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By R. B. Russell

SINCE Cahn's¹ paper on plastic deformation in orthorhombic (a) uranium an increasing amount of work is to be expected on orientation of single crystals and preferred orientation in this metal. It would seem desirable to have a table of angles between crystallographic planes (hkl) and (HKL). Table I shows these angles as distances from (loo), (0l0), and (00l), and in Fig. 1 as a standard (001) stereographic projection. Only the locations of poles whose diffracting planes produce Cu Ka reflections up to 0 = 70.5" (i.e. (154) ) are given." The relative reflection of these planes are represented by circle diameters. It is hoped that the projection may also be used in making inverse pole figures, originally suggested by Harris.' Values of 4 were calculated from the expression hH kK 1L cos = hH/a²+kK/b²-lL/c² where the lattice parameters a, b, c, and the spac-ings d were taken from the work of Jacob and Warren." (They report a = 2.852 kX (2.8578 A), b = 5.865 kX (5.8768 A), c = 4.945 kX (4.9550 A).) The parameters reported by them may be subject to revision,4,5 accordingly the interplanar angles are listed to only the nearest tenth of a degree. References ¹R. W. Cahn: Acta Metallurgica (1953) 1, p. 49. ¹G. B. Harris: Philosophical Magazine (1952) 43, p. 113. 3C. W. Jacob and B. E. Warren: Journal ACS (1937) 59, p. 2588. 4J. S. Lukesh: Acta Crystallographica (1949) 2, p. 420. ³ J. Thewlis: Nature (1951) 168, p. 198.

Jan 1, 1954

By John H. Smith, Michael B. Bever

Pure gold was deformed by wire drawing at room temperature and 78°K. After deformation at room temperature, the stored energy and the resistivity increment reached nearly constant levels at high strains, whereas the yield stress continued to increase with strain. After deformation at 78K, the stored energy, the reszstivity increment, and the yield stress were larger than after deformation at room temperature mzd increased continuously with strain. Annealing at THE stored energy and the changes in properties resulting from cold working of Au-Ag alloys by various processes have been the subject of a series of investigations in this laboratory.'-' The work reported here room temperature after deformation at 78°K did not affect the yield stress appreciably. The stored energy, resistivity increment, and Lncrease in yield stress after deformation at room te-lnperature can be explained primarily in lerrns of dislocations while point defects, as well as dislocations, contribute to the changes in these properties after deformalion at 78°K. extends this research to pure gold. The stored energy, the resistivity increment, and the tensile properties after deformation by wire drawing were measured as functions of the strain at room temperature and at 78°K. The effect of the testing temperature and the effect of intermediate annealing at room temperature before testing at 78°K on the tensile properties of gold deformed at 78°K were also investigated. wire drawing made it possible to use a large range of strains, which was desirable because previous work on the deformation of gold had been carried out mainly at relatively small strains.'-l2 Also, wire specimens

Jan 1, 1969

Professional Divisions I-Institute of Metals Division* GEORGE K ELLIOTT, Chairman GEORGE C STONE, Vice-chairman WILLIAM M CORSE, Secretary-treasurer Executive Committee D K CRAMPTON SAMUEL L HOYT R I, SUHL W K FRANK ZAY JEFFRIES A E WHITE H W GILLETT H C JENNISON R F WOOD STANISLAUS SKOWRONSKI II-Petroleum Division F JULIUS FOHS, Chairman EDWARD L ESTABROOK, Vice-chairman C P WATSON, Secretary-treasurer

Jan 1, 1923

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-' Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.' To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-' Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-' Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- ' and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By G. Thodos, R. J. Smialek

