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By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By H. H. Spain, R. C. Rumble, H. E. Stamm

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By P. W. Ramsey, G. L. Werley

THERE have been numerous examples in recent years of the similarity between aging behavior and diffusion behavior, where a plot of the logarithm of the aging rate versus the reciprocal of the absolute temperature yields an approximate straight line, analogous to a similar plot of the diffusion coefficient D (log D vs. 1/T). Austin and Rickettl have pointed out that this linear relationship holds empirically for the de- composition of austenite into pearlite and bainite in carbon steels, and Robertson' has shown similar trends in the aging of 24S-type aluminum alloys. Jenkins and Bucknall³ have also demonstrated the association between aging and diffusion rates for nickel-silicon-copper alloys. Jetter and Mehl,4 however, have shown that the maximum rate of dilation of a series of aluminum-silicon alloys does not show this linear relation and Mehl5 has pointed out that careful study of available knowledge indicates that "aging rates increase with temperature approximately exponentially, whereas D increases precisely exponentially." He further notes that "the rate of aging at a given temperature is the greater the lower the melting point of the alloy, which is also true for D." This paper describes the aging changes occurring in a zinc-25 pct manganese-15 pct copper-0.1 pct aluminum die casting alloy. It was found that this alloy does show this linear relationship and use was made of this relationship to estimate aging rates at low temperatures from data acquired at elevated temperatures. It should be noted that the aging reaction is being studied only indirectly, using changes in certain properties as criteria of the progress of the phenomenon. This alloy is purely an experimental one and is not available commercially. Zinc-Manganese-Copper System: The zinc-rich portion of the zinc-manganese-copper diagram which is of significance in the present work is quite uncertain. X ray examination of the alloy as die cast shows a phase similar to the epsilon phase (hexagonal close packed) of the copper-zinc system. All of the data accumulated indicate that the epsilon phase of the zinc-manganese-copper alloy is stable at high temperatures; that is, 500°C or above. Below this temperature a new phase is precipitated on annealing, and a decrease in specific volume occurs. At elevated temperatures this phase change occurs quite rapidly, while at room temperature the alloy has shown no change after several years. According to X ray data, this precipitated phase resembles the gamma phase (cubic) of the copper-zinc system, a hard and brittle structure. From examination of the microstructure and from X ray examination of the alloys annealed at

