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By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

By William G. Pariseau

A plasticity theory for anisotropic geologic media has been applied to the problem of quasi-static wedge penetration of rock under confining pressure. Numerical evaluation of the governing system of stress equations in the transversely isotropic and orthotropic cases using representative material properties shows that the consequences of initial anisotropy for the penetration process are by no means trivial. In the transversely isotropic case, a threefold increase in the vertical force required for penetration to a unit depth occurs as the inclination of the axes of anisotropy are rotated through 90° with respect to the penetration path. The horizontal force required varies from zero to a maximum at approximately 60° then back to zero as the axes of anisotropy are rotated. The maximum is of the order of magnitude of the force required in the isotropic case. Similar results are observed in the orthotropic case. Practical aspects of the post-elastic phenomena associated with anisotropic rock indentation within the context of drilling problems include: bit yaw, hole deviation and bending stresses in the drill rod, all of which vary with strata dip but which can be quantitatively evaluated given the bit geometry, interface friction and rock properties. In a broader context, the analysis reveals the necessity for well conceived experimental work and sound theoretical research concerning post-elastic behavior of geologic media as a function of confining pressure, the effects of induced anisotropy, and the variation of strength parameters with loading path changes in the post-elastic range.

Jan 1, 1971

By Wayne S. Cavender

During the past year, geochemical prospecting appears to have come of age as an exploration method, and its acceptance by the mining industry is widespread. There is a growing recognition that applied geochemistry is a scientific tool and must be performed and interpreted by scientific personnel who are trained in its utilization. At present, most personnel training is done by geochemical departments in government organizations and industry groups. Most schools in the United States and Canada do not offer geochemical training, particularly at graduate levels, due to faculty limitations, lack of budgetary support and the erroneous impression that applied geochemistry is not sufficiently academic. As a result, some companies have found it expedient to send selected personnel to European schools for advanced training. A critical personnel shortage now exists will probably continue into the near future. Indications are that the rate of development of new geochemical techniques has levelled off, and the probability of new breakthroughs is not high. Present research is essentially limited to efforts by government agencies and a few private companies. Progress has been the most rapid in the development of analytical techniques, but the need remains for investigation into sampling technology and the development of more quantitative methods for the interpretation of geochemical results. Geochemists need a better understanding of the numerous physical and chemical factors which affect and control primary and secondary dispersion phenomena in all geologic environments. Detailed studies must be made of the relationship between geologic, geochemical and geophysical factors. With better interpretive techniques, the return on the geochemical exploration dollar will increase.

Jan 2, 1968

By A. Perry Thompson

Discussion of the paper of A. PERRY THOMPSON, presented at the San Francisco meeting, September, 1915, and printed &apos;in Bulletin No. 100, April, 1915, pp. 645 to 677. ARTHUR S. EAKLE, Berkeley, Cal.-At the old Morning Star mine in Alpine County, where large masses of enargite were found some years ago, I looked particularly for evidences of replacement of pyrite by the enargite. While I have not made a particular study of any of the specimens, I judge that the pyrite and enargite were precipitated together. They were both primarily in those rocks. Of course, by using Mr. Graton&apos;s method of determination we might possibly find a situation somewhat different, but I should say that the enargite is not replacing the pyrite, but was simply precipitated at the same time. The bodies occurred there within 50 ft. of the surface, so it is probably not a case of secondary enrichment. H. W. TURNER, San Francisco, Cal.-In the case where secondary chalcocite shows a crystalline structure and cleavage lines, what is the evidence of the secondary nature of it? C. F. TOLMAN, Stanford University, Cal.-You can find practically all the evidences we have discovered in the microscopic study of ores. You can find all stages in the process of replacement of earlier minerals, especially bornite, by chalcocite, from a stage, in which the process has but just started with only occasional fragments of chalcocite set in bornite, to a stage where remnants of bornite are set in chalcocite. The replacement may take place along the cleavage lines or along the crystallographic directions of the earlier mineral, or it may take place irregularly. In one type of replacement you may find in one spot a few cross-cutting veins, and in another spot the latter may be so enlarged that there remain only a few individual specks of the replaced mineral.

Jan 12, 1915

By M. Gensamer

THE stresses which initiate deformation processes in metals are funda-mentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals1 has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.2 It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. ? Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals.

