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By H. D. Outmans

In steady vertical flow, the interface of an immiscible liquid-liquid displacement is horizontal for any flow rate below the critical. In nonvertical flow, however, the shape of the interface in the steady state does depend on the flow rate, and the purpose of this paper is to calculate the unsteady interfaces during the transition of one steady state of flow to another. A knowledge of these transient interfaces is of considerable importance in reservoir engineering where the calculation of breakthrough recovery depends on the instant the interface reaches the producing wells and on the shape of the interface at that time. Although the emphasis is put on transient interlaces, which eventually approach stable equilibrium, it is shown that if the displacement exceeds a critical rate no equilibrium is possible. The interface is then unstable and viscous fingers are formed during the displacement. The critical rate and the shape of the transient and equilibrium interfaces are affected by the effective interfacial tension; but since this effective interfacial tension appears in the calculations only in combination with the inverse square of the thickness of the medium, its effect in the reservoir would appear to be negligible compared to its significance in model experiments. INTRODUCTION Stability criteria and the early growth of interfacial disturbances in a plane parallel to the boundaries of a dipping formation in which oil is displaced by an incompressible fluid were described in a previous paper.l This type of instability is significant in thin reservoirs. However, if the reservoir has appreciable thickness, then interfacial stability in vertical planes, normal to the upper and lower boundaries, also becomes important (the displacement is supposed to be parallel to these vertical planes). The difference between the two stability problems is that, in the first case, the intersections of the interface with planes parallel to the boundaries are normal to the direction of the displacement; in the second case, the intersections, this time with vertical planes, are not normal to the displacement. Instead, they are tilted at an angle which depends on the displacement rate. The tilt of steady interfaces was calculated by Dietz2 who also determined the critical rate of displacement for stability in the vertical plane by assuming that this rate would coincide with an interfacial tilt equal to the dip of the formation. The critical rate thus calculated is the same as has been found for thin reservoirs (see Eq. 1.1 of Ref. 1 and of the present paper). Dietz's calculation of the stable tilt was verified by laboratory experiments and the agreement was found to be fairly good.3 It is doubtful, however, that stable tilts actually exist in the reservoir because a change in production rate is not followed by an instantaneous adjustment of the interface to the new rate but, rather, by a transition period during which the interface changes from one equilibrium tilt to the other. The principal objective of this paper has been to describe these transient interfaces without putting any restrictions on the flow conditions or the shape of the interface, as had been done previously. The second objective was to compute the critical velocity, taking into account capillary effects, and the third was to evaluate, at least qualitatively, the shape of the front at rates above the critical, again without making the simplifying assumptions introduced by previous investigators.2,3 In the following sections two examples are given of the calculation of interfacial motion. The first describes this motion for an initially horizontal interface in a dipping layer, and the second for a vertical interface in a horizontal layer. The mathematical formulation of the problem is nonlinear in the boundary conditions, and this prohibits its solution in closed form. Instead, the solution is obtained in the form of higher-order approximations. 1 Before proceeding to a description of the mathematical model, however, we define two quantities

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By Harlan A. Walker

ROCK-DRILL steel has an important bearing on costs in many mining operations, both directly and indirectly. Direct factors include such items as shop expense, steel consumed per ton of ore produced, cost of distribution and the dust hazard. The latter, although no specific amount may be assigned to it, is an ever-present problem, and is receiving increased attention as the science of mining progresses. Indirectly drill-steel performance affects consumption of compressed air, maintenance of drills and drilling speed. The latter, in turn, increases or retards the tempo of mining and development. These factors, while not all inclusive, are preponderant in their importance. Thus it is evident that in an extensive operation drill-steel expense may run to many thousands of dollars and that thoughtful research leading toward more efficient practice is warranted. EXPERIMENTAL WORK During the late spring of 1939, experiments were undertaken at Homestake in reducing changes in drill-steel gauge from 1/8 in. to 1/16 in. [ ] In drifts and crosscut headings mounted machines were set up and holes were drilled with 1/8-in. bit-gauge changes and other holes a few inches

