2 in terms of the rate of solution of metal soaps which form as a result of the chemical reaction between the surface-active agent and the metal. According to this interpretation, the "weakening" effect is controlled by the rate of solution of the soaps which depends upon the concentration of surface-active agents. At low concentrations, the number of metal soap molecules formed is low; at high concentrations, the rate of solubility is low, because of the high degree of saturation.

Jan 1, 1963

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By L. A. Rapoport

This paper is intended as an aid in the perfornzance and interpretation of experimental studies of multi-phase flow in porous tnedia. The mathenmatical formulation of incompressible, two-phase flow phenomena in a three-dimensional porous medium is presented. The resulting equations which account for the effects of gravitational and capillary forces are used to derive general scaling laws permitting accurate representation of water-oil displacement processes by means of experimental flow models. The significance of the scaling laws is examined in the light of the physical concepts of micro-behavior of fluids in porous media. Formulations of scaling con(litions obtained by application of dimensional analysis are reviewed. The principles of application and the limitations of flow model studies are discussed. INTRODUCTION Most of the problems facing a reservoir engineer involve three-dimensional, two-phase flow systems. influenced by the effects of gravitational and capillary forces. Present computational procedures generally do not permit the evaluation of such systems without introducing greatly simplifying assumptions. The actual reservoir configuration is usually replaced by one or a combination of several "equivalent" linear systems, and the effects of capillarity and gravity are considered to be negligible. While these assumptions may in many instances be justified, there are a number of important practical problems for which the results obtained on the basis of such simplifications remain open to question. An alternate approach to the problems that are not amenable to analytical treatment consists of seeking their solution by experimental laboratory investigations. The main difficulty of such investigations lies in the fact that multiphase flow phenomena subjected to gravity and capillary forces proceed differently at different rates and in systems of different dimensions. Therefore, unless great discrimination is exercised in selecting the conditions and interpreting the results of laboratory tests, such tests may be entirely misleading in regard to field applications. The purpose of this paper is to present a theoretical background for the performance of laboratory tests that are more nearly representative of field behavior. It will be shown that simulation of field behavior can be achieved by conducting laboratory tests under conditions selected in accordance with definite scaling laws. The formulation of conditions required for the scaling of two-phase flow experiments in porous media has been presented in the literature on several occasions.12,3,4 One of these formulations advanced by Leverett1, cannot be considered applicable to most practical cases inasmuch as it does not cover generally the regime of laminar flow. An adequate treatment, based on the consideration of dimensional analysis, was presented by Engelberts and Klinkenberg.2 Their treatment, however, is concerned primarily with the scaling of linear flow systems, and hence somewhat limited in scope. Accordingly, the formulation of more general scaling laws, applicable to three-dimensional systems, appeared to be warranted. It appeared, furthermore. desirable to establish this formulation on the basis of a mathematical treatment, rather than by application of general principles of dimensional analysis, to permit more explicit

Jan 1, 1956

By Cyril Stanley Smith, W. Earl Lindlief

A study of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published' giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. Preparation of Allots The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 per cent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2 in. dia. cast-ing, the turnings being separated into three parts according to the position

Jan 1, 1932

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer's method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By J. H. Wernick

IN a study of the rate of decomposition of ½ -in. cubes of limestone, dolomitic limestone, and dolomite in a sweeping nitrogen atmosphere, Joseph, Beatty, and Bitsianesl found that the zone of calcination advanced at substantially a constant rate at a given temperature. The purpose of this paper is to show that their data indicate at least two processes occurring when the above carbonates decompose. It is suggested that there are two processes occurring temperature range and the other the limiting process over another temperature range. The data of Joseph and co-workers have been extended by use of the Arrhenius equation, Eq. 1, a relation beween the velocity constant k of a reaction and the absolute temperature T.

Jan 7, 1954

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957