Jan 1, 1938

By D. F. Hewett

[In an increasing degree in recent years, especially since the war, men in many parts of the world are turning their attention to the problems of the future, attempting to appraise the basis and extent of man&apos;s progress and interpret the problem that he faces in the near future. The war made clear to ma persons the degree to which modern industry depends upon t continuous flow of enormous quantities of raw materials, a especially of the minerals. In many circles throughout t world, the question of adequate supplies of the mine especially the fuels and metals, for near as well as more remo needs is receiving serious consideration. As a result, persons representing the state as well as industry are looking to geologists and engineers for all the data that throw light on the distribution, extent and availability of the minerals that must serve coming generations.] Obviously, in a brief research I have been able to consider only a few sources of the metals in Europe, perhaps fifty out of a total of many hundreds. In order that the conclusions may have value, however, I have chosen districts which have been important sources during some epoch of the last three hundred years or more.

Jan 1, 1932

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By C. E. MacQuigg

BY and large the education of the engineer has been conservative and the reasons for this are obvious. Quite properly it has been a tradition of engineering education that facts and not fancies must be adhered to. Without a doubt, those men who formed the mold of our engineering philosophy as much as it is possible for such molds to be established-rightly held the highest standards of intellectual honesty. Fortunately, it was unthinkable to them to temporize with untried theories and naturally the men whom they trained as engineering educators carry this philosophy in turn to their students, thus handing down the tradition of stability.

Jan 1, 1943

By F. F. Aplan

Pollution control will be of utmost importance in the 1970&apos;s. In this area, the mineral process engineer has a special competence to understand and remedy many pollution situations. There is an old adage that goes, "Build a better mouse- trap and the world will beat a path to your door." Would that it were so, but the reality of the situation is such that, just as a supplier must sell his machine, a professional man must sell his competence. It is a sad but true fact that mineral processing engineers have not done a very good job in selling their extensive competence in the control of a broad range of pollution problems. Recently one of our students visited a paper pulp mill where he was shown a foam fractionator used to remove paper pulp fibers from plant discharge waters. "Foam fractionator hell, that&apos;s a flotation cell!&apos;&apos; was his comment. Ah so, it would appear that large numbers of technical people consider themselves experts on "foam fractionation" Or is it that we have been very remiss in demonstrating the usefulness of our equipment and processes and our professional competence to solve, these pollution problems?

Jan 1, 1970

By A. L. Lee, M. H. Gonzalez, R. F. Bukacek

Experimental viscosity data for methane are presented for temperatures from 100 to 340F and pressures from 200 to 8,000 psia. A summary is given of the available data for methane, and a comparison is presented for that data common to the experimental range reported in this paper. Correlation of the data is presented, and predicted values are given for temperatures up to 460F and pressures up to 10,000 psia. INTRODUCTION The increasing ranges of temperature and pressure at which fluids are produced, transferred and processed in the petroleum and chemical industries stress the need for accurate information on physical properties, both for engineering calculation and for improving the methods used to estimate physical properties. A survey of the literature reveals that disagreements between published data on the viscosity of methane are common and that most investigations have been conducted over restricted temperature and pressure ranges. This situation made it desirable to undertake an investigation with a scope common to most of the literature data available. APPARATUS AND MATERIALS The apparatus used in this investigation was the capillary tube viscometer&apos;described by Dolan,10 with modifications introduced in the general design and operation of the instrument. It has an effective pressure range from 14.7 to 10,000 psia and a temperature range from room temperature to 400F. The design of the viscometer is based on the establishment of a manometric head between two vessels containing the test fluid and a volume of mercury. The reservoirs are connected by a capillary tube through which the test fluid flows and a tube through which mercury flows. A pressure gradient is established by elevating one of the vessels above the other, the resulting flow of mercury displacing the test fluid through the capillary. The schematic diagram of the system (Fig. 1) shows the arrangement of the equipment auxiliary to the viscometer. The density cells assembly (E, Fig. 1) was not used in this investigation since reliable data are available on methane. 23 The assembly consists of a bank of eight 316 stainless steel pycnometers. Experimental values of the density of a natural gas19 and i-butane14 samples have been obtained for pressures up to 8,000 psia and temperatures up to 340F. The methane used was obtained from the Southern California Gas Co. Mass spectrometric analysis showed a composition of 99.8 percent CH4, 0.1 percent C2H6 and 0.1 percent C3H8. EXPERIMENTAL VALUES AND ACCURACY OF DATA Determinations were carried out at several temperatures. With the temperature in the cabinet controlled at a given level, a series of runs were made at various pressures. To establish pressures lower than that obtained from the methane cylinder, it was necessary to vent the gas slowly to the atmosphere until the desired pressure was reached. The consistency of the test run time for a particular condition can be used as a criterion for the accuracy of the data. A further check is obtained by comparison of the viscosity values obtained using different driving heads. To establish the instrument&apos;s reproducibility, a large number of runs were made at three completely different conditions of temperature and pressure. Data obtained were analyzed statistically to determine the most reliable value for the variance of the experimental data. It was found that the variances of the data taken at different experimental conditions were not statistically equivalent, but they were small. The largest variance was found at 8,000 psia and 100F, where the standard deviation was 0.385 micropoise. Therefore, 99.9 percent of the data can be expected to fall within 1.15 micropoises of the population mean, except for the intervention of systematic errors in operation.