Jan 1, 1940

By C. H. Jr. Herty

THE removal of sulfur from steel has been studied by many investigators, but the quantitative relationships between the factors involved have not been determined. This is undoubtedly due to the number of variables encountered in practice, an attempt to study any one reaction or relation being affected by other reactions the relative importance of which cannot be estimated. The factors that affect the extent of removal of sulfur in the basic open-hearth process are generally considered to be: 1. Basicity of the slag: (a) Iron oxides in the slag; (b) carbon in the metal, or carbide in the slag; (c) temperature. These factors affect the reactions: FeS + CaO = CaS + FeO FeS + CaO + C = CaS + CO + Fe. 2. Amount of sulfur in the gas. 3. Amount of manganese in the metal. The factors which affect the rate of removal of sulfur include, in addition to these 4. Fluidity of the slag: (a) Normal changes in fluidity with temperature; (b) changes in fluidity because of the addition of special reagents such as fluorspar. 5. Agitation of the bath.

Jan 3, 1925

By N. A. Ziegler

THE chief difficulty in determining oxygen in steels is its tendency to form a variety of compounds. Almost every element, found as an ingredient in steels, maybe expected to be present as an oxide. Some of these oxides have widely differing properties, and consequently behave differently when attempts are made to reduce them by the vacuum fusion method. As I pointed out in a paper published in the Transactions of the A.S.S.T., Vol. 20, No. 1, many experimenters are spending considerable time and effort in attempting to deter¬mine the degree of completeness of the above reactions, and hold different opinions on the matter. In studying this subject the following table, taken from Hodgman and Lange's "Handbook of Chemistry and Physics" may be used as a guide.

Jan 1, 1933

By John Wulff, David A. Stevenson

The rates of solution of copper, nickel, and three copper-nickel alloys in liquid lead were studied at 527° and 727°C under dynamic conditions. The relative velocity at the solid-liquid interface was varied from 8.65 to 125 cm per sec. Analysis of the data for the pure metals indicates that the solution rate is transport corztrolled at lower velocities, but a transition to mixed control occurs at higher velocities, higher temperatures, and higher percent saturation. 1 HE present work concerns the effect of relative velocity at a solid-liquid interface on the dissolution kinetics of pure solid materials in liquid metals. This general problem is of interest in electrode kinetics, in electrolytic processes, and more recently in the field of liquid metal corrosion. Considerable work has been done on dissolution kinetics in aqueous environments because of the obvious importance to electrolytic processes.1,2 In purely metallic systems investigation has been more limited. There are, of course, extensive data from loop tests which are used in an engineering evaluation of liq- uid metal corrosion. Here, however, the dissolution process is complicated by several interdependent processes. In general, one of two factors is considered to be rate limiting in the dissolution process: the transport of material from the solid-liquid interface into the bulk liquid, or an activation process directly at the interface. A number of studies of the dissolution rates of solid metals in liquid metals under static conditions have been published.3- Since the attendant hydrodynamic conditions imposed by thermal gradient convection and concentration gradient convection are difficult to analyze, it is doubtful if a clear interpretation of the experimental findings of these papers in terms of the mechanism involved in the dissolution process can be made. A clearer picture of the dissolution process is provided by

