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By J. L. Huiatt, D. G. Foot

The Bureau of Mines, U.S. Department of the Interior, investigated methods of recovering potash values from process and waste brines. Laboratory pan evaporation of four chloride brines produced crude salts containing predominantly sylvite, halite and carnallite. Six sulfate- chloride brines produced crude salts containing primarily schoenite, kainite, leonite, sylvite, carnallite, and halite. Potash grades ranged from 7.2% to 22.2% K20, and recoveries by crystallization ranged from 85% to 99%. Sylvite flotation from chloride evaporites with amine collector, recovered 90% to 97% of the potash in a concentrate containing 54.3% to 60.3% K20. Fatty acid flotation of the high sulfate evaporite recovered 78% of the sulfate minerals in a 28%-K20 concentrate. Flotation of the remaining chloride minerals with amine collector recovered 80% of the potash in a 59.7%-K20 concentrate. Solar evaporation of 37 854 L (10,000 gal.) of brine recovered 99% of the potash in a crude evaporite containing 24.5% schoenite and 20% sylvite. Flotation in a 45-kglh (100-lblh) continuous flotation unit recovered over 95% of the potash in schoenite and sylvite concentrates, containing 28% and 62.3% K20, respectively. An economic evaluation is included.

Jan 1, 1985

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By H. H. Podgurski, Hsun Hu

Large cryslals of high-purily iron (99.996+ pcl) cannot be obtained by the usual strain-ameal technique. Repealed phase transformation by thermal cycling prior to crilical deformation improves the capabilily of cryslal growith but fails to yield satisfactory crystals. Imperfect columnar crystals can be produced by the phase-transition method. The addition of a small amounl (0.005 wl pet) of nilrogen IT was reported'-4 that for metals of very high purity the usual procedures of the strain-anneal technique fail to produce large crystals. This was eliminates practically all the difficulties in crystal growth by the normal strain-anneal procedures. An actual example is presented, showing that most parts of a strip have been converted into a large crystal by this method. The addition of nitrogen, which can be removed from iron with less difficulty, is believed to be more desirable than carbon additions for the same purpose. thought to be due to the strong tendency for recovery in the high-purity metals: hence the critically strained matrix undergoes polygonization instead of recrystallization upon annealing for crystal growth. Talbot1,2 succeeded in overcoming this difficulty by adding 0.03 to 0.04 pct C to high-purity iron before critical deformation. followed by annealing in hydro-

Jan 1, 1965

Jan 8, 1950

Jan 1, 1897

By H. N. Wolcott

AMONG the many cases of replacement of one mineral by another, that of quartz or silicates by pyrite, or even other sulphides, is not uncommon, but the reverse of this process does not appear to have been recorded, even if it has been observed. It, therefore, seemed to the writer that the case described below was worthy of record. FIG. I.-GROUND MASS OF CHALCOPYRITE (C) CONTAINING ROUNDED GRAINS OF PYRITE (P) SHOWING DIFFERENT DEGREES OF REPLACEMENT BY QUARTZ (Q), AND ALSO QUARTZ VEINLETS CUTTING THROUGH THE PYRITE. (PHOTOGRAPHED BY REFLECTED LIGHT.) The specimens described in this paper were obtained by R. B. Morton of Idaho Springs, Colo., from the Old Town Mine, in Russell Gulch, and are in the collection of Cornell University, where the writer studied them. In the rough, the specimens appeared to consist largely of chalcopy- rite, with some grains of tetrahedrite. The polished surface of some of