By H. M. Myers, J. E. Funk

The two-phase flow of a drilling fluid in a diamond drill bit is investigated by deriving and solving the steady-state continuity and momentum equations. Parameters in this analysis are rotational speed of the bit, local rate of addition of drill solids, non-Newtonian nature of the drilling fluid and drilling rate. The describing equations relate the flow and pressure drop to the design characteristics of the bit. The equations are integrated numerically yielding the flow-rate pressure drop characteristics for the bit, flow distribution in the bit and velocity and static pressure as a function of position in each flow channel of the bit. Results are presented for a particular bit design. This paper shows that under normal drilling conditions certain parameters may be neglected in the hydraulic calculations for a diamond drill bit. Therefore, shortened forms of the equations presented can be used to fit the proper diamond bit to the drilling fluid hydraulic system. INTRODUCTION Like the conventional bit, the diamond drill bit is a key component in the circulating system of a well. The conventional rock bit is fitted to the circulating system by selecting the flow nozzles which provide the system with the proper flow-rate pressure drop relationship. Fluid behavior across the face of the diamond bit must be better understood so the bit can also be fitted to the circulating system. Data from field-operated diamond bits are presently available and do yield some information regarding the flow-rate pressure drop relationship. However, the number of factors affecting this relationship is quite large. Drilling parameters and conditions such as bit penetration rate, bit weight and rotational speed are important. Moreover, flow channels in the bit are part of the cutting head, and introducing drilled solids into the flow channels reduces the flow area, causes additional drag and influences the pressure drop. Many tests would have to be performed if field tests were required to study all parameters which might influence fluid behavior in the bit. A logical approach to this problem is to investigate analytically the fluid behavior in the bit, including parameters that are present under normal drilling operations. This approach, which seems to offer the best method for future studies, is presented in this paper. Following is the general procedure. 1. Equations describing the most general flow channel are written and include the addition of drilling solids (which is related to penetration rate), rotation of the bit, design parameters of the bit and non-Newtonian properties of the fluid. 2. A typical bit is designed and the bit parameters are substituted into the equations. 3. Parameters are assumed (penetration rate, rotational speed of the bit, mud weight, etc.). 4. The describing equations are numerically integrated to obtain the pressure drop across the face of the bit as a function of flow rate. 5. The pressure-drop contribution of each component (friction, acceleration, etc.) is obtained from the numerical solution, and those factors which largely influence the total pressure drop are identified. Classifying the drilling fluid is important in establishing the friction factor relationship since the frictional pressure losses are the main contributors to the total pressure drop. High-density drilling fluid is commonly assumed to be a Bingham plastic. 1-3 Govier4 presented a method for selecting a friction factor in the laminar flow region from the rheology properties of the mud and a modified Reynolds number. Metzner5 presented a criterion for selecting the friction factor in the turbulent flow region. The bit design used in conjunction with the solution of the equations has divergent flow channels. Stall, which is the backflow of fluid in the channels due to eddies that occur on the outer perimeter of the flow stream, can occur in these divergent channels (or diffusers). When stall does occur the static