Jan 1, 1951

By D. C. Hilty, W. Crafts

L. S. Darken—Laboratory investigation of deoxidizing and other steelmaking reactions is usually centered, at least first, on the determination of the equilibrium or equilibria involved. This seems a reasonable procedure since equilibrium, if attained, depends only on composition, temperature, and pressure; hence conclusions derived from data on small experimental quantities are applicable to a heat of steel providing eauilibrium is attained in both cases. A knowledge of equilibrium serves as a useful framework even though we may know that practical conditions do not correspond to complete equilibrium. On the other hand, nonequilibrium or rate phenomena depend on a wider variety of conditions and are more difficult to interpret; conclusions applicable to laboratory conditions may or may not apply to larger scale phenomena. Hence the attainment or nonattainment of true equilibrium in the experiments here reported is of critical importance in evaluating their significance. Since some of the statements in this paper and in the closely related preceding one (on aluminum deoxidation) imply some doubt on this matter, I should first like to ask the authors whether their conditions are intended and believed to represent equilibrium. I should like to point out three considerations which seem to cast considerable doubt on the achievement of equilibrium, at least of the particular equilibrium under consideration. 1. In the experiments on manganese deoxidation the authors point out that they could not maintain the manganese-oxide slag on top of the metal in their rotating crucible, and hence they substantially dispensed with this slag. This leads to serious trouble in the interpretation of the results, for any equilibrium is, of course, a particular specific equilibrium—in this case Mn + O = MnO The experimental deletion of the upper layer of manganese oxide means that if equilibrium is attained at all it is attained between the metal and the MnO which has soaked into or adhered to the crucible (under the metal) and has dissolved substantial amounts of the crucible material including impurities. These impurities may constitute a significant portion of the slag by virtue of the small total amount of slag, even though the crucible is relatively pure. Hence there would seem to be a strong presumption that the equilibrium (if attained) involves not a pure MnO (or MnO — FeO) slag but one saturated with alumina and containing perhaps considerable impurities which substantially lower the concentration and activity of MnO, causing the above reaction to proceed to the right further than it would in the absence of alumina and impurities. Hence it is not surprising that manganese here appears as a better deoxidizer than found by other investigators. The present results may represent equilibrium with a slag of unknown composition which seems unlikely to be particularly related to plant experience. 2. The curves representing the observed silicon deoxidation (figs. 3, 4, and 5) are all drawn with a discontinuity in slope at about 0.02 pct oxygen. This point is interpreted as corresponding to the three-phase equilibrium, metal, slag, solid silica. The type of construction shown in these figures (though apparently fitting the data) is contrary to a fundamental principle of heterogeneous equilibrium as pertains to the construction of phase diagrams. According to this principle, the two solubility curves (each of the two portions of the curves in figs. 3, 4, and 5) must intersect in such manner that their (metastable) extensions must lie outside the homogeneous field rather than inside as in these figures. In other words, the "point" in these curves should be aimed in the opposite direction, if it is to be interpreted as corresponding to the three-phase equilibrium. The construction adopted is in violation of the second law of thermodynamics. This matter is discussed in detail in several texts and also by Lipson and Wilson.&apos;" The same criticism applies to the later figures representing conditions for manganese additions. The occurrence of this discontinuity or break at 0.02 pct oxygen casts further doubt on its interpretation. The earlier investigation of this system by Korber and Oelsen is in substantial agreement with the several recent findings of Chipman and coworkers that the oxygen content of iron in equilibrium with silica and silica-saturated iron oxide slag is about one third to one half that (0.24 pct at 1600") of iron saturated with pure iron oxide; thus there seems reliable evidence that iron saturated with silica and iron silicate slag at 1600" contains about 0.1 pct oxygen, or certainly much more than the 0.02 pct proposed in this paper. 3. In the quarternary system iron-silicon-manganese-oxygen one of the equilibria involved may be written 2 Mn + SiO2 (solid) = 2 MnO <slag> + Si The activity of SiO, is constant (if equilibrium is attained) by virtue of its presence as a substantially pure solid. At not too low metallic manganese content, the activity of MnO in the slag is constant by virtue of the fact that the slag is substantially pure manganese silicate saturated with silica and hence of constant composition. Thus the equilibrium constant for the above reaction is asi/a2Mn. Barring unanticipated large changes in the activity coefficients, the equilibrium constant may be adequately approximated for the composition range covered as [% Si]/[% Mn]2. Thus a plot of log [% Mn] against log [% Si] would be expected to be linear with a slope of one half as found by Kijrber and Oelsen. In the present investigation the slope (shown in fig. 15) is found to be one. It is difficult to believe that this finding represents a correct equilibrium determination, since it is at odds both with prior experimental investigation and with. theory. In view of the above points it seems that, although this paper reports many interesting findings, there is room for considerable skepticism as to the attainment of equilibrium and as to the conclusions drawn. N. A. Gokcen—The authors consider that Si% x O2% product is constant. This product is a function of the asi X a0 activity of Si02. The true constant is -------------. If the asio2 slags of this investigation were always saturated with SiO2 then Si% X O2% product would be constant,

