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By K. M. Rolls, R. M. Rose, H. B. Shukovsky

Studies of the phase structure, critical current density, and resistive critical magnetic field of a 45 pct Nb-55 pct Zr superconducting alloy after final-size heat treatments are reported in this paper. A combination of optical metallography, X-ray diffraction, and electrical-resistivity measurements were used to determine the phase structure. Superconductivity measurements, made with heat-treated wires, are correlated with microstructure. Although no quantitative relationship between microstructure and critical current density is found, it is shown that SINCE Kunzler1 as well as Berlincourt, Hake, and Leslie2 first described the high-field, high-current-density superconductivity of Nb-Zr alloys, it has be- the critical current density is highest when the microstructure is finely divided by fibering, coring, precipitation, or fine-scale phase dispersions. The resistive critical field is very sensitive to the compositions of the phases present. Since the alloy investigated here is near the maximum resistive critical field for the Nb-Zr system, any phase decomposition results in a lower H,. Elimination of the effects of cold work lowers H, also. A possible interpretation of the latter in terms of internal surface superconductivity is suggested. come apparent that the resistive critical field and the current-carrying capacity of such alloys are, in large measure, dependent on composition and processing. The resistive critical magnetic field (Hr) for low current densities has been found to increase progressively with zirconium content until a flat maximum is reached between 50 and 65 pet Zr.3 For any single composition, a characteristic maximum value of H, is attained by heavily cold-drawn wire.4 critical current density (J,) depends not only upon cold work but also, apparently, upon microstructure. Heat treatments of cold-worked wires generally

Jan 1, 1965

By DeVerle P. Harris

Risk for most mineral investments is greater than that of average business ventures, because the physical and economic characteristics of the mineral deposit are never known with certainty. Inasmuch as the merits of a potential mineral investment cannot be fully appraised without consideration of the impact to the investor of the possible unfavorable events associated with the adoption of the project, methods of risk analysis are important in project evaluation and investment selection. The conceptual framework for risk analysis and the means by which some of the recommended practices might be implemented are examined. In addition to the normal business risk due to market forces, the physical and economic characteristics of the mineral deposit are never known with certainty, for only partial or indirect information is available, such as data from drill cores or surface and underground workings. Consequently, risk for most mineral investments is greater than that of average business ventures. Inasmuch as the merits of a potential mineral investment cannot be fully appraised without consideration of the impact to the investor of the possible unfavorable events associated with adoption of the project, methods of risk analysis are important in project evaluation and investment selection. This paper examines the conceptual framework for risk analysis and means by which might be implemented some of the recommended procedures. Utility Theory A discourse on risk and its impact upon investment selection quite often leads the reader into the concept of utility theory, for utility theory is a device constructed by economists to measure the satisfaction an individuai receives from a good; in the case of investment analysis, that good is the outcome of an investment. It briefly is reviewed here to describe the reaction of the individual to risk and as a stepping stone to other techniques more suited to risk analysis at the level of the firm. Utility theory proposes that an investor possess a utility map (curve), such as indicated in Fig. 1, which indicates the value in utiles of potential monetary rewards to an individual with some specific endowment of resources. Points on this map are obtained from the following relationship:

Jan 1, 1971

By C. Schlumberger

SINCE the beginning of .the year 1928 the senior authors and their associates have applied a series of procedures which makes possible the detailed study in situ of the formations traversed by a drill hole before the casing has been landed. They have given the name "electrical coring" to the ensemble of these processes, which now replace in a large measure the mechanical coring performed by the drillers, and permit the gathering of bottom-hole data hitherto unobtainable. Three years have elapsed since the technique and interpretation of these measurements emerged from the experimental stage and entered the field of industrial application on a large scale. The total length of drill holes so far surveyed by the authors and their associates, all over the world, amounts to several millions of feet. Practical and strongly built equipment has been evolved, which permits the examination in a short time of an open hole several thousand feet long. No comprehensive paper has yet been published discussing the essential principles of the processes applied and bringing into evidence their economic interest. This is the object of the present paper.1 Numerous examples of field work performed under varied geological conditions are given, constituting a concrete illustration of the services rendered by the new methods. The study in situ of the formations penetrated by a drill hole is based on the measurement of a given physical factor or parameter associated with these formations. Generally. the measurements are made syste-matically along the whole length of the open hole. The physical factors or parameters which are now utilized by us to this end are: (1) the resistivities of the rocks; (2) their porosity; (3) their electrical anisotropy; (4) their temperature; (5) the resistivity of the muds. In order to

