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By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By Ancel St. John

During a session on coal and coke at the February, 1926, meeting of the American Institute of Mining and Metallurgical Engineers, the writer called attention to the important work on the X-ray analysis of coal1,2 being carried on in England by C. Norman Kemp and his associates. This aroused so much interest that a paper on the subject was requested for the October meeting. It has seemed advisable to make this paper a preliminary survey of the present status in the application of X-ray methods to coal problems and to follow it from time to time with further articles as the art develops. A survey of this sort naturally divides itself into two parts, radio-scopic analysis of the distribution of constituents through the body of the coal, and diffraction analysis of the state of association of the elementary components. In this article the subject matter concerning radioscopic analysis has been drawn almost entirely from the writings of Kemp and his associates and the illustrations have been sptcially furnished by him. It is a pleasure to record here a great indebtedness for this courtesy and cooperation. The subject matter and illustrations concerning diffraction analysis are taken from the author's unpublished researches. Nature and Properties of X-rays Before proceeding it is well to recall the nature and some of the properties of X-rays, as well as our present conception of atomic structure According to the accepted theory atoms are composed of electrically-charged particles. A positively-charged center, called the nucleus,

Jan 1, 1927

By N. A. Zeigler, T. D. Yensen

Aging is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in non-ferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more constituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the A1 transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, O, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2. Based on the theory that magnetic properties are intimately connected with the regularity of the lattice, it now follows quite logically that a greater effect on this regularity may be obtained when the above impurities are precipitated as very fine particles of Fe3C, Fe4N, FeO, etc., more or less uniformly dispersed within the grains. But if this is the case, it follows also that there must exist a relationship between the size

Jan 1, 1935

By N. A. Zeigler, T. D. Yensen

Aging is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in non-ferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more constituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the A1 transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, O, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2. Based on the theory that magnetic properties are intimately connected with the regularity of the lattice, it now follows quite logically that a greater effect on this regularity may be obtained when the above impurities are precipitated as very fine particles of Fe3C, Fe4N, FeO, etc., more or less uniformly dispersed within the grains. But if this is the case, it follows also that there must exist a relationship between the size

Jan 1, 1935

By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg2SiO4) and fayalite (Fe2SiO4) in solid solution. The name olivine was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Olivine is the principal component of the rock dunite, which itself is a member of the peridotite group of ultrabasic igneous rocks. European uses of the terms olivine and dunite are somewhat different than US usage. In commerce European usage defines dunite as containing 36 to 42% MgO, 36 to 39% SiO2, and loss on ignition of approximately 10%. The term olivine is used to designate a material containing approximately 85% forsterite, with a chemical composition of approximately 45 to 50% MgO, 40 to 43% Si02, 5 to 8% Fe2O3, and ignition loss of 1 to 2%. Uses The principal use of olivine is in various applications involving hot metal. Table I shows the best estimate available as to the amount of olivine consumed by various industries worldwide. In excess of 90% of world uses involve hot metal, with approximately 75% as a slag conditioner in the blast furnace production of pig iron. Approximately 15% of total olivine usage is as a special foundry sand in mold making for the brass, aluminum, magnesium, and manganese steel foundries (Schaller, 1957, 1958; Snyder, 1957; Anon., 1977). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as hand-cobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, has found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). The use of olivine as an additive in the blast furnace is relatively new, having been developed during the last decade. J.W. Currier (Private communication, 1978) describes the behavior of olivine in the blast furnace as follows: Olivine (Mg, Fe2, Si04) represents a unique lime-free source of magnesia and silica as a blast furnace charge component. Only recently has the magnesia-rich mineral been recognized as beneficial cleaner for blast furnace experiencing the problems associated with excessive alkali inputs and/or low coke stabilities. For some time it has been known that alkalis tend to recycle and accumulate in blast furnaces. In the high temperature region of volatilization the elemental alkalis formed attack the integrity of the graphite structure. This alkali attachment is enhanced when poor coke is used. Higher in the furnace stack volatile alkali cyanides condense and oxidize. This accumulation of alkalis tends to agglomerate the burden materials, producing scabs and scaffolds. These structures not only inhibit the downward movement of burden materials and the upward passage of wind, but also lead to erratic furnace performance