Jan 1, 1962

By W. L. Fink, L. A. Willey

This paper is the nineteenth of a series from the Aluminum Research Laboratories, presenting the results of the investigations of equilibrium relations in aluminum-base alloys made from electrolytically refined aluminum. In previous papers equilibrium relations have been determined and correlated for 12 binary systems. Equilibrium relations have also been determined for portions of the aluminum corners of three ternary systems (aluminum-iron-silicon, aluminum-magnesium-silicon and aluminum-copper-magnesium). The object of the present paper and those to follow is to increase our knowledge of the aluminum corner of the more important ternary systems. In 1926 Dix and Keith † suggested a new method for designating the phases encountered in alloy systems. The system has been used to a very limited extentl,2,3 The system has since been slightly modified and will be used in this and future papers. In the system as modified, a phase is designated by placing in parentheses the chemical symbols of the elements essential to the formation of that phase. The symbols in the parentheses are separated by dashes in order to clearly distinguish them from a chemical formula. Elements that are not necessary to the formation of the phase in question, but which may be present in solid solution, are not indicated in the designation. If two or more phases would have the same designation according to these rules, they are distinguished by prefixing Greek letters, and are definitely identified by X-ray diffraction patterns. Previous Investigations The solid solubility of magnesium in aluminum has been well established by the work of Dix and Keller4, Schmid and Siebe15, and Saldau and Sergeev6. There is no agreement as to the composition of the magnesium constituents at the aluminum end of the binary aluminum-magnesium system. Hanson and Gayler7 report Mg2Al3; Boyer8 found that the alloy

Jan 1, 1937

By H. B. Fuqua, B. E. Thompson

For a very brief description of the North Texas area and the general geological features with which it is associated, the reader is referred to the summary for 1935. As in previous years, the authors have been unable to undertakc the almost impossible task of isolating statistics for the hundreds of productive "spots" which are included within the generally productive areas of the several counties. However, pools that appear to be definitely isolated—as, for example, the Foard County production and the new pool recently developed southeast of Gainesville in Cooke County—are covered separately. During the year 1936, both routine development in proven or scmi-proven areas and exploratory drilling showed a decrease over the year 1935, there having been a total of 1453 wells drilled in the district during 1936, as compared to 1619 in 1935. It is also of interest to note that abandonments exceeded completions in 1936. Developments during 1936 While a number of local productive spots were found in Wilbarger, Archer and Wichita Counties, and numerous minor local extensions to older producing areas were developed in practically all the producing countics in the district, only two discoveries of sufficient importance to justify special mention were made. Anderson and Kerr No. 1 Bruhlmeyer, about two miles southeast of Gainesville in Cooke County, was completed in April, at a total depth of 2014 ft., for an initial production of 315 bbl. daily from a sand of Pennsylvanian (Canyon) age. Development has been rapid and the field is about drilled up. During November the 100 wells in the field averaged about 40 bbl daily. The structure appears to be a small fold associated with the northeast flank of the main uplift, which extends in a northwest-southeast direction across Cooke and Montague Counties.

Jan 1, 1937

By W. R. Crane

The support of roof in mines is dependent largely on the character of the top rock and its occurrence. The formations overlying the orebed in the Birmingham district are sandstone and slate. The sandstone occurs in beds of sufficient thickness to constitute important elements in the system of support; the slate is relatively strong but is thinly stratified. The alternating beds of sandstone and slate furnish an excellent combination in that the former are strong and the latter are impervious; however, their continuity is broken by jointing or slip planes. The thickness, and consequent weight of the overlying formations, is important in so far as the size and arrangement of pillars are concerned but may be relatively unimportant, temporarily at least, as a factor in the support of the roof. The position of the respective beds of sandstone and slate, their relative thickness, and their inherent weakness because of the occurrence of faults and folds, may exert a predominating influence on their support in place, which is affected only in part by the weight of the cover. The only mine in this district that operates under a cover of approximately 2000 ft. (1900 ft.) is the Shannon so-called "twin slope," situated 14,000 ft. southeast of the portal of the No. 7 mine of the Tennessee Coal, Iron, & Railroad Co. The conditions in this mine indicate what may be expected in other mines when the same depth is attained; in fact, the effect of pressure is shown in several mines that have not reached two-thirds of that depth. It is evident, then, that conditions affecting the support of roof will not improve but rather will become more difficult with the extension of the mines into the valley under a constantly increasing weight of cover. Further, the difficulties will probably be augmented by the occurrence of faults and other disturbed ground, the presence and position of which at present are largely unknown.