Jan 1, 1932

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By O. B. Bucklen, J. P. Matoney, P. G. Meikle, R. L. Terry

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also holds true for loading and storage facilities. Where once a 1 million st per yr (910,000 mt/yr) mine was rare, 3-5 million st per yr (2,730,000-4,550,000 mt/yr) mines are not uncommon today in the bituminous industry. This great increase in production, made possible through mechanization, requires greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend to- ward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw-coal storage and blending facilities. The development of the unit train with its attendant economics has contributed more than any other factor to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has added to the need for faster and larger loading facilities. In this climate of rapidly changing technology, any written ac-

Jan 1, 1979

By C. G. Bieber, R. F. Decker

The effects of minor constituents on the malleability of nickel alloys are described. These effects are related to the atomic diameter, valence, and position on the Periodic Table. The basic methods for removal or neutralization of deleterious elements are then reviewed. Finally, practical methods for melting nickel alloys are described in detail and related to minor constituent control. L HE first malleable nickel was produced by Fleit-man in about 1870 by the addition of manganese and magnesium to the molten metal to counteract the harmful effects of sulfur. Merica and Waltenbergl explained the mechanism by which these elements accomplished the desired result. They showed that sulfur in concentrations in excess of about 0.005 pct produced films of a brittle low melting eutectic of nickel-nickel sulfide which completely surrounded the grains. When manganese was added to molten nickel it reacted with the sulfur to form manganese sulfide which precipitated as widely scattered globules in the grain boundaries. The further addition of small amounts of magnesium converted the sulfur to a very stable sulfide of magnesium which was relatively insoluble in both the liauid and solid states and therefore occurred as finely divided particles within the grains where it had relatively little detrimental effect upon the malleability of nickel or its alloys. The practice of treating nickel with manganese and magnesium came to be called "deoxidation" and was employed without appreciable modification for the commercial production of wrought nickel and high nickel alloys (in this paper—50 pct or more nickel) until about 1930 even though the results were never entirely satisfactory. At that time a more extensive study was made of the effects of minor constituents on malleability and metallurgical quality. The results, small portions of which have been published,2-4 are presented here with other pertinent data. EFFECTS OF MINOR CONSTITUENTS UPON NICKEL Systematic additions were made of 0.5 pct or less of each of most of the elements of the periodic ta- ble. It was established in this study that some minor constituents other than manganese and magnesium were extremely influential. The malleability, as evaluated by the reduction of area in tension tests, depended roughly on temperature as shown in Fig. 1. Four temperature zones are of interest; the cold malleable zone (up to about 1000° F), the red short zone from roughly 1000° to 1500' F, the hot malleable zone around 2000° F and the incipient melting zone. Most of the malleability problems are associated with the red short zone and the discussion will concern this mainly. The reduction of area in normal tensile tests on high-purity nickel (see curve A of Fig. 1) appeared to have no

Jan 1, 1962

By R. E. Grace, H. W. Schadler

DARKEN1 has established the theoretical relation between the self-diffusion coefficients and the Boltzmann-MatanO Or interdiffusion coefficient: D is the Boltzmann-Matano or interdiffusion coef-

Jan 1, 1960

By Potts N. L., Eilerts C. K., Summer E. F.

The second-order, nonlinear, partial- dillerential equation representing the transient radial flow of gas - condensate fluids in reservoirs has been integmted by using finite -dillerence equations and electronic computers. Effect was given to pressure -dependent permeability, viscosity, and compressibility and to distance-dependent permeability. The influence of a second-degree velocity term in the Darcy equation was investigated. Implicit methods were used and practical, convergent solutions were obtained with material balance to less than 6 x 10-4 for recovery of one- hall the reserve at constant flow rate. Integration results provide the productive period of a reservoir for a given constant rate and the fraction of the fluid initially in place that can be recovered in that period. The properties of a lean and a rich fluid are represented in a set of integrations designed to demonstrate the effect of different constant-recovery rates and significant variables emphasized one at a time. INTRODUCTION A method is needed for computing the availability or reserve of a gas in a formation, making use of all technical and engineering information that is pertinent. As a step in this direction, a program for computing transient linear flow1 was developed that utilizes principles of earlier finite-difference computing for a similar purpose2-4 and gives effect to significant pressure- and distance-dependent properties of reservoirs and their contents. The present paper pertains to transient, radial flow of gas-condensate fluids. In the partial-differential equation of flow, effect is given to the variables viscosity and compressibility,5 and also to permeability. Included in the study is the quadratic form of the Darcy equation of flow that has been the subject of field tests6 and that has been applied to a gas with constant properties in transient flow computing. 7 Inclusion in the differential equation of variable coefficients to represent properties greatly complicates the higher derivatives of the equation. Because it was impractical to make a required improvement in certain of the finite-difference derivatives by Taylor-series expansion, five-term derivatives were used in the implicit computing. Related methods were developed that can improve general facility in manipulating finite-difference equations. BASIC EQUATIONS PARTIAL DIFFERENTIAL EQUATION The basic partial differential equation for transient radial flow in the direction of decreasing radius is l_ a(vpr) _? .......(1) r gr at where r = radius, L v = apparent velocity aIong radius, L/t p = density, M/L3 t = time, t Ø = porosity, dimensionless. In this equation, only the porosity is regarded constant. The density is where p = pressure, m/Lt2 M = molecular weight of fluid, m T = constant temperature of fluid, T z(p) = pressure-dependent compressibility factor, dimensionless R = gas Constant, mL2/t2t. The physical boundary of the reservoir is at re, and the producing boundary is defined to be at tq with rq = re /200. By definition,