Jan 1, 1983

By H. Larson, J. Chipman

The ferrous and ferric oxide concentrations of slags, expressed as j = Fe+++/(Fe+++ + Fe++), have been established through gas-slag equilibrium at 1550°C in a range of oxygen pressure of 10-I to 10-9 equilibriumatm. The value of j is increased by basic additions (BaO, CaO, MgO, MnO) and decreased by acidic oxides (SiO2 and TiO2). Oxygen pressure is shown graphically as a function of composition for slags which are analogous to those at the slag-gas interface of the open hearth furnace. THE progress which has been made in recent years in understanding the chemistry of metallurgical slags has been based largely on studies of slag-metal and slag-gas equilibria. There is a considerable body of knowledge which is applicable to reactions occurring at the slag-metal interface in open hearth steelmaking. There is little information concerning reactions of the slag with the furnace atmosphere and hence little basis for an understanding of the transfer of oxygen, sulphur, or hydrogen between gas and slag. The oxygen pressure of the open hearth atmosphere is normally of the order of 10-1 to 10-3 atm which differs by several orders of magnitude from that of about 10" atm at the slag-metal interface. The chemical properties of the slag, for example, the ratio of ferric to ferrous iron and the ability of the slag to hold sulphur in solution, are greatly affected by changes in oxygen pressure. This investigation was undertaken to enlarge our knowledge of the effect of oxygen Pressure on steel-making slags. Using air or controlled mixtures of CO a CO2 a range of oxygen Pressures from 10.' to 10.' was covered. Review of the Literature There are only a few references in the literature which pertain directly to this investigation. The most important is that of Darken and Gurry1,2 on the system iron-oxygen. This work included the determination of the phase diagram of the system and also a study of the field of homogeneous melts and their oxygen pressures. Their apparatus and procedure were very similar to that used in this study. Iron oxide was melted in a platinum crucible under an atmosphere of CO2:CO, CO2:H2, H2O, CO2, air or O2 depending upon the partial pressure of oxygen desired. After equilibrium was reached, the sample was quenched and analyzed for ferrous and ferric oxide. By appropriate calculations these authors were able to determine the oxygen and iron activities in the various slags, heats of formation of the oxides of iron, and heats of solution of iron and oxygen in the liquid slags. In a subsequent paper' the same authors made a less thorough investigation of the effects of additions of lime and manganese oxide on the composition of iron oxide melts. Only a few experiments were made and those in a narrower range of temperature and oxygen pressure. Darken' has investigated the fusion temperature of iron oxide in contact with silica under various atmospheres. He found that the temperature changes from 1120° to 1447°C as the gas composition changes from CO2/CO equal to 20.8 to pure oxygen. A comprehensive paper by White" predates the work of Darken and Gurry. The decomposition of ferric oxide into oxygen and lower oxides of iron was studied from 1000° to 1650°C and under oxygen pressures from 2 to 76 cm of mercury. The effect of

Jan 1, 1954

THE slag performs two useful functions. in open-hearth steel-making. First, it is the means of disposal of all the impurities, save carbon, which are removed from the charge materials in refining the steel, so it must be suited to receiving and retaining as much as possible of undesirable elements with minimum loss of iron and useful alloying elements. Second, the slag serves as a buffer between the flame and the bath and transfers oxygen to the metal at a measured pace contrasted with the violent and difficultly controlled oxidation of the bessemer process. At the same time, the slag is a thermal insulator that limits the rate at which heat can be delivered to the metal from the flame, and a heavy slag blanket thereby serves as a brake on production rates. It has been said with justification that the secret of good steel- making is to make a good slag and the steel will take care of itself. In a broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of: (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) SO2, MnO, MgO, and other oxides charged as such or introduced incidentally with ores or fluxes or by refractory erosion, and (3) lime charged or fed to the heat to neutralize the "acidic" oxides present (SiO2 and P2O5). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined, and the control problem would be solved. Unfortunately, only a somewhat imperfect control over these factors is possible, so the operator must begin during the lime boil and continue through the refining period to discover and correct departures from the normal pattern of slag development. To do this as the heat progresses, the first helper must be able to make quick estimates of the composition and physical state of develop-

Jan 1, 1951

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By A. M. Nicholas

WHEN attempting to lift mill pulp containing a considerable percentage of wolframite, in an ordinary bucket elevator, difficulty was encountered from the tendency of the tungsten minerals to settle, on account of their high specific gravity. Lifts not exceeding 20 ft. (6m.) could be accomplished without particular difficulty, because there was insufficient time for consolidation of the heavy minerals in the bottom of the bucket; but with higher lifts, the heavy tungsten minerals would settle so solidly that when the bucket turned over at the top of the elevator the contents could be only partially dumped. In this case it ,was necessary to lift the material a distance of 34 ft. (10m.); hence some means had to be adopted to prevent settling, at least to such an extent that the material could be dumped from the buckets. To reduce the carrying time to a sufficient extent would have required a belt speed of 475 ft. (144.7m.) per minute, which was not feasible. It was decided to try, by vibrating the belt about midway of its span, to keel) the material sufficiently agitated during elevation to prevent settling. Underneath the rising side of the belt was placed a 12-in. (30.48-cm.) idler pulley, 18 ft.-(5.5 in.) up in the total lift of 34 ft. The idler pulley was set eccentric by 3/4 in. (19 mm.) and it was hoped that the vibration thus imparted to the belt, running at a speed of 280 ft. (85 m.) per minute, would prevent settling in the buckets. It was found that the pressure of the belt on the idler, due to the small inclination of the elevator, was not sufficient to overcome sliding on the idler, and the agitation was insufficient to accomplish the desired purpose. The idler was then connected to the drive shaft of the elevator through an intermediate pulley, gearing down to a speed of 20 r.p.m., so that a positive vibration was imparted to the belt; this imparted enough motion to the belt to prevent settling and the contents of buckets clumped satisfactorily.