Jan 6, 1917

By John H. Walthall, Raymond L. Copson, Travis P. Hignett

In October 1942, the War Production Board requested the Tennessee Valley Authority to undertake investigations to determine the feasibility of producing alumina suitable for reduction in aluminum cells, from clays and other domestic materials, by a lime-sintering, soda-ash leaching process. The work was undertaken by the chemical engineering staff of the Authority under the general direction of the War Metallurgy Committee of the National Academy of Sciences. The investigation included small-scale tests to determine the most suitable conditions for the process, and construction and operation of a pilot plant to obtain data for evaluation of the process and for design of a plant. The results of this investigation are described in the present paper. Sources of Alumina Alumina for the commercial production of aluminum is obtained from bauxite by the Bayer process. The tremendous demand for aluminum for wartime uses is causing rapid exhaustion of the high-grade bauxite deposits in the United States. On the other hand, there is an abundance of aluminous materials such as clay and lower grades of bauxite, which are not suitable for treatment by the Bayer process because of their high silica content. The Tennessee Valley Authority has conducted research and pilot-plant work for more than 5 years on methods for the production of alumina from clay and low-grade bauxite. Particular attention has been given to the high-grade white kaolin found in Carroll County, Tennessee. Exploratory drilling has demonstrated that at least 4 1/2 million tons of kaolin containing in excess of 34 per cent AlzOI is available in this area by strip-mining methods. It has been estimated that hundreds of millions of tons of clay of similar quality occur in the Tennessee Valley region. The Process The process is illustrated in the flowsheet (Fig. I), and consists essentially of the following steps: I. Heating a mixture of clay and limestone to form a sinter containing calcium aluminate and dicalcium silicate. z. Leaching this sinter with a dilute sodium carbonate solution, to form a sodium aluminate solution and a calcium carbonate, calcium silicate residue, which is discarded. 3. Treating the sodium aluminate solution with carbon dioxide to precipitate aluminum trihydrate and regenerate the sodium carbonate solution, which is recycled. 4. Heating the aluminum trihydrate to produce alumina. The process was considered promising because of the abundance and cheapness of the two raw materials, clay and limestone; and because, as compared with an acid process, smaller amounts of critical

