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By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By F. Keller, E. H. Dix, R. W. Graham

Aluminum alloys containing relatively small amounts of magnesium and silicon are of commercial interest because they are readily workable in the annealed form and may be hardened and strengthened by suitable heat treatment. An intermediate temper can be produced in these alloys by quenching after a Solution heat treatment and the alloy in this condition can be formed easily. Artificial aging is required to obtain the maximum mechanical properties but this aging does not cause distortion nor require elaborate heat-treating equipment. The hardening of the alloys after quenching is attributable in part to the retention of the compound Mg²Si in solid solution, while the maximum hardness obtained by subsequent artificial aging is attributed to the fact that the solid solubility of the compound Mg²Si in aluminum decreases with decreasing temperature. Considering the importance of aluminum alloys susceptible to heat treatment, it is surprising how few fundamental investigations have been carried out on the aluminum-magnesium silicide alloys. This paper deals principally with the solid solubility relations of the compound Mg2Si in aluminum and is the sixth paper of a series1 from the laboratories of the Aluminum Co. of America reporting the results of investigations of equilibrium relations in aluminum-base alloys made from high-purity aluminum."

Jan 1, 1931

By Lawrence Addicks

T HIS has been a most momentous year in the annals of the Institute. We have been in the midst of a situation which, were it not for the convulsions of social unrest with which life is surrounded on every side, would have attracted the attention of the world at large. I do not refer to the desperate campaign for new members. That has gone on much as usual except that, this being leap year, the annual proposal to the M. & M. Society has been omitted. Nor do I refer to the desperate situation which we found in other directions, the spread of Bolshevism, the burning of the Engineers' Club, the fact that the selling of copper appears to have become one of the lost arts. No, I speak of the great question which has to be. settled once and for all, as to whether this great Institute should adopt simplified spelling. The whole trouble started in the ranks of the California Hysterical Society. It appears, while most of the San Francisco members can read and write, several of them cannot spell. It also appears that the Secretary, in editing the Transactions, has perhaps made just a little bit too much of a point of employing the correct Stoughton idiom. At any rate, the rebels filed an amendment to the constitution, and the stage was set for civil war, with perhaps more stress on war than on civil.

Jan 1, 1920

By W. B. Wise, H. D. Attra, W. M. Black

The purpose of this paper is to illustrate a comparatively new approach for solving a problem that has plagued oil producers for many years—how to make the most money with available field production capacity. In a very basic operation such as a top-allowable one-well field, a computer and staff of engineers are not required to determine that the best operation is to produce that well at its maximum for as long a time as it will produce. However, as the problem becomes more complex and the number of wells and number of reservoirs increase, it probably will be a wise choice to devote some engineering thought and calculation time to determine the best way to operate that field on both an ultimate and day-to-day basis. Continued developments in the field broadly referred to as "operations research" have led to a number of useful engineering analyses for optimizing field operational problems. One of these techniques, termed linear programing, is parlicularly interesting because of its potential applications to the study of complex oilfield operating problems. Linear programing is concerned with the problem of planning a complex set of interde~endenl activities in the best possible (optimal) fashion. A field application of linear programing is being used to maximize daily income from a multi-reservoir producing operation. The initial results of this study indicate that the linear programing technique (I) can be applied effectively to field problems, (2) can be used to detect unsuspected avenues for improving operations and (3) can effect a significantly improved means of controlling field operations through the use of the highspeed computer. INTRODUCTION The usual approach for studying complex field operational problems has been to look in detail at several basic plans suggested by judgement and experience and, then, to choose the best plan from those investigated. This approach is entirely satisfactory provided: (1) that judgment and experience alone will reliably pick the best or near the best program as one of the plans to be investigated; and (2), and most important, that the factors which control field production will not change. This paper deals with the large group of field operations which are at least one-step removed from a satisfactory solution using the conventional method of analysis. Problems such as pipeline- and gathering-system design, transportation studies, large field development projects and multi-reservoir producing operations fall in this latter category. To find the best program for handling these problems when the best program is not obvious, a complete optimization study is required, and high-speed computers are required to continually update the program once it is selected. Operations of this type have an extremely large number of possible solutions. However, only one will result in maximum economic return and, more important, this one program must be re-evaluated and adjusted constantly to accomodate such changing field factors as the number of producing days, the price of crude, the discovery of new reserves, declining reservoir pressure with subsequent decline in production and a host of other factors which characterize specific operations. One of the most widely used, direct methods of optimization is a numerical procedure termed "linear programing", which is designed to investigate systematically each of the possible solutions involved in a given problem, determining rapidly and uniquely the optimum answer. As implied by the name, linear programing requires that all field variables be either defined or expressed in a series of interdependent linear equalities or inequalities. These relationships are solved simultaneously, using a form of matrix solutions to determine the optimum values for each producing variable that will maximize net profits. The solution techniques used in a recent field case study is termed the "simplex method" and is discussed in full detail in Ref. 1.