Jan 1, 1951

By T. E. Leontis, R. S. Busk

WORK was initiated several years ago at The Dow Chemical Company to determine the applicability of powder metallurgy processes to magnesium and its alloys. Although it was found possible to apply the normal techniques of compacting and sintering, it was discovered early that the technique of extrusion offered special promise. This technique and the alloys produced were therefore studied extensively, and the present paper is a partial report of those studies. It is expected that a second paper will discuss more extensively some of the alloy systems simply mentioned here. Although the literature on powder metallurgy is very extensive, there are only two articles dealing with magnesium13,14 and there is no reference to the direct extrusion of the powder of any metal without the preliminary step of compacting. Furthermore, no mention has been made of the possibility of designing alloys by the technique of powder extrusion, particularly alloys that cannot be made in any other way. Sauerwaldl3 discusses the extrusion of magnesium and aluminum powder to produce alloys containing nonequilibrium phases, but again he emphasizes the importance of pre-compacting before extrusion. There seems to be general agreement that some form of hot-pressing is essential to obtain in a compact the full theoretical density of the metal used.&apos;-" The nearest approach to the technique of direct powder extrusion is that of extrusion of pre-sintered compacts,&apos;-" for which the best review through 1944 is that by Kieffer and Hotop.11 Ensign* discussed a specialized technique of "extruding" already compacted and sintered gears for the purpose of sizing. Sauerwa1d13 discussed the compacting and extrusion of magnesium and magnesium-aluminum alloy band-saw chips. The properties of the extruded compacts were found to be comparable with those of extrusions prepared from solid billets. He also extruded a compacted mixture of magnesium and aluminum powder and found the properties to be somewhat different from those obtained on an extrusion made from a cast billet of the same composition. The second reference dealing specifically with the powder metallurgy of magnesium is Stern&apos;s patent," in which is described the extrusion of scrap chips and turnings following a hot-pressing and sintering step. Considerable emphasis in most of these articles is placed on the necessity of atmospheric protection to minimize the danger of oxidation. Experimental Procedure The first experiments were made with the small extrusion press shown in fig. 1. With this press, billets of about 1/2 in. diam are used to produce wire

Jan 1, 1951

By L. Larson

SMELTERMEN in the copper industry know that punching the tuyeres of a copper converter is a difficult, disagreeable, and at times a hazardous job. Knowing this, many men in the industry have given serious consideration to punching by mechanical means. As evidence of such consideration, a great many patents have been issued covering various mechanical devices or machines for doing this task. In 1942, as war-created manpower shortages became more acute, it became increasingly difficult to get men to punch tuyeres. Faced with this situation at the McGill smelter, it was decided that an all-out effort should be made to develop some sort of a mechanical punching device. The various patents were studied over thoroughly but none of the devices seemed suitable, all were discarded and it was decided to develop one, using the ideas of the personnel at McGill. Initial test work indicated that a separate punching device should be attached to each tuyere. This meant that an adapter would have to be developed which would accommodate such a device; the adapter to be so constructed that it could be substituted for the regular Dyblie valve head, and be punched either by mechanical means or by hand. Also a method for quickly attaching or detaching the punching unit would have to be devised. If the punching unit was attached to the adapter, then the punch rod and tip would have to remain inside of and reciprocate within the tuyere pipe. This last requirement meant that the punching device, the adapter, the piston rod, and punch rod must be in perfect alignment. The whole arrangement thus would become an integral part of the converter and would rotate along with the tuyere line to all the positions required for converter operation. If the puncher was to rotate with the converter, there was also a problem of limited clearance. The construction of a device to meet all of these conditions imposed many problems. In the latter part of 1942, two pieces of equipment were constructed and tried out under test-stand conditions. Both of these devices were very crude, but test-stand operation indicated that progress was being made. Neither of the units was considered good enough to be attached to and tried out on a tuyere of an operating converter. In May 1943, work was started on another device and in August of that year it was attached to and actually punched a single tuyere of a converter on an experimental basis (fig. 1). This unit was essentially a cylinder 3 in. in diam and about 15 in. long inside. Valve ports were so located as to provide a 1-in. cushion on each end of the stroke. The cylinder ports were piped to a 3/4-in. four-way disk valve. High pressure air (90 psi) was delivered to the valve by means of a long hose, thus making it possible to supply air to the device at all operating positions of the converter. The forward and return punching strokes were accomplished by shifting the valve handle as required. With the 3/4-in. valve, stroke velocities from 15 to 18 fps were achieved. Punching with this experimental arrangement was carried on for some time, but many difficulties were encountered. The punch rod tips often stuck in the tuyere accretion, indicating that more energy of some sort was necessary to avoid sticking the punch rod. To overcome sticking, experiments continued with a speeded up unit and although progress was made, troubles of various kinds continued to appear. On this unit, piston cup seals passed the valve ports which proved to be of very poor construction. Also the piston, driven forward at approximately 28 fps, would often bottom metal to metal in the forward end of the cylinder causing both mechanical and operational trouble. Sometimes the punch rod and at other times the piston rod would break loose and be shot through the tuyere pipe into the converter. Bottoming and poor timing of valve reversal caused a bounce and a hesitation at the end of the forward stroke, with the result that the punch rod