Jan 1, 1944

By Wilbur T. Stuart

TO assist the mining industry in attacking problems of water control, the U. S. Geological Survey has begun a program of research in mining hydrology. In certain fundamental respects water control is similar to development of water supplies from wells or to the drainage of agricultural lands, as many of the tools developed in recent years for quantitative ground-water problems are applicable, with modification, to mine-water problems. In 1952 a 30-day pumping test conducted jointly by the Eureka Corp. Ltd. and the Defense Minerals Exploration Agency provided an opportunity to gain knowledge concerning water movements around a flooded mine shaft. The methods of analyzing the data may be used as a guide for the evaluation of similar problems elsewhere. The Fad shaft of the Eureka Corp. is on Ruby Hill, 1 1/2 miles west of Eureka, Nev. The shaft was completed at a depth of 2465 ft in November 1947 at a site adjacent to the downfaulted block in which the ore was found. As the drift on the 2250 level progressed toward the ore zone, a large flow of water was encountered after the Martin fault was intersected. This flow exceeded the installed pump capacity, and an unsuccessful attempt to recover the shaft and the 2250 level was made in 1948.1, 2 Geology and Hydrology: The complex structure of Ruby Hill is that of an anticline broken first by thrust faulting and later by normal faults. The present orebody comprises several mineralized zones within a block of the Eldorado limestone of middle Cambrian age which was downfaulted 1400 to 1600 ft, and it may be related to a similar body mined at a higher level south of the Ruby Hill fault. At the depth of the largest zone of ore the block is roughly rectangular in shape, about 1000 ft wide and 1500 ft long, and dips about 30" NE, see Fig. 1. It is apparently bounded on the south by the Ruby Hill fault, on the east by the Jackson fault, on the north by the Martin fault, and the west by the Bowman fault. Within the block, but between the Ruby Hill and the Martin faults, are the Office and Adams Hills faults; west of the block and the Bowman fault are the Albion and Spring Valley faults. There are many conflicting reports concerning the water-yielding characteristics of the Eldorado limestone and the condition of the fault zones, that is, whether they are open or tight. However, the diamond-drill records indicate that open spaces as much as 2 or 3 ft across were encountered, and considerable cementing and lining of holes was necessary to maintain circulation of drilling fluid. There is also evidence that the Eldorado limestone was cavernous where it was mined in the early days south of the Ruby Hill fault. At the site of the Fad shaft the formations encountered from the surface down included the Pogonip limestone, Dunderberg shale, Hamburg limestone, and Secret Canyon shale. These formations did not yield large quantities of water to the shaft. The Pogonip limestone, which appears to be permeable and might yield water elsewhere, is above the water table in the vicinity of the shaft. The Secret Canyon shale, immediately overlying the Eldorado in some places but in most places separated from it by the Geddes limestone,3 is apparently tight and does not transmit water. During the 30-day test period the shale briefly confined the water in the underlying formations so that artesian conditions were observed in drillholes E and F, which are cased into the Eldorado limestone, whereas unconfined conditions were observed in drillholes B, C, and D, which were open to the shale. The Geddes limestone, which normally lies between the Secret Canyon shale and the Eldorado limestone, was not encountered in the Fad shaft. The Geddes, a flaggy, fractured limestone, is reported capable of yielding large volumes of water. Water stored in the interstices of this thin-bedded limestone within the Ruby Hill fault zone on the 1200 level of the Locan shaft drowned the pumps in 1923 when the Richmond-Eureka Mining Co. attempted to explore the area along the fault. Eldorado limestone was not encountered in the Fad shaft. In the ore-block area the Eldorado limestone was not entirely offset from other water-yielding formations by movement along the Bowman fault; therefore it may be hydraulically connected with the other formations. Adjacent to the Ruby Hill, Jackson, and Martin faults, the Eldorado lies in contact with other possible water-yielding formations. One of these, the Prospect Mountain quartzite, is separated from the Eldorado by thin, sheared, and broken beds of the Geddes within the Ruby Hill fault zone. A limited examination by the author of the Prospect Mountain quartzite in the Richmond mine at a higher level and south of the Ruby Hill fault indicates that the quartzite is poorly permeable. The monzonite mass south of the quartzite would be a further barrier to the flow of water. The poor permeability of this area is substantiated by records of levels at which water was encountered south of the Ruby Hill fault. In view of the normally low rate of ground-water recharge, if this desert area had been permeable, water levels could not have been maintained at altitudes of many hundred feet above the present water table west and north of Ruby Hill. Thus the ore-bearing block of Eldorado limestone is in contact with possible water-yielding rocks on at least two sides, and if the fault zones are possible conduits for water circulation the geologic and hydrologic conditions are suitable for the infinite-aquifer type of analysis as used and modified here. History of Pumping: During sinking of the Fad shaft a maximum pumping rate of 1500 gpm kept the shaft dewatered sufficiently, but in March 1948, after the 2250 level drift passed through the Martin fault into the Eldorado limestone, the pumps and shaft were flooded. Subsequently additional pump-

Jan 1, 1956

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By John Chipman

IN the manufacture of rimming steel-which constitutes the bulk of the world's production of mild steel-the factors that determine the quality of the product are very closely associated with the pouring and solidification of the steel in the ingot mold. The behavior of the metal in the mold is, on the one hand, the resultant of the complex processes through which the liquid metal has passed, and, on the other, it is an indication of the probable behavior of the ingot during subsequent rolling and finishing operations. A detailed study of the mechanism of solidifica-tion of rimming ingots ought to yield information that will be useful iii controlling the structure of the ingot and the quality of the ultimate product. The first step in such a study is to determine the rate at which the solid shell of the ingot forms from the liquid metal in the mold. A knowledge of the rate of solidification will make it possible to correlate observations of rimming action and gas evolution with studies of the structure, porosity, and segregation within the ingot. Thus, if the metal in the mold is observed to fall, let us say one minute after pouring, the portion of the structure associated with this fall will lie located in the part of the ingot that is solidifying at that particular moment. The knowledge that the ingot solidifies to a depth of ¾ in. in the first minute enables us to locate in the ingot the structural features corresponding to the observed fall. Conversely, the blowhole condition associated with a rising or growing ingot will be found in the part of the ingot that is solidifying at the time the phenomenon occurs. The time required for the complete solidification of an ingot has long been a matter of speculation. It is of considerable practical importance in connection with charging and heating in the soaking pits. Too rapid handling of the ingot through heating and rolling processes has been thought to be associated-with excessive pipe and other internal defects, so that a further object of this investigation was to attempt to estimate the time required for complete solidification, or the minimum practical time within which the subsequent operations can be performed with the minimum hazard.