A method has been developed that permits the correlations of Mehra and Thodos8 and Dastur and thodos2 for binary systems to be used for the prediction of the vapor-liquid equilibrium constants of the light and heavy constituents, Kland Kh, of a ternary hydrocarbon mixture. Furthermore, the unique relationship observed in this study, i.e., a plot of log Ke/Ki vs log Kp/K h is linear and passes through the origin, permits the calculation of the K-value for the intermediate component. This approach has been used to establish K-values for the constituents of the three ternary hydrocarbon systems used to develop this method and has also been applied to two additional ternary hydrocarbon systems to yield an average deviation of 7.7 per cent resulting from a total of 294 points for the five ternary systems considered. INTRODUCTION The rigorous calculation of vapor-liquid equilibrium constants for systems containing two or more components is a difficult problem and becomes extremely complex at elevated pressures and for conditions approaching the critical point. Although thermodynamic relationships can be developed to account for the vapor-liquid equilibrium behavior of simple systems, their use is limited because the necessary PVT data for these systems are not generally available. To establish a method for calculating K constants directly, without any recourse to the PVT behavior of a system, Mehra and Thodos8 applied the principle of corresponding states to the vapor-liquid equilibrium constants of binary hydrocarbon systems. They developed a series of charts which made possible the prediction of K-values for all binary hydrocarbon systems not containing methane. This work has been extended by Dastur and Thodos2 to include binary hydrocarbon systems containing methane. The charts developed in these two studies cover the high-pressure region and are applicable to conditions in the vicinity of the critical point. The ability of this approach to predict vapor-liquid equilibrium constants of binary hydrocarbon systems suggests that this method may be extended to the prediction of the K-values of the components of ternary hydrocarbon systems. In this investigation, the charts developed for both the methane and non - methane binary systems,2,8 together with mixture rules developed in this study, have been used to predict the K-values of the light and heavy components of a ternary hydrocarbon system. These calculated values are then used to establish the K-value of the intermediate component through the use of a novel relationship developed in the present study. DEVELOPMENT OF METHOD FOR PREDICTING K-VALUES OF TERNARY SYSTEMS The application of the corresponding state charts developed for binary hydrocarbon systems is restricted to those systems containing two components. The extension of these correlations to three-component systems requires that the ternary system be reduced to an equivalent binary, which can be treated in a manner consistent with the corresponding state development. To establish such an approach, the vapor-liquid equilibrium constant of the light component K is first calculated by assuming that the ternary mixture consists of the light component and a pseudo-heavy component of the intermediate and heavy constituents of the original ternary. To establish the vapor-liquid equilibrium constant of the heavy component Kh, the light and intermediate constituents of the ternary are combined to form a pseudo-light component of another equivalent binary system. The calculated values Kl and Kb are then utilized to calculate the vapor-liquid equilibrium constant of the intermediate component EQUILIBRIUM CONSTANT FOR LIGHT COMPONENT K To calculate the K value of the light (most

Jan 1, 1965

By Donald F. Saunders

Means and relative standard deviations were calculated for eU, eTh, K, and their ratios for aerial gamma-ray spectral data in 29 quadrangles at 1:250,000 scale. Known or suspected uraniferous provinces were characterized by: 1) Higher eU, eTh, and K means (due to generally higher radioelement concentrations); 2) Higher relative standard deviations for eU, eU/eTh, and eU/K (reflecting the presence of local uranium enrichments); and

Jan 12, 1979

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.' Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By W. C. Knopf, G. Samsel

For several years International Minerals & Chemical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large- scale plants. Natural potassium is composed of three isotopes -K39, K40 and K41. Five other isotopes, artificially produced, have been detected. In natural potassium only the K40 isotope, with a half life of 1.4 x 109 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes.

Jan 10, 1958

By J. D. Mooney

(San Francisco sleeting, September, 1915) THE accompanying chart has been drawn for the convenience of engineers as a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The, calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: p = kgW (L + 1OH) Where, p = the correct number of plies k = a constant, depending on the type of drive g = the weight in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = 1/250,000 For a simple drive, with a rubber-lagged pulley, k = 1/300,000 For a tandem dive, with bare pulleys, k= 1/375,000 For a tandem drive, with rubber-lagged pulleys, k = 1/455,000 The chart is drawn for a simple drive, with a bare pulley (k =1/250,000;

Jan 9, 1915

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

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2'3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By Franklin Moeller