Jan 1, 1925

By Yang Tsang Woo

I will endeavor to describe the methods of silver-mining and smelting employed by the natives in Mongolia. Modern methods have been applied there, but with little success; and, since they are familiar to most members of the Institute, I will simply mention that the failure was due to the high price of coke used in smelting the ore in modern furnaces, and to the unsuitable mill-machinery employed for concentrating the galena, which is finely distributed in the ore. The Jehol silver-mines are situated about 45 miles NE. of Jehol, the capital of Mongolia. They embrace two mines, 5 miles apart,—the Ku Shan Tze mine and the Yen Tung Shan mine. They were first worked by natives 50 years ago, about the time when mining was so flourishing in other parts of the world,—for instance, in California and Australia. The upper part of the vein is galena mixed with iron-stone, and is 2 to 4 ft. thick. At lower levels the vein is composed of silver-lead ore running between quartz-porphyry walls. Limestone, talc and black shale, colored by graphite, are found in other parts of the mine. Crystalline limestone is found 1 mile NE. of Ku Shan Tze. Granite is encountered in the Yen Tung Shan mine. Mining.—The native method of working the mines is most primitive. The same method may have been employed a thousand years ago. A small inclined shaft, 4 ft. by 4 ft., is sunk in the vein-stuff where the appearances are most favorable. Another shaft is sunk 20 or 30 yds. away, for ventilation. The shaft follows the vein in a zigzag fashion in whatever direction the vein appears to be richest. Timber is used only in soft ground. Where the ground is hard, the roof is cut into an arch-form. In some places, instead of using ladders, steps are cut in the rock, just wide enough to hold one foot. The deepest native workings are 400 ft. below the

Jan 1, 1903

By H. M. Boylston

Metallic manganese was first produced in 1773, by Sven Rinmann, a Swedish mineralogist. In 1799, William Reynolds, of Ketley, England, obtained a patent on the use of manganese dioxide in the manufacture of steel, and in 1808 an English patent was granted to John Wilkinson covering the use of manganese ore, or manganiferous ore, as an addition to iron ore in the blast furnace for the production of a superior grade of pig iron. Karsten showed in 1816 that manganese increased the hardness of iron without decreasing its malleability or toughness, while it caused pig iron to be more white in fracture and more fusible. The first practical application of manganese to steel-making, however, is attributed to Josiah Heath who discovered in 1839 (less than 90 years ago) that manganese conferred upon steel the properties of being more easily worked and welded under the hammer. When Bessemer invented the pneumatic process of steel-making which now bears his name he was at first successful because, as it afterward developed, he was using a Swedish pig iron high in manganese. When his supply of this material ran out, he used a low-manganese pig from English sources and failed signally to produce a steel which could be rolled, while his Swedish licensees were continuing their successful application of his method. And it was not until Robert Mushet, in 1856, suggested the addition of manganese in the form of spiegeleisen to the molten product of the converter that success again came to Bessemer. In 1866, William Siemens patented the use of ferromanganese as an addition to molten steel to counteract the bad effects of sulfur. It was in 1888 that Robert Hadfield published at some length his account of the effect of manganese as an alloying element in steel and described the unique properties of the now famous Hadfield manganese steel containing about 12 to 14 per cent. manganese and 1.25 per cent. carbon. Function or Manganese in Steel-making Bessemer's failure at one period of his experimental work to make steel which could be forged successfully was due to the fact that the