Jan 2, 1918

By B. L. Averbach, Morris Cohen, S. A. Kulin

The martensitic transformation can be initiated by elastic stresses at temperatures above M. in a steel containing 20 pct Ni and 0.5 pct C. Shear strains and normal tensile strains acting on a potential habit plane promote the transformation but compressive strains oppose it. THE strain sensitivity of the martensitic transformation has long been recognized. It is now well known that martensite formation can be induced by plastic deformation at temperatures below, and not too far above, the M, point.' However, the exact role of elastic vs. plastic strains and of the concomitant stresses has proved to be a very elusive matter. Many investigators2-' of the steel hardening reaction have made use of the stresses resulting from volume changes to account for such observations as the existence of retained austenite and its variation across the section of a bar, the change in the amount of retained austenite with quenching rate, and the self-stopping nature of the transformation when the cooling is stopped. The effect of applied strain as an independent variable has been studied in 70 pct Fe-30 pct Ni alloys by Scheil7 and McReynolds.8 Some data are also available for lithium and Li-Mg alloys,9 Cu-Zn,10 Cu-Sn and Cu-A1 alloys," and aus-tenitic stainless steels."-" It has been found that martensite formation can be induced isothermally, even at temperatures above M,, by mechanical deformation of the parent phase. The competitive nature of plastic yielding by slip and by the martensitic reaction has been depicted by Scheil.7 Basically, Scheil postulated that: 1—at temperatures not too far above M, (where austenite is less stable than martensite), a critical resolved shear stress (within the elastic range) is required to promote the transformation to martensite; 2—at and below M,, the austenite lattice becomes mechanically, as well as thermodynamically, unstable and shears over spontaneously into martensite without the application of external stress; and 3—at temperatures sufficiently far above M8, the critical resolved shear stress for martensite formation increases to a level above that required for slip, and plastic flow then supersedes the transformation when external stress is applied. Scheil's concepts were tested by McReyno1ds8 ho found no change in the elastic moduli (measured both statically and dynamically) of 71 pct Fe-29 pct Ni alloys in the vicinity of the M, temperature. Since the moduli did not approach zero or become negative on cooling to M,, it was concluded that the austenite lattice does not become mechanically unstable at M2, as postulated by Scheil. McReynolds also reported that M, is not raised by elastic stresses. Accordingly, plastic deformation was considered to stimulate the transformation by generating martensite nuclei in the distorted regions of the parent phase. The above issues with regard to the role of applied stress require clarification, if a basic understanding of the martensitic transformation is to be obtained. For example, in the reaction-path theory,'"," it is postulated that strain embryos exist in the austenite that provide part of the activation energy for the nucleation process. These embryos are visualized to be regions of localized strain in which the atoms in the austenite lattice are displaced part way along the path to their ultimate positions in the martensite. Consequently, it would

Jan 1, 1953

By E. Orowan

LONG before the role of dislocations in the plastic deformation of crystals was recognized, the stress-strain field around dislocations received considerable attention in the theory of elasticity. It seems that Weingarten1 was the first to consider dislocations as simple and typical sources of internal stress in elastic solids, and Volterra2 and Timpe3 investigated their elastic field. Fig 3-1 shows the two basic types of dislocations considered by Volterra. The first arises by making a straight-edged .plane cut in a solid, displacing the two surfaces of the cut in their own plane relatively to one another by a constant amount in a direction perpendicular to the edge, and welding them together; this is shown in Fig 3-la, where the outer cylindrical surface represents the boundary of the solid, and the thin spiral cylinder around the edge of the cut has been removed in order to avoid infinities of stress and strain. The second type of dislocation is shown in Fig 3-lb; here the surfaces of the cut have been displaced relatively to one another by a constant amount parallel to the edge, and then welded together. After J. M. Burgers,4 these two types are called edge and screw dislocations, respectively. They represent simple limiting cases; in the general case, the surfaces of the cut are displaced by a constant vector that lies in the plane of the surface but has components both parallel and perpendicular to the edge of the cut. This vector is the Burgers or slip vector. The name “dislocation” was given by A. E. H. Love;5 it was bor-