Discussion of the paper of FRANKLIN MOELLER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 343 to 354. K. A. PAULY, Schenectady, N. Y.-I read with interest Mr. Moeller's paper descriptive of the mechanical parts of the new electric hoist at the Granite Shaft of the North Butte Mining Co. and as the paper treats largely of the mechanical equipment I have little discussion to offer. There is, however, one question which I would like to ask and that is, why the discrepancy in hoisting cycles between the curves given in the paper read by Mr. Sykes for the American Institue of Electrical Engineers at San Francisco and those given in the paper under discussion? In Mr. Sykes' curves the acceleration period is shown to be 16 sec. for all depths from 2,000 to 4,000 ft. inclusive, while Mr. Moeller in Fig. 2 shows 25 sec. throughout the range and in Fig. 4 shows 35 sec. Mr. Moeller's curves also show the following reductions in the peak load during acceleration: Level, Feet Mr. Sykes, Horsepower Mr. Moeller, Horsepower 2,060 3,500 3,130 3,000 3,800 3,480 Fig. 2 4,000 4,100 3,800 2,250 1,595 Fig. 4 As the purchaser's specifications called for 15 or 16 sec. I would like to know whether or not any modifications have been made in the requirements since the equipment has been installed.

Jan 5, 1916

By Donald F. Saunders

Means and relative standard deviations were calculated for eU, eTh, K, and their ratios for aerial gamma-ray spectral data in 29 quadrangles at 1:250,000 scale. Known or suspected uraniferous provinces were characterized by: 1) Higher eU, eTh, and K means (due to generally higher radioelement concentrations); 2) Higher relative standard deviations for eU, eU/eTh, and eU/K (reflecting the presence of local uranium enrichments); and lower mean eU/eTh and eU/K values (showing uranium loss from "average" rocks to form local enrichments). "Uranium favorability indexes," i.e., combinations of the sensitive variables, show an excellent qualitative relationship to known occurences and geologic favorability. Results appear to confirm the existence of long-term crustal uranium provinces formed at the time of emplacement of the oldest known rocks.

Jan 1, 1980

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

All the Technical PUBlications and Preprints published in 1932 are available at Institute headquarters. They are also on file in public, university and technical libraries and, when so indicated in the list, may be found in the Transactions. Copies of the Technical Publications have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Insti-tute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Copies of Preprints may also be obtained from the Secretary's office. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. Nonmembers may purchase the papers at the prices mentioned. Metal Mining Technical Publi- Title Author Meeting Trans. cation Volume No. and Page* 484-A.45 Propeller Type Mine Fan at Moose A. S. Richardson New York 102, 88. 95 F.52 Shaft. Butte. Montana (13) Feb.. 1932 487-A.46 Progress in the Improvement of Max H. Barber New York. Methods and Equipment at Feb., 1932 Open-pit Iron Mines on the Lake Superior Iron Ranges (9) Pre. Sand Filling through Pipes and Lucien Eaton New York, 102, 33, 41 Boreholes (9) Feb., 1932 Milling And Concentration 445-B.37 Soap Flotation of the Nomulfides Will H. Coghill New York. H.19 (18) J. Bruce Clemmer Feb., 1932 461-B.38 Principles of Flotation—An Experi- I. W. Wark New York. mental Study of the Effect of A. B. Cox Feb.. 1932 Xanthates on Contact Angles at Mineral Surfaces (48) Iron and Steel Division 447-C.81 Electrochemical Potentials of Nitri- Shun-ichi Satoh New York, fied Steels (31) Feb.. 1932 450-C.82 Reaistanoe of Iron-aluminum Alloya N. 9. Ziegler New York. 100, 267. 670 E.143 to Oxidation at High Tempera- Feb., 1932 tures (8) 451-C.83 Pressure Welding of Low-carbon C. H. Austin New York. Steela with Theoretical Con- W. S. Jeffries Feb.. 1932 siderations on the Mechanism of Such Welding (42) 453-C.84 Inclusions—Tbeir Effect, Solubility C.E.Sims New York, 100, 154, 176 and Control in Cast Steel (24) 0. A. Lillieqvist Feb., 1932

Jan 1, 1932

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer's personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company's office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893

IRON AND STEEL DIVISION Established as a Division February 22, 1928 K C. McCutcheon, Chairman T. L. Joseph, Past Chairman J B Austin, Vice-Chairman E K Miller, Vice-Chairman T. J. McLoughlm, Vice-Chairman Ernest Kirkendall, Secretary-Treasurer CO M M I T T E E S EXECUTIVE J. A. Bowers '54 J. S. Marsh '55 R. W. Campbell '54 D. L. McBride '53 Walter Carroll '55 G. B. McMeans '53 K. L Fetters '53 F. L. Toy '54 H. M. Griffith '55

Jan 1, 1952