By W. W. Anderson

A formula for quantitative efficiency is proposed, in which the efficiency value is a function of the improperly distributed material at the, gravity of separation effected by the cleaning equipment. The misplaced material is expressed as a percentage of the total material discharged from the equipment. Numerous examples are given, demonstrating application of the formula to various types of separation, including multiple-product separations.

Jan 1, 1950

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By J. G. Paterson, J. A. Meech

Abstract-Activated carbon is a strong adsorbent for amyl xanthate, capable of removing from solution up to a quarter of its own weight in xanthate. In selective flotation systems where depression is unstable, separation efficiency increases with activated carbon additions. The improvements observed are brought about by two mechanisms. First, by removing stripped and residual collector ions from solution, competition between depressant and xanthate is reduced and depression is stabilized. In addition, the texture of the froth phase at high pine oil concentrations is modified by activated carbon such that better drainage between the air bubbles takes place, alleviating the mechanical entrapment of depressed mineral particles. In treating a bulk copper/lead concentrate produced from GECO ore, selectively between galena and chalcopyrite is increased when activated carbon is used. Although the rate of flotation of galena is marginally lowered by activated carbon, a small extension in the duration of flotation allows the lead recovery to increase by 19% at the same recovery of copper. An addition rate of 0.75 kg/ton (1.5 lb/st) of bulk concentrate is suggested as optimum from this testwork. However, the actual level wed in the mill is dependent upon the residual concentrations of collector and frother in the bulk concentrate Pulp.

Jan 11, 1978

By George J. Young

(Cleveland Meeting, October, 1912.) I. GENERAL. THE recurrence of mine-fires in Nevada during the past decade is not only a matter of interest, but also one of considerable concern to engineers and mine-managers. The more important fires may he enumerated as follows: Forman Shaft fire., Gold Hill, April 21, 1903 ; shaft-house, machinery, and shaft, destroyed; loss estimated at $50,000.; Cause Unknown. Union Shaft fire, Virginia City, July 14, 1904; shaft-house, machinery, and shaft in part destroyed; loss estimated it $100,000; cause of fire stated as the careless throwing of a match in the rope-house. Sutro Tunnel fire, Virginia City, Jan. 27, 1909 ; 700 ft. of tunnel-timbering destroyed, and direct damage of $10,000; cause ' probably electric wires." Belcher Shaft fire, Gold Hill, Aug. 9, 1910; shaft-house destroyed, machinery ruined, and upper part of shaft damaged; damage, $25,000; no cause given. Belmont Mine fire, Tonopah, Feb. 23, 1911; fire started in winze ; 17 men killed. Giroux Mine fire, Kimberly, Aug. 23, 1911 ; fire originated iii shaft-station from unknown cause; 7 men killed, and $34,¬521 damage caused. (NOTE 1.-On June 11, 1912, some time after the present paper was written, a fire broke out in the pump-room on the 2475 station of the Ward shaft, Virginia City. This fire was caused by the short-circuiting and exploding of the starting-switch on No. 5 pump. The oil in the switch was scattered about and set fire to the timbers and laming of the pump-room. The pump-roan in charge notified the surface, and the * Professor of Mining and Metallurgy, Mackay School of Mines.

Oct 1, 1912

By Fred C., Fred C. Bond

Comminution energy is principally energy of deformation before breakage, which appears as heat. An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories are compared.