Jan 1, 1954

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By H. L. Talbot, A. J. Hall, R. S. Young

A method for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators as responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control pur- poses. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or siinilar elements has come to the authors'notice. Experimental Procedure There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; Al2o3, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents as used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1949

By Notman, Arthur

THIS is a day of surpluses, some good and some not so good. One can hardly pick up a newspaper, magazine, review or economic treatise without confronting the fact that we have or are threatened with more .of certain goods than we have use for, whether it be corn, wheat, cotton, coal or oil, -lumber, 'leather, newsprint, automobiles, zinc, lead, copper or what not. How did this unprecedented state of affairs arise? Who is to blame? How shall we avoid smothering ourselves in our own production? The voice of the farmer is raised in appeal to the Government to relieve him from the dilemma of his own fertility. In answer the Government employs thousands of experts and spends millions of dollars to aid the farmer. But to what end? To make him still more efficient so that he may produce even greater surpluses? Not satisfied with the result, it spends other millions to prepare vast areas of the arid land of the West for more farmers to cultivate and insure yet larger surpluses. Then what? Naturally another appeal to the Government to fix prices by financing the

Jan 1, 1928

By J. Chipman, N. J. Grant, J. C. Fulton

This paper contains data on the distribution of silicon between liquid iron-silicon-carbon alloys saturated with respect to graphite and CaO-SiO2-Al2O3 slags under 1 atm of CO at 1600°C. The ranges of slag compositions studied were extended from the dicalcium silicate saturated liquidus composition up to silica concentrations at which Sic appeared as a stable phase. IN blast furnace operation it is not to be expected that slag and metal reach equilibrium with one another. Nevertheless, the silicon content of the metal varies with slag composition and with temperature in a manner which would be predicted from equilibrium considerations. Similarly, the distribution of sulphur between slag and metal does not attain an equilibrium state, yet the influence of slag composition is strongly analogous to its effect on the distribution equilibrium. The desulphurizing power of metallurgical slags has been shown to be highly dependent upon the FeO content of the slag. Moreover, the rate of removal of sulphur from slags is influenced by the oxygen potential of the slag-metal system. Thus it was shown by Grant, Kalling, and Chipman1 that the presence of MnO in slags which are low in FeO causes a marked slowing down of the transfer of sulphur from metal to slag. This led to the hypothesis that the slow removal of sulphur by blast furnace slags of more acid composition might be due in part to the effect of SiO2 on the oxygen potential of the system. This was verified in the work of Grant, Troili, and Chipman,' who found that the desulphurizing power of the more acid blast furnace slags could be markedly improved by an increase in the silicon content of the underlying metal. Their explanation of this improvement was that the higher silicon content of the metal decreased the rate of transfer of more silicon and, along with it, of oxygen from the slag to the metal. The slowness of the transfer of sulphur from metal to slag was the result of the slow reduction of SiO2 from slag to metal. Attempts to study the rate of sulphur removal had in the past resulted in very slow rates corresponding to the rates of silica reduction. It has become evident on the basis of these studies that further experimental studies on the rate of removal of sulphur must take these factors into consideration if there is to be a clear understanding of the rate of sulphur transfer under conditions simulating those existing in the blast furnace. It will be necessary, at least in a part of such study, to employ combinations of slag and metal in which the disturbing effect of silica reduction has been eliminated; in other words, to employ slag-metal combinations which are already in equilibrium with respect to the transfer of silicon. In preparation for such studies of desulphuriza-tion, a preliminary program of research on the distribution of silicon between slag and metal has been undertaken. This will ultimately include a comprehensive survey of the effects of temperature and slag composition on the equilibrium distribution of silicon between slag and metal. The present paper is a report on experimental methods employed and on

Jan 1, 1954

By A. S. Nowick, E. S. Machlin

ONE of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.1 During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time required for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error.2~3 This method of showing stress-rupture data has been adopted by many investigators and the KACA.4 By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, 100, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time for rupture on stress, temperature, com- position, and structure. In order to obtain this information, an investigation was made at the KACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given com- position and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efficiency and power output of gas turbines used in aircraft propulsion can be increased. THEORY The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 eveloped by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate- process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process.'' For example, in a chemical reaction the unit process is

Jan 1, 1947

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. [ ] In the latter part of 1925, a survey of the tunnels and gangways of the company's Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. QUANTITIES AND TREATMENTS OF TREATED TIMBER PURCHASED In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required on their receipt, on the basis of the piece or tonnage

Jan 1, 1942

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear's, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942