Jan 1, 1951

THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as upon control of furnace practice. This chapter deals only with the raw materials of the basic open-hearth process that are important in determining the composition of the steel or slag. They are the metallic charge, oxygen-bearing materials, fluxes, alloying and deoxidizing additions, and certain refractory materials used for maintenance of bottoms. Other refractories, which may affect the slag composition, are discussed in Chapter 3. Wide variations are possible in the type and composition of charged materials but certain limiting relations among the elements of the charge must be observed. Since the process consists essentially of refining by the oxidation of undesired dements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters 2 and 7). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme is the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not oxidized or eliminated by, any other reaction, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type is found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should be low in copper, or a sufficiently high ratio of pig iron to scrap should be charged to dilute the copper from the

Jan 1, 1951

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-&apos; using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By Leonard B. Lipson

Boyer, Morgan and Muskat,&apos; with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,&apos; have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/&apos;E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By L. E. Shiffman

This paper describes the operation of two kerosine flotation plants in Alabama for cleaning —10 mesh bituminous coal. One plant treats washer sludge, the other raw coal. Data on capacity efficiency and capital and operating costs is given. Methods for increasing cell capacity are discussed. IN cleaning coal it has long been recognized that methods which give excellent results for the coarser sizes may give poor or even no cleaning for the finer sizes. Effective cleaning of the fines, therefore, is usually a separate and distinct problem. For many years the problem of fines was considered of relatively minor importance. Now there is growing interest in methods of cleaning the fine sizes of coal because: 1. There are more fines. Increasing mechanization and the adoption of full seam mining methods have resulted in the production of a greater percentage of smaller particles than were produced by hand loading methods. 2. The fines have deteriorated in quality. The same causes that have led to increased quantity have also operated to decrease quality through greater contamination with slate, rock, and other diluents. 3. The fines have become more valuable. When coal was comparatively cheap, loss of the finer sizes was tolerated but, with the rapid increase in the cost of mining coal, it has become imperative that the maximum amount of clean coal be recovered from the mixture of coal and rock delivered to the tipple. 4. In many cases, the fines have become a stream pollution problem. Increasing governmental activity and legislation to prevent stream pollution often have made it necessary to retain the fine material which formerly was permitted to escape with the washer effluent into flowing streams. The Sloss-Sheffield Steel and Iron Co. operates four coal mines, all within a 20-mile radius of Birmingham, Ala., with a total annual production of 1,-250,000 tons of washed coal. Three of these mines are in the Mary Lee seam and one in the Jefferson seam. Although some steam and domestic coals are produced, the major portion of the coal is used to make coke for blast furnace operation. Fine coal is desirable for coking, and all the coal so used by Sloss is crushed to 1/4 in. Therefore, there is no problem of an outlet for even the finest sizes of coal. Since the coal is used for metallurgical purposes, low ash is of greater importance than would be the case if it were used for steam generation or domestic heating. Based on present blast furnace practice at Sloss, it is calculated that each percentage of ash in the coal carries a penalty of $0.22 per ton of coal. Thus there is a considerable margin for operating costs in a fine coal cleaning method that will result in materially lowering the ash content of the cleaned coal. Development of Fine Coal Cleaning Problem In 1942 Sloss reopened its Bessie mine and constructed at this location a new preparation plant to clean 11/4 in. x 0 coal from the Mary Lee seam.