Jan 1, 1937

By William Hurst

THE content of this paper is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which b the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The paper is divided into two parts-the main portion and appendix. The main body is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir.

Jan 1, 1942

By R. Ebeling, M. F. Ashby

The paper is in two parts. The first develops the formulae and method needed to calculate the size, nu)nber, spacing, and volume fraction of hard or inert particles in the interior of a specimen from measurernents made on an extraction replica; throughout, the spread of- particle sizes in a single specimen is taken into account, and the extraction efficiency of the replica is considered. A method for testing whether the particles are randotnly distributed in space is described, and the spacing of randomly distributed particles is discussed. The second Part describes the application of the method to copper containing spherical particles of silica; the description includes an estimate of the errors involved, and a comparison of this with alternative methods. All parameters except uolume fraction can be determined satisfactorily, and the method offers advantages over other electron-,rzicroscopic techniques when dealing with hard particles in a softer matrix, or inert particles in a chem-ically less inert matrix. 1 HE experimental measurement of sizes and numbers of discrete particles of a second phase embedded in a matrix material from opaque, plane sections has been considered by many authors, notably by Fullman.' It is assumed that, when the specimen is sectioned, the particles are also sectioned, so that the diameters of the circles of intersection of particles with the plane of the cross section ("surface diameters") are measured. It is difficult to derive the distribution of true particle diameters ("volume diameters") from measurements of the distribution of "surface diameters" on a plane section. The measurement of size and numbers of small second-phase particles by transmission electron microscopy through thin foils of matrix containing the particles has been described by Cahn and ~uttin~' and by ~illiard.~ Because of overlap and the fact that particles which intersect the foil surface may be sectioned whereas those in the bulk of the foil are not, it is again difficult to measure the true distribution of particle sizes. The use of replicas for this sort of measurement has not been analyzed in detail. A replica made from an opaque cross section, thus replicating the circles of intersection of particles with the plane of section, is analyzed by Fullman's method and suffers from the same difficulties. Under certain circumstances, however, extraction replicas can be used, and offer a special advantage in that they make the determination of the true distribution of particle diameters particularly simple. It is the purpose of this paper to describe this extraction replica method. Consider the example of an alloy consisting of SiOz particles, whose mean diameter is about 1000A, dispersed in a copper matrix. When the alloy is sectioned and mechanically polished, the particles are not sectioned, because they are much harder than the matrix, and so will be either left in the surface or pulled out whole, and because the particle size is smaller than the abrasive size of even the finest abrasive. The particles are chemically inert in solutions which chemically etch or electropolish the matrix, so that chemical treatments do not section the particles either. (Experimental measurements of particle shape in this alloy confirm this—truncated particles are never seen.) Small, hard or inert, particles are therefore not sectioned when the specimen is sectioned and polished. An extraction replica taken from this polished surface shows the true "volume" diameter of each extracted particle; the distribution of diameters seen on the replica is the surface distribution of true "volume" diameters, and the volume distribution of true "volume" diameters is easily derived from it. The extraction replica method is not subject to the difficulties associated with sectioning of particles, and avoids the problem of overlap from which the transmission method suffers. The method is well-suited for studying hard particles in a soft matrix. Examples are provided by internally oxidized alloys, oxide-dispersion strengthened metals like T.D. Nickel, and carbides, nitrides, and strong intermetallic compounds in metals. It should be possible to adapt polishing techniques in alloys containing softer but inert particles to avoid sectioning the particles (say by electropolishing or etching). The method is tested and illustrated in Sections 8 and 9 by applying it to a dispersion of spherical SiO2 particles in a copper matrix. I) SYMBOLS Symbols are defined where they first appear in the text. Volume fractions of particles are denoted by the symbol f, particle diameters by x, center-to-center particle spacings by D, and numbers of particles by N. Mean particle diameters and standard deviations about these means are denoted by x and a. Both arithmetic (subscript A) and geometric (subscript G) means are employed. In this paper we measure the distribution of true diameters of particles which touch or pass through a random-plane section of the specimen. We may want to know the distribution of particle diameters in the