Jan 1, 1927

By E. E. Mason

The Canadian National Railway system is completing construction of the first major tunnel in North America to use the coarse-aggregate (+ ½ -in.) shotcrete technique of primary support and lining. The tunnel was driven 29 X 20 ft in cross section, 10,760 ft long, passing under an industrial and residential area of Vancouver. With the exception of 1400 ft in soil (mainly impervious tills), the tunnel passes through a very young series of flat-lying sedimentary beds, to a large extent so incompletely consolidated as to fall apart on exposure. For a conventional steel-support system, it was estimated 8 WF, 28-lb steel should be used at 5-ft centers. Cost of erection including lagging would amount to $120 per linear ft of tunnel at 304 per lb. With 8-in. concrete cover on the steel, lining would cost $280 per linear ft at $82 per cu yd. Thus, minimum cost of support and lining would have amounted to $400 per linear ft. It is now estimated that at least 90% of the rock tunnel would have required support and 100 % required lining. Specified shotcrete support was 6 in. in the arch and 4 in. in the walls. Cost of this work was roughly $100 per linear ft. In addition, another $10-$12 per ft has been incurred in drainage and waterproofing wet areas and in measures to correct experimental and operational errors, thus finalizing the support as a lining (Fig. 1). The tunnel was driven three shifts five days weekly, no blasting being allowed by city ordinance between midnight and 7.00 a.m. A six-drill jumbo was used to drill a 10-ft round, 110 holes blasted three times daily. A 2-in. layer of shotcrete was applied to the newly blasted arch commencing within 45 min of blasting. This was done from a flying deck that extended over the muck pile from the jumbo (Fig. 2). Also during the mucking cycle, the preceding incomplete arch support was brought up to 6-in. specification. The walls were sprayed 4 in. thick during the drilling cycle (Fig. 3). The shotcrete machines and aggregate bins were mounted on the jumbo.

Jan 1, 1970

By E. S. Bardwell, R. J. Lapee

Twenty years ago, W. T. Burns, in his paper presented at the Butte Meeting of the Institute,' discussed the general scheme then in use in the electrolytic copper refinery of the Anaconda Copper Mining Co. at Great Falls, Mont., for removing impurities from tank-room electrolyte and controlling its acid content. Since then marked changes have taken place in copper-refinery practice at Great Falls. The electrolytic copper refinery in use in 1913 has been replaced by a new and entirely modern plant capable of producing up to 27,000,000 Ib. of cathode copper per month. With the building of the new plant in 1916, the treatment of converter anodes was discontinued. At first the substitution of refined anodes for converter anodes resulted in a decrease in the impurity content of the anodes, but as time went on, changes in metallurgical practices at the smelter resulted in substantial increases in the impurity content of the anodes. The leaching of the silver slime to remove copper before shipment to Raritan for treatment further added to the purification problem. The fact that the scheme of purifying electrolyte which Mr. Burns described in his paper has proved adequate for our needs under a wide variation of conditions speaks well for its essential soundness. Method of Purification Briefly, the method adopted for purifying tank-room electrolyte at Great Falls has been as follows: Each day a certain volume of tank-room electrolyte is run off and sent to the purification plant, where it is boiled down to approximately 46' 136. The concentrated electrolyte is then sent to crystallizing tanks where the bulk of the copper is crystallized out as copper sulfate. The mother liquor is then passed through insoluble anode tanks to remove the last of the copper and most of the arsenic and antimony. It is then either returned to the tank room direct or boiled down to 55' Bé, the iron and nickel salts crystallized out and the mother liquor returned to the tank-room circuit as restored acid. Prior to 1930 all of the evaporating was done in lead-lined tanks 13 ft. in diameter by 4.5 ft. deep, provided with lead heating coils through which steam at 30 lb. gage pressure was circulated.