Jan 1, 1951

By R. H. Eckhouse, M. R. Geer, H. F. Yancey, C. L. Allyn

Four coals were treated in the Humphreys spiral concentrator, and the products were examined by float-and-sink and screen-sizing tests to determine fundamental performance characteristics. The efficiency of the separation between coal and impurity was shown to be influenced greatly by particle size. FOUR coals exhibiting different washability characteristics were washed in the Humphreys spiral concentrator and the products examined by float-and-sink and screen-sizing tests to determine the mechanics of the separation between coal and impurity. With one coal, each 1/2-in. increment of the full width of the stream in the spiral was examined separately to determine where each size and specific-gravity fraction of the feed was stratified. The basic performance characteristics of the spiral were found to be the same for all of these coals. The coarsest fraction of heavy impurity stratified so far out in the stream that it could not be removed through the refuse ports and thus either entered a middling product or contaminated the washed coal in the case of a two-product separation. Impurity particles finer than about 100-mesh also were carried out in the main body of the stream and therefore were not removed in the refuse product. Little loss of clean coal in the refuse occurred in sizes coarser than 28-mesh or finer than 100-mesh, but considerable coal of intermediate size stratified in the stream that was drawn off through the refuse ports. Because of this modifying influence of particle size, the spiral is unable to make an efficient two-product separation between coal and impurity without some retreatment. Recirculation of a middling product through the same spiral as a means of obtaining more efficient operation was not attempted in this investigation. The size and specific-gravity composition of the middling product are, however, such as to render it amenable to simple hydraulic classification for recovery of coal. Retreatment of a middling product would improve the efficiency of the spiral, but even when making a substantial amount of middling, considerable clean coal enters the refuse product. Consequently, retreatment of a combined refuse-middling product would appear to offer greater promise for providing maximum efficiency. Because of the sizing characteristics of the spiral, a classified feed can be treated with higher efficiency than is possible on a natural raw coal. For this reason, semiclassified feeds, such as silt-bank or classifier-underflow materials, can doubtless be treated with higher efficiencies than those shown for raw coals in this report. Performance is, of course, only one of many factors that enter into the choice of cleaning equipment. The fact that the one company now using the spiral for cleaning coal has built a second spiral plant is ample evidence that the inherently low efficiency of this unit may be overshadowed by the low operating costs afforded by its extreme simplicity. Introduction A number of factors enter into the selection of coal-cleaning equipment, and most of them bear directly on the final cost of prepared coal. One of these factors is performance of the cleaning unit in terms of the efficiency of the separation it effects between clean coal and refuse. The importance of performance in the selection of a coal-cleaning unit varies with the difficulty of the cleaning problem. Obviously, if the character of the coal is such that only certain types of cleaning units are capable of yielding a clean product meeting market requirements, performance is of prime importance. If, on the other hand, the cleaning problem is so simple that any type of cleaner will provide coal of suitable quality, performance is important only insofar as it affects costs by determining the amount of salable coal lost in the washery refuse. With the objective of providing the coal industry with information that is helpful in the selection of

Jan 1, 1951

By Richard H. Jahns

Such minerals as beryl, lepidolite, sheet muscovite, spodumene, and tantalite-columbite are obtained chiefly from pegmatite bodies that are internally zoned. As shown by examples of such pegmatites from the Southwestern and Southeastern States during World War II, studies of their internal and external structure have value in prospecting and the planning of exploration, development, and mining.