Jan 1, 1967

By G. W. Poling

Chemical and physical properties of thiol collectors are re-examined to compare the prospects,of heavy metal-thiolate or disulphide surface reaction products acting as actual collector species. Recent evidences for the existence and importance of each of these types of adsorbed species on sulphide minerals are also discussed. A conclusion is reached that partial coverage by chemisorbed heavy metal thiolate is often sufficient to confer practical levels of hydrophobicity and floatability. Only on a few highly conducting and "noble" sulphides does adsorbed disulphide-type collector oxidation product appear to be significant.

Jan 1, 1976

By Henry Rawdon

THE structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i.e., manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the inclosures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in "pure" metals in general (etching pits).

Jan 9, 1917

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

Joseph Esrey Johnson, Jr., had already achieved rare distinction as an able metallurgist, clear thinker, brilliant author, and wise consulting engineer to bankers and operators; he had achieved the essentials of a great career when dcath cut short his activities on Apr. 4, 1919, in the forty-ninth year of his age. He belonged to a family of iron blast-furnace men and mine managers. His father, Major J. E. Johnson, after serving with distinction in the Army of the North, identified himself with the iron mines and blast furnace at Longdale, Va., with which he was connected during almost his entire business life. It is significant, that, during those troublous times of reconstruction in the South, he enjoyed always the affection and respect of his neighbors and associates alike. From him his son obtained not only a thorough training in blast-furnace practice and iron mining, but great personal courage and force of character. His mother, who survives both her husband and sons, possesses rare intellectuality, humor and a tenderness and human sympathy which those who were privileged to know well J. E. Johnson, Jr., recognized beneath his exterior of aggressiveness and will power. In a recently published analysis of the qualities which characterize the world's great men, three traits stand out preeminently; viz., independence, courage, and intellectuality. Each of these characteristics J. E. Johnson, Jr., possessed in extraordinary degree. His early education was obtained under a private tutor at Longdale, and this circumstance probably enhanced a natural tendency to independence of character and individuality which, however, under the control of his unusual power of straight thinking and clear analysis never allowed him to go far astray. It has been said of him that if once he set his mind to a problem, however knotty, he scored a bull's-eye before the subject was dropped. His manner of attacking a subject involved first mastering the details of the available knowledge; then, putting this acquired information to one side, with an untrammeled mind blazing out a path of his own, so clear, so well-defined, and expressed in such simple terms that he illuminated the whole subject without distorting the original data or discussion. His two books, "Blast-furnace Construction in America" and "The Principles, Operation, and Products of the Blast Furnace, "on the iron blast furnace together form the most comprehensive, the most enlightening, and the most useful treatise on the subject ever produced in any language. But his ability did not end with the mastery and elucidation of principles enunciated by his predecessors; his own

Jan 1, 1920

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks' and to the precipitation of second phase particles,2'3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these '(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By T&apos Kê, ing-sui

INTRODUCTION ACCORDING to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. Such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, Zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on inelastic effects are, important in many fields of metals technology. Thus, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.' However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties of metals in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often can be obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion," the stress-induced diffusion of particles,8-12. and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we can - demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in. the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1948