Jan 1, 1950

By Bernard MacDonald

THE writing of this paper was prompted by the discussion by H. M. Chance, in the April Bulletin, of the paper written by Thomas M. Chance which appeared in the February Bulletin., and by the remarks of the Editor in which lie stated that while the matter contained in discussion did not refer to the original paper it "was presented as of interest to the operators of cyanide and other lixiviation processes dealing with fluid mixtures of varying specific gravity." For some years past the principle enunciated in the discussion referred to has been known to the writer and demonstrated by him to be an efficient and economical way of separating water or solution from solids in the cyanidation, lixiviation or acid leaching of ore pulps: In utilizing this principle in commercial practice he has invented a method whereby not only the separation of solution from solids may be effected in any given tank, but also the counter migration of the solids and solution may be effected continuously through a series of tanks in which the hydro-metallurgical treatment of ore pulps is being carried on. In effect this method is analogous to the counter-current system, but is different physically in that it is carried on throughout a series of tanks on practically the sane level, continuously and automatically, by hydrostatic pressure and gravity-flow, without the aid of intervening pumps or elevators, at the same time that agitation is being carried on in the same tanks. In the Parral system, agitation is effected in tanks by a number of air lifts of comparatively small diameter through which the pulp is continuously transferred from the bottom of the tank and spouted horizontally on top of the charge. The spouting force of the several streams thus discharged maintains a rotary flow in the pulp charge which extends from top to bottom of the tank. This continuous transfer of pulp and the spiral flow from top to bottom of the tank maintains the pulp constituents in uniform proportions and meets the requirements of efficient treatment in a most economical manner. The quantity of. compressed air required is very small, as the pulp is not lifted but simply trans-

Jan 7, 1918

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 L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By H. C. Chao, Y. E. Smith, L. H. Van Vlack

ThE phase relationships for the MnO-MnS system have been investigated only in the eutectic region. wentrupl reported a eutectic at 1280°C (2345°F) with approximately 50 wt pct of each component, as based on the earlier work of Andrew, Maddocks, and Fowler.2 More recently silverman3 corrected these figures to 2275° ±10°F (1246°C) with 63 wt pct MnS and 37 pct MnO. Neither Wentrup nor Silverman investigated the solid-solution limits in this system. However, Wentrup did suggest with his phase diagram sketch that the maximum solubility of MnS in MnO is 10 wt pct, and the solubility of MnO in MnS is nearer 20 wt pct, Fig. 1. These figures have been utilized in subsequent publications without further verification.4 There had been evidence found in this laboratory that the above solid-solution figures were high. An investigation was therefore conducted using the following procedure. Samples containing MnO and MnS were contained in platinum foil, heated just above the eutectic temperature in a purified nitrogen at- mosphere, and quenched into distilled water. The MnO had been prepared by calcining reagent grade MnCO3 in nitrogen at 1400°C. Only MnO was detected in subsequent X-ray diffraction analyses. The MnS had been prepared by sulfur deoxidation of reagent grade MnSO4 according to the reaction: MnSO4 + S2 ? MnS + 2SO2 The details of the sulfide preparation procedure, which utilized atmospheric sulfur pressures at 950°C, are discussed elsewhere.5 The sulfur content of the sulfide was determined to be 36.8 * 0.2 pct, which matches the stoichiometric value of 36.9 pct. No evidence of either MnO or MnSO4 was detected microscopically or by X-ray diffraction. The single-phase combinations of MnO and MnS at the eutectic temperature indicate the limit of solid solution as shown in Fig. 2(a) and (c), and the revised phase diagram is shown in Fig. 2(d). The melting temperature for MnO is that provided by Glasser.6 The eutectic temperature of 1232° ± 5°C and eutectic composition of 64 wt pct MnS are in close agreement with Silverman's correction of Wentrup's work. The maximum solubility of MnO in MnS was determined to be 1.7 ± 0.2 wt pct. The maximum solubility of MnS in MnO was determined to be 1.8 ± 0.2 wt pct. These figures represent the lower limit for the presence of liquid at 1260°C and are significantly lower than the earlier estimated solid-solution figures. The authors wish to acknowledge the support of U.S. Steel's Edgar C. Bain Laboratory for Fundamental Research. The comments and critical suggestions of Drs. A. S. Keh, R. Rickett, and R. B. Snow are appreciated.

Jan 1, 1963

By John A. Meech, J. G. Paterson

Activated carbon is a strong adsorbent for amyl xanthate, capable of removing from solution up to a quarter of its own weight in xanthate. In selective flotation system where depression is unstable, separation efficiency increases with activated carbon additions. The improvements observed are brought about by two mechanisms. First, by removing stripped and residual collector ions from solution, competition between depressant and xanthate is reduced and depression is stabilized. In addition, the texture of the froth phase at high pine oil concentrations is modified by activated carbon such that better drainage between the air bubbles takes place, alleviating the mechanical entrapment of depressed mineral particles. In treating a bulk copper/lead concentrate produced from GECO ore, selectively between galena and chalcopyrite is increased when activated carbon is used. Although the rate of flotation of galena is marginally lowered by activated carbon, a small extension in the duration of flotation allows the lead recovery to increase by 19% at the same recovery of copper. An addition rate of 0.75 kg/ton (1.5 lb/st) of bulk concentrate is suggested as optimum from this testwork. However, the actual level used in the mill is dependent upon the residual concentrations of collector and frother in the bulk concentrate pulp.