Jan 1, 1966

By J. L. Craig, C. L. Edwards, M. D. Harper, J. M. Ray

The Los Alamos National Laboratory executed 19 intermediate scale cratering experiments in oil shale at the Colony Mine in Garfield County, Colorado. These experiments have led to a better under- standing of fracture characteristics and fragmentation of & - oil shale by use of a conventional high explosive. Geologic site characterization included detailed mapping, coring, and sample analyses. Site-specific geology was observed to be a major influence on the resulting crater geometry. The joint patterns at the experimental site frequently defined the final crater symmetry. Secondary influences included vugs, lithology changes, and grade fluctuations in the local stratigraphy. Most experiments, in both the rib and floor, were conducted to obtain data to investigate the fragmentation results within the craters. The rubble was screened for fragment- size distributions. Geologic features in proximity to the explosive charge had minimal effect on the rubble due to the overpowering effect of the detonation. However, these same features became more influential on the fracture and rubble characteristics with greater distances from the shothole. Postshot cores revealed a direct relationship between the grade of the oil shale and its susceptibility to fracturing. The Colony Mine experiments have demonstrated the significant role of geology in high explosive/oil shale interaction. It is probable that this role will have to be considered for larger applications to blast patterns and potential problems in retort stability in the future of oil shale development.

Jan 1, 1983

By H. J. Mutz

THE International Nickel Co. of Canada Ltd. operates five underground mines and an open pit. Four of the mines, the Frood-Stobie, Creighton, Murray, and Garson, are on the south range of the Sudbury Basin, map above, within a radius of 10 miles of the city of Sudbury, Ontario. The fifth mine, the Levack, is on the north range of the Sudbury Basin, 30 miles to the northwest of the city. The open pit is operating on surface ores of the Frood-Stobie orebody.

Jan 1, 1953

By C. H. Mathewson

CHARACTER OF THE WORK IN HAND IN planning the present experiments, we have made a particular effort to secure that adjustment of working conditions which would render the forthcoming tests most serviceable by way of indicating the comparative properties of the three different commercial grades of copper used. More specifically, we have endeavored to obtain certain definite information with respect to the relative behavior under test of ordinary electrolytic copper and furnace-refined lake copper containing (a) a moderate percentage of arsenic and (b) a rather large percentage of arsenic, in addition to the usual content of silver and other impurities. These comparisons were made systematic and comprehensive by testing throughout a series of (eight) reductions running from 0 to 70 per cent. in the case of cold-rolled metal, and throughout a series of (15) temperatures running from 100° C. to 1,000° C. in the case of annealed metal. In other words, a survey of properties similar to that made by Grard,1 in the case of electrolytic copper, was here repeated (with modifications) and extended to two other commercial varieties of copper.