Jan 1, 1951

By Raymond B. Ladoo, C. A. Stokes

Bruce C. Netschert—It is unfortunate that the authors of this paper consider it necessary to begin with an expression of concern over possible false interpretations of the word "economics." In their preoccupation with the definition of economics, they have adopted a definition of mineral economics which is, to say the least, unduly narrow. Just as the broad field of economics is not confined to a study of the profitability of business concerns, but includes the problems of production, distribution, and consumption as they pertain to society as a whole; so an inclusive definition of mineral economics should not be confined to the determination of the profitability of mineral-producing and processing enterprises, but should include the significance of the unique characteristics of mineral resources as raw materials for the use of society. Such features as the exhaustibility and localized, haphazard occurrence of deposits, the existence of a secondary (scrap) supply, and the increasing cost of operation during the life of a mining enterprise are obviously factors which concern those businesses which are producing mineral raw materials, since they partially determine the profitability of such enterprises. They are also of concern to society as a whole, however, as characteristics of one of the basic elements of the economic system. In the last analysis, the contribution which mineral economics can make as a means of determining and guiding social policy with respect to the production and utilization of mineral resources is perhaps more important than its use as a basis for determining the cost accounting procedure of individual firms. The list of "economic factors peculiar to the industrial minerals" which the authors present is in reality an application of such a broad definition of mineral economics. An inconsistency appears, however, in the inclusion of items 8 and 9 in the list. As this writer sees it, the point in question is: What influences do the characteristics of industrial minerals have on the characteristics and operating procedures of industrial mineral enterprises which are not present in the metallic mineral field? In answering this question with items 8 and 9, Messrs. Ladoo and Stokes do not recognize that there are two distinct types of differences between the two fields of enterprise. There are, on the one hand, important basic economic distinctions due to inherent economic characteristics of industrial minerals which do not pertain to metallic minerals. On the other hand are those characteristics of the industrial mineral enterprises peculiar to them alone, but which are superficial and temporary, in that they may be changed or eliminated at the discretion of the managers of those enterprises. The lack of adequate research and development in industrial mineral production, processing, and marketing (item 8) is not due to an inherent characteristic of industrial minerals. It is true that one may perhaps describe the field of industrial mineral enterprise in terms of such a deficiency, just as one could, until recently, point to a similar lack of research and development in the coal industry; but unless it can be shown that the deficiency has been wholly or partially due to the very nature of industrial minerals themselves it is not an "economic factor peculiar to the industrial minerals" but a temporary characteristic peculiar to the industry. In the writer&apos;s opinion, the authors have not demonstrated that the former relationship exists. Similarly, item 9, the "influence of technologic developments," is also not inherently peculiar to industrial minerals. Nowhere in the discussion of this item do the authors mention anything that is not equally applicable to the field of metallic minerals. This is not meant to imply that the specific technologic developments which the authors list are of equal significance in both fields. It does mean that such a statement as, "technological advances together with new consuming areas to provide markets make deposits commercially valuable which once were of no interest" cannot be considered as an argument that technological developments have significance in the field of industrial minerals alone. In considering the problem of stockpiling, the authors note that the stockpiling of nonstrategic materials might be desirable if future wartime needs could exceed domestic production capacity, but dismiss this as hardly adequate to justify such stockpiling. The problem, however, can be stated in broader economic terms, i.e., the real costs (as distinguished from the money costs) of prewar versus wartime production. In other words, it might well be that the labor and capital required to produce a given amount of a certain mineral raw material could be used more efficiently in another industry. In such a case it is obviously advantageous to stockpile the material in prewar times rather than forego the benefits of additional production in another line of endeavor during wartime under conditions which demand the optimum use of all resources, including manpower and capital. To the writer&apos;s knowl-

Jan 1, 1951

By L. A. White

IN this paper it is proposed to follow the developments in the design of the lead blast furnace at Port Pirie from the time The Broken Hill Associated Smelters Pty. assumed control in 1915 to the present time, with special reference to the development of the system using two superimposed rows of tuyeres as is now in operation. Lead smelting operations first commenced in 1889, when the British Broken Hill Pty. Ltd. started its first furnace. This was followed by installing two more furnaces during the same year and another the following year. In 1892, Broken Hill Proprietary Co. Ltd. acquired the smelting works and combined operations with those at Broken Hill, New South Wales; by 1897, the whole of the smelting operations had been transferred to Port Pirie and thirteen blast furnaces were built to treat the Broken Hill ore production. In 1915, The Broken Hill Associated Smelters Pty. Ltd. took over from the Broken Hill Proprietary and have carried out operations since that time. From its inception, the present company started on a long range program of reconstruction, in which the development of the lead blast furnace has played a prominent part. A definite trend in plant development has been towards the simplification of plant control by a reduction in the number of operating units. The great advantages of technical control which resulted from the very simplified flowsheet established in the continuous refining process stimulated the desire to extend the principle to the smelting operation. Thus in the sequence of furnaces described here, it will be noted that the trend has been towards larger and, of course, fewer units. With each such development it is significant that the operating conditions and metallurgical results have shown steady improvement. Standard Furnace In 1920 there were seven furnaces operating, five of a type subsequently called the standard furnace and two of the original thirteen smaller furnaces, the latter type being used for the treatment of drosses, etc. produced from the refinery section, while the standard type carried out the main, lead-smelting operations. The standard furnace (figs. 1 and 2) had the dimensions given in table I.

Jan 1, 1951

By F. S. McNicholas

Various methods of block caving and draw practice are classified and the advantages, disadvantages, rock, treatment, size of orebody, costs, and profit comparisons, and other factors which determine the selection of the proper method are outlined.