Jan 1, 1934

By Sheldon Rideout, E. L. Kamen, B. S. Lement, Paul A. Beck, W. D. Manly

The 1200°C isothermal sections of the following ternary phase diagrams were investigated: Cr-Co-Nil Cr-Co-Fe, Cr-Co-Mot and Cr-Ni-Mo. In all these systems the u phase was found to form extended solid solutions. Two new ternary phases of unknown structure were identified. The existence range of intermediate phases of transition elements was correlated with 3d electron vacancy concentrations. THE occurrence of extensive ternary d solid solutions in the Cr-Co-Ni and in the Cr-Co-Fe systems was described in a brief note.' More recently d- solid solutions were also found in the Cr-Fe-Mo system by two independent groups of investigators.2,3 The existence of binary d phases in the V-Co and V-Ni systems, predicted in ref. 1, was experimentally discovered recently by Duwez and Baen and independently by W. B. Pearson, J. W. Christian, and W. Hume-Rothery.5 Duwez and Baen stated two general conditions for the occurrence of the d phase in alloys of the transition elements: "(1) The atomic diameters of the two metals do not differ by more than 8 per cent. (2) One of the two metals has a body-centered cubic structure while the other is face-centered cubic, at least in one of its allotropic forms." In the course of an extensive research program conducted at this Laboratory under the sponsorship of the NACA, several ternary systems, containing d solid solutions and also certain new ternary phases, were investigated. The present report describes the investigated portions of the 1200°C isothermal sections of the following ternary phase diagrams: Cr- Co-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo. It was found that the range of existence of the d phase in these four ternary systems, as well as in one of two ternary systems which were investigated by others, can be fairly consistently described in terms of electron vacancy concentrations. This supports the suggestion of Sully and Heal" that the d phase is an electron compound. Experimental Procedure The ternary alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. Lot analyses of the metals used are given in Table I. Specimens of all alloys were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting mainly of

Jan 1, 1952

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By C. S. Smith, Chih-Chung Wang

D. Turnbull—In the opinion of the writer the most interesting result described in this paper is that the distribution of tin with respect to solidification temperature has several fairly well-defined maxima. It appears that each peak may be associated with a catalytic impurity of some rather specific composition. Recently we have obtained some additional evidence in favor of this viewpoint in experiments on the supercooling of lead droplets coated with different surface films. The distribution of lead droplets, ostensibly coated with lead sulphate, with respect to solidification temperature exhibited two distinct and reproducible maxima, one at 20" supercooling and the other at 47". On the other hand, when the droplets were ostensibly coated with halide films, no solidification was perceptible until the aggregate was supercooled more than 55". Upon further cooling a single well-defined peak centering at 60" supercooling was observed. Since the particle size distribution was the same in these two sets of experiments it appears that the most reasonable interpretation of the results is that the sulphate surface film or its reaction products with lead are much more effective in catalyzing the nucleation of lead crystals than are lead halide films. C. S. Smith (authors' reply)—Dr. Turnbull's experiments with lead drops coated with various surface films are most interesting. However, before drawing conclusions from the cooling curves described in the paper as to the existence of a few nucleus types effective at a few different temperatures, one must consider the state of subdivision of the liquid metal. In the A1-Sn alloy used, the tin was not in uniform droplets but tended to collect in three distinct shapes—in long interconnecting prisms along grain edges, in somewhat elongated interdendritic branching pools. and in isolated droplets. A single nucleus will solidify only the metal in contact with it, and the heat evolved will be proportional to the connected volume. A uniform distribution of nuclei of random effectiveness in such an alloy will cause peaks on the specific heat curve on cooling, which correspond to the volume distribution of tin and tell nothing about the nucleus type. In any real alloy both effects will be combined, and it seems impossible at present to distinguish between them. M. B. Bever—The thesis of this interesting paper is supported by a combination of positive and negative evidence. The authors have shown that under certain conditions a liquid phase may undercool, if it is dispersed in a thoroughly discontinuous manner throughout a solid matrix. They also found that undercooling

Jan 1, 1951

By C. G. Dunn

With respect to theories of recrystalliza-tion in metals plastically deformed. it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in poly-crystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins3 indicated that some data were consistent with primary nucleation OCcurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried Out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere.4 PReparation oF Specimens and Experimental Procedure The material used in the present investigation was taken from the same heat of steel as that .used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0,075 Mn, 0.03I A1 and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with 8-in. diameter rolls, the plane of the sample in each case coinciding with an XY plane (the plane of projection for the stereo-graphic plots) and the elongation occurring in the X direction. In general, elongations were held to about 3 or 4 per cent.

Jan 1, 1945

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942