Jan 1, 1979

By Thomas J. Menner

Jan 1, 1983

By V. H. Gottschalk, R. S. Dean

In the theoretical study of metallurgical reactions, it is necessary to make certain assumptions concerning the nature of metal-gas systems. The assumption usually made is that the reaction in such systems takes place predominantly with gas that is in "solution" and that the amount of solution follows the rules which have been developed for aqueous solutions; namely, Henry's law. The purpose of this paper is to inquire whether these assumptions are the best ones that present knowledge of gas-metal systems permits us to make. In the first part the extent to which a gas will dissolve in a metal and still follow Henry's law is considered. The conclusion is believed justified that the number of molecules of gas that can dissolve in a metal and have the system follow Henry's law must be small indeed. It is therefore improbable that the first assumption concerning the predominance of these dissolved molecules in reaction is correct. It is suggested that some improvement in the correlation of the probabilities with the assumptions made in the mass law equations would be made by the use of the dp law of Sieverts in place of Henry's law. However, the amount of gas that may be held in a metal so that it follows either Henry's or Sieverts' law is considerably outweighed in most metallurgical reactions by that held in gas-metal systems of entirely different structures and concerning which little experimental evidence is available. Some speculation concerning the nature of these is offered. The conclusion is that attention should be given to the determining of the nature of gas-metal systems and that the really fruitful application of the mass law and its connected calculations will have to await a more complete knowledge of these systems than we now possess. DISCUSSION (Paul D. Merica presiding) P. D. Merica, New York, N. Y. (written discussion).—The solubility relations of gases in metals, in so far as they are known from the pioneer work of Sieverts and others, have from the first presented certain challenging peculiarities. The authors have emphasized the significance of these characteristics and suggest that they point

Jan 1, 1933

By L. P. Davidson

The new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, 111., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the , equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment snd recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutid'ns can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—either as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" BC. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1944

By J. S. Koehler, F. Seitz

THE dislocation theory of plastic flow originated in 1928, when Prandtl1 suggested that the internal damping of metals of plastic origin might arise from the motion of a crystalline imperfection. Following this, Dehlinger2 employed a similar imperfection in a theory of recrystallization. The first detailed theoretical discussions were those of E. Orowan3 and G. I. Taylor4 in 1934. The resulting theory was gen- eralized by J. M. Burgers5 in 1939. Mott and Nabarro, in England, and Seitz and Read,6 in the United States, started an extensive examination of the atomic theory of dislocations in the period between 1939 and 1941. However, this development was arrested by the mar and was not taken up again until after 1945. Since 1946, the field has been the object of very intense activity, particularly in the United States and England. Dislocations are beautiful and intricate imperfections; they are sufficiently complicated to account for the great variety of phenomena encountered in the field of plastic flow. Above all, the dislocation concept enables us to understand how a metal or other plastic solid can deform inelastically under very small stresses at temperatures far below the melting point. Suppose we attempt to shear a perfect crystal plastically. This can be done by sliding one entire atomic plane simultaneously through one atomic distance with' respect to the near-

Jan 1, 1954

By Lyman Taylor, Alexander R. Troiano

STUDIES of the transformation of austenite at constant subcritical temperatures have been numerous since the work of Davenport and Bain.1 Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of austenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. EXPERIMENTAL PROCEDURE Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8-in. round bars. Bars were softened at 650° to 700°C. before the specimens were cut. [ ] Metallographic Method Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examination of partially reacted specimens. Thees specimens were approximately ½ by ¼ by 1/8 in. in size. Specimens of the 9 per cent Cr steel were held 10 to 12 hr. at 1200° to I225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 ½ hr. at 1200°C. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. No. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed in Table I. X-ray Methods Constituents were identified and martensite axial ratios determined from Debye

Jan 1, 1945

By Frederick Rhines

PURE copper that has been allowed to oxidize at an elevated tempera-ture in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cupric oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig. 1a). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composed of oxide particles precipitated in a matrix of metallic copper that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,1 it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but will separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (1) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940