Jan 1, 1951

By O. J. Hassel, W. T. Maidens, J. H. Calbeck

The rotary gas fired reheating furnace used by the American Zinc Oxide Co. at Columbus, Ohio for Therotarygasfiredreheatingfurnacerefining lead-free zinc oxide is described. The outstanding features of this operation are that the color of the zinc oxide is greatly improved, sulphur is eliminated, and cadmium arethatrecovered without densifying the product to an objectionable degree. IN 1919 Leland S. Wemple obtained a patent for a process of reheating zinc oxide wherein the "coarsening of grain due to excessive heating was avoided." He taught in his specification that if solid carbonaceous material, such as lamp black, was added to the zinc oxide in proper amounts prior to reheating, objectionable sulphur compounds could be removed and the color would accordingly be improved and no objectionable densification would occur because of the relatively low temperature required. The situation that made this invention imperative was the newly opened zinc oxide plant of the American Zinc, Lead & Smelting Co. in Hills-boro, Ill. This was one of the early Western Type American Process zinc oxide operations. Characteristic of all of these early Western operations using Tri-State and Western ores was the great difficulty encountered in obtaining a product low enough in sulphur to compete with the Eastern Type American Process zinc oxides which were made from ores containing very low sulphur percentages. Wemple demonstrated that the refining process of his invention produced a superior color and although this was true and a most welcome feature, the primary purpose of the early refining operations at Hillsboro was to reduce substantially the high sulphur content of the crude zinc oxide. Although many and varied attempts had been made for refining zinc oxide none of the processes had a commercial history of any consequence until Wemple&apos;s invention became standard practice for the American Zinc, Lead & Smelting Co. in 1919 and their operations have been unique in that substantially all of their lead-free zinc oxide has been reheated since the first installation at Hillsboro. This process has become known in the industry as refining. The furnace developed by Wemple and continued in use by the company from 1919 until 1943 was unusual and merits some consideration by way of review in this paper. The furnace was essentially a double hearth coal-fired muffle furnace with a mechanical raking system consisting of a central shaft supporting six rabble arms in each muffle. The untreated or "crude" zinc oxide was fed onto the outer rim of the top muffle, moved to the center where it dropped to the lower muffle and progressed to the outer rim where it was discharged into an alloy screw conveyor. The retention in this furnace was extremely short, about 5 min, and the shallow zinc oxide bed on the hearths of the muffles was being continuously turned by the fast moving rabbles. Soft coal was burned on the grates below the lower muffle and the long yellow flame necessary to carry the heat around both muffles resulted in a very inefficient combustion of the fuel. The temperature of the top of the lower muffle seldom exceeded 65 °C although the oxide itself often reached 700°C before discharge. The capacity of this furnace was approximately 1/2 ton per hr. In our plant at Columbus it was necessary to keep four of these furnaces running in parallel to take care of the production because, as mentioned above, every pound of zinc oxide produced during these 24 yr passed through one of these refining furnaces. An essential part of this refining operation was the use of carbonaceous material admixed with the zinc oxide fed to the furnaces. Between 1 and 2 pct of a bran produced in the processing of cotton seed was added to all zinc oxide charged to the furnaces. The bran ignited on the top hearth and was still burning when the charge fell from the top hearth to the bottom hearth making a cascade of sparks. The rapid turning of the zinc oxide caused these particles of bran to flash on the hearths behind each rabble; but the combustion, of necessity, had to be complete by the time the charge reached the outer rim of the bottom hearth, otherwise the finished product would be contaminated with the charred particles of bran which would give the zinc oxide an unsatisfactory color. Although this operation was initiated to reduce objectionable sulphur percentages, as time went on new properties of the product were appreciated which made advisable continuing the refining process long after other methods of sulphur reduction became known in the industry. The particle size and particle size distribution, the absence of colloidal fines and perhaps a unique surface condition gave this product an outstanding performance when used in paints. The Wemple furnaces installed in Columbus in 1919 had to be rebuilt frequently and were extravagant in the use of fuel. The raking mechanism and the muffles required excessive maintenance expense and as the furnaces wore out the problem arose whether to continue along this line or to explore the possibilities of obtaining similar or better results in the simpler and more commonly used rotary furnace. To this end special research was initiated in 1941 on a small laboratory rotary

Jan 1, 1951