Jan 7, 1916

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult's law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of 'TiCr, is —0.76' lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,' no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

Jan 1, 1970

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By G. Donald Emigh

Nothing is more important to life-plant and animal-than phosphate. Its compounds are essential to the energy functions of all living systems and for the formation of bones and teeth. Animals get their phosphate from eating plants and other animals, or domestically from feed supplements. Plants get their phosphates from the soil. Man's most important use of phosphate is for fertilizer; approximately 95% of the world's phosphate rock production is consumed by fertilizers. Most of the balance is processed in electric furnaces into elemental phosphorus, the important raw material for making industrial phosphates. Recovery of uranium from phosphates has been possible but not widely used. However, recent significant developments have generated interest in such recovery in the US and elsewhere. Phosphate occurs in all igneous and sedimentary rocks, and in all fresh and salt water. However, economical recovery is limited to deposits where natural concentration of the phosphate mineral has occurred. Occasionally natural concentration is great enough that the material can be used as mined; generally, however, the ore is low grade_ and must be concentrated. Phosphate rock is produced in 31 countries. Fig. 1 shows the location of major phosphate rock producers as well as some of the known phosphate deposits not yet in production. In the last decade the world phosphate industry has experienced steady growth. World production rose from 98 Mt of phosphate rock in 1973 to 140 Mt in 1982. Fig. 2 shows the growth curve of rock production and graphically illustrates the almost straight-line rise since 1945 in both US and world production. Table 1 gives the breakdown, by countries, of world rock production, 1974 through 1979. Table 2 shows US rock production by producing areas. Definitions of Terms Used in the Phosphate Industry Phosphate Rock: Commonly called rock in sedimentary deposits and apatite in igneous deposits. Those expressions generally include any mined, or mined and beneficiated, fluorine-containing calcium phosphate used as the raw material for the next stage of manufacturing. The average phosphate content in rocks is 0.1 to 0.2% P2O5, as documented by McKelvey (1973). About 200 minerals contain more than 1 % P2O5. However, the important mineral in igneous rocks is fluorapatite, [Ca5 (PO4),3 F], containing about 42% P205 and 3.8% F2; in sedimentary rocks the important mineral is francolite, a carbonate fluorapatite containing up to 2% molecular CO2. Both are in the apatite family of minerals. Most phosphate rock, whether beneficiated or not, is a fine-grained material. The expression phosphate rock has no relation to its phosphate content. For example, phosphate rock from Idaho used in the production of phosphorus may contain about 24% P205, whereas rock from Morocco may contain 36.6% P2O5. Phosphorite: A deposit of phosphate directly or indirectly of sedimentary origin, which is of economic interest. Grade of Phosphate Rock: The calcium phosphate content of phosphate rock is expressed in different world areas by one of the following terms: BPL (bone phosphate of lime) TPL (triphosphate of lime) P2O5 (phosphorus pentoxide) P (phosphorus-not commonly used) An illustration of relationship is: 80% BPL = 80% TPL = 36.6% P5O2 = 16% P

Jan 1, 1983

By D. J. McAdam, R. W. Mebs

The technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. According to the prevalent view,8 the technical cohesive strength of a metal. in any particular state as regards prior mecharlical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress. In two previous papers by one of the authors, evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion Limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.' In this paper, as in the previous papers,14.15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated 33, and the intermediate principal stress will be designated S². The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress."l4, .l5 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,15 however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average Of the three principal stresses.* This in fluence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers,".'5 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant • Any stress system ma? be resolved into a polarsymmetric stress causing pure volume strain and a combination of pure shearing stresses. which cause no change of volum

Jan 1, 1945

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis' and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations' that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By Alexandre Mitinsky

The theory of elasticity, the science of the strength of materials, and all our calculations regarding engineering structures are based on Hooke&apos;s law, that in loaded bodies the deformations are proportional to the load producing them. Without this law it would be impossible to design intelligently engineering structures such as bridges, frames, axles, etc. This being the case, the proportional limit,l that is, the point at which deformation ceases to be proportional to load, is the most important factor in engineering design. Further, the working fiber stress should be fixed in reference to the proportional limit instead of, as is usual, in reference to the ultimate strength. The incorrect use of the ultimate strength instead of the proportional limit in setting the working fiber stress is probably due to two reasons: (1) it is a more delicate operation to measure the proportional limit; (2) it is usually assumed, though incorrectly, that the proportional limit is determined by the ultimate strength. In Germany the poin&apos;t at which permanent set first appears is often taken instead of the proportional limit. The two points will coincide if Gerstner&apos;s law, that elastic deformations are proportional to the loads producing them both before and after permanent set, is true; and the limit of proportionality and the elastic limit or point of permanent set will both be represented on a stress-strain diagram, by the point at which the line ceases to be a straight line and becomes curved or changes its inclination. It is to be further noted that the difference in definition between proportional limit and elastic limit introduces a difference in methods of determination in the testing laboratory. The German method of determining the elastic limit by alternately loading and unloading the test specimen is a lengthy process and time has in itself a very considerable influence on the results of physical tests.

Jan 1, 1916