By A. H. Roberson, L. H. Banning

DURING the past few years, a considerable tonnage of ilmenite has been produced as a byproduct of a monazite dredging operation and stockpiled near Boise, Idaho. This ilmenite has not been marketed because of the long distance from ilmenite-consuming areas and its comparatively low TiO2 content. Production of monazite from the alluvial sand deposits of Idaho is a mar- ginal venture when it is the only marketable product, and it will be necessary to establish a byproduct market before the operation becomes economically stable. Early in 1954, the Bureau of Mines Northwest Electrodevelopment Laboratory at Albany, Ore., conducted a series of tests which demonstrated that arc furnace smelting could be utilized to produce commercial quality pig iron and a high titanium content slag from these ilmenites. Additional studies showed that the slag chlorinated readily to produce a satisfactory yield of TiCl4. The investigation was carried out by two research teams. The Ferrous Metals Branch, with adequate

Jan 1, 1956

By H. J. Modi, P. L. De Bruyn

IN recent years interest has been aroused in flotation rate studies both from a technical and a more practical aspect. With increasing fineness of grind becoming a necessity in treatment of low grade ores, difference:; in flotation rates of various size ranges will assume importance in the evaluation of overall recovery results. Theoretical analysis of flotation kinetics was initiated by Schuhmann,&apos; who sought to define flotation rate of a given mineral and specified size range in terms of certain physical variables of the flotation system. Using as a basis for his analysis the bubble-particle encounter hypothesis previously advanced by Gaudin,&apos; Schuhmann writes for the rate of flotation (R,.) of particles of average size x, Rx = PcPa(x) V F. [1] In this relation Pc and Pa represent, respectively, the probability of collision between particle and gas bubble in a given time interval and the probability of adhesion of particle to the bubble after collision. Rigorously speaking, the term PC does not have the significance of a probability factor, since it depends on the time interval and therefore can be numerically greater than unity. The term c(x) expresses the concentration of particles of an average size x in the flotation cell in weight per unit volume of pulp, and V denotes the total volume of pulp in the cell. The product, P,c(x)V, defines the frequency of particle-bubble collisl.on, and when it is multiplied by P,, the number of collisions per unit time resulting in successful adherence is obtained. The factor, F, measures the froth stability and is introduced because after fruitful bubble-particle contact some particles may still riot reach the froth launder. Coalescence of bubbles in the froth column or too short a bubble life could account for this effect. Schuhmann also introduced the concept of "specific flotation rate" (Q) to allow for the relative abundance of different mineral species in the flotation pulp. The specific flotation rate, having the dimension of reciprocal time, is defined as Eq. 2: Qx =Rx/c(x)v [2] and it also follows from Eq. 1 that Qx = PcPaF. [31 The theoretical aspects of flotation kinetics were also considered by Sutherland,3 who tried to improve Eq. 1 by expressing the probability factors in terms of such physical variables as particle radius (x), bubble radius (X), velocity of bubble relative to particle (v), the number of bubbles per unit volume of pulp (N) and the induction period (A) necessary for air-mineral adhesion. According to Sutherland&apos;s treatment, the rate equation, Eq. 1, transforms to R, = [3pX x v N] [sech2 (3 v ?/4 X) ] ?c(x) V [4] where the first term in brackets on the right-hand

Jan 1, 1957

By AIME AIME

THE revised program for the San Francisco meeting, with assignment of the various papers to the several sessions is now available and is printed below : MONDAY, OCT. 7 . General Meeting, 11-12 A.M. Chairmen: Frederick W. Bradley and E. A. Hersam. Opening of the session by the Chairman of the San Francisco Section-E. A. Heraam. Address of welcome by the President of the Institute- Frederick W. Bradley. Address: The Mining problems of the West--Charles W. Merrill.

Jan 1, 1929

By R. S. Dean. J. R. Long T. R. Graham, Roberson A. H., Armantrout C. E.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig&apos; &apos;) has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig&apos; &apos;) has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.&apos; In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-&apos; Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.&apos; although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation&apos;s petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,&apos; Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;&apos;-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>&apos; the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.&apos; Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .&apos; the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969