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By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By H. Brandhorst, C. G. Dunn

THE main purpose of the present note is to provide further information on the effect of orientation on strain-induced grain boundary migration in sheet material. A secondary purpose is to draw attention to the presence of a possible (hkl) dependent surface energy driving force, when the two grains of a bicrystal specimen have different (hk2) planes at the gas-metal interface, and to suggest means of eliminating this effect from the strain effect. If two grains A and B of a bicrystal have specific surface energies ? A and ? B respectively, there exists a driving force for grain boundary migration equal to 2(? B - ? A)/t, where t is the thickness of the specimen.' When t is quite small and the residual strain energy densities €A and €B of grains A and B, respectively, adjacent to the boundary are nearly equal, it is possible that the surface effect may be larger than the strain effect. he difference € B - € A gives a driving force per unit area of grain boundary due to an applied strain.)2 However, with increasing t the surface effect decreases while the strain effect presumably remains constant. Therefore, at some sufficiently large value of t, it is possible to ignore surface energy driving forces.* On the other hand, the surface effect is eliminated for all value of t when both grains have the same (hkl) orientation or have identical values of surface energy. Although the previous study provided information on the effect of orientation on strain-induced erain boundary migration,' no orientations with the (100) plane in the plane of the sheet were included. The present paper provides information of this kind. A seed crystal reorientation technique4 was used to prepare a large bicrystal of silicon iron (3 1/4 pct Si) consisting of two (100) grains in the (100) [001] and (100) [Oil] orientations. After a cold rolling strain (7 pct reduction to 3/4 mm final thickness), small specimens were prepared as before2 and then annealed in hydrogen. The boundary migration was such that the grain in the (100) [011] orientation always grew. After overnight anneals at 1100° or 1000°C, none of the initial (100) [001] grain remained. An anneal of 30 min at 950°c, however, provided information on the start of boundary migration. Fig. 1 shows both the initial position (lower line) and the final position (upper curved line) of part of the boundary, as revealed by thermal grooves. In a different area, part of the final boundary was not revealed by thermal grooves; the rate of boundary migration presumably was too high for the growth front to be defined by the time dependent thermal grooving process. In another area there was a vacated intermediate position connected to the initial position of the grain boundary. This indicates that only part of the boundary

Jan 1, 1962

Upon nomination of the President, _the following Committee on Membership was appointed: Karl Eilers, Chairman, Arthur. S. Dwight, Lewis W. Francis, Louis D. Huntoon, Arthur L. Walker. The following resolution was then unanimously passed: WHEREAS, the integrity and life of this nation is dependent upon its ability to successfully defend itself against foreign aggression and attack, and WHEREAS, it is necessary that the nation he properly prepared to the end that our untrained patriotic volunteers he not uselessly slaughtered and our country disgraced and defeated, be it therefore RESOLVED: That the Board of Directors of the American Institute of Mining Engineers believe that compulsory universal military training should be at once instituted and that adequate, complete and immediate preparedness, should he provided. BE IT FURTHER RESOLVED: That, we believe that thorough and complete preparedness in the army, the navy and the industries of the country is vital; anything less is unsatisfactory and inefficient and may result in disaster to the nation.

Jan 5, 1917

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By C. G. Dunn

MANY investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal orientation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the, complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.1-3 Furthermore, it is believe that high-stress regions exist in the vicinity of these bands4a and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallization.5,6 Similar evidence has been published for nonferrous metals.5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins existed prior to recrystallization.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary orientation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha irons Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing. three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involve more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure" of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.1 LAW OF SIMILARITY The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simultaneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size. 5,6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increas¬ing section size (Fig. x). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By Evert Hoek

An empirical criterion is presented for use in estimating the strength of heavily jointed or weathered rock masses. This criterion incorporates the intact strength of the rock material and introduces two dimensionless parameters m and s which characterize the behaviour of the interlocking particles in a jointed rock mass. The use of rock mass classification systems for estimating the values of these parameters is discussed. The application of this non-linear failure criterion to the analysis of slopes is illustrated by means of a worked example.

Jan 1, 1983

By J. Doig, A. A. Bauer, F. A. Rough

AN investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems was conducted by studying alloys ranging in composition from uranium-31.5 at. pct Mo to uranium-34 at. pct Ti. A ternary cut showing these phase relationships is presented upon the basis of thermal-analysis data obtained and upon the basis of metallographic and X-ray examination of heat-treated and quenched specimens. Isothermal ternary sections, inferred from phase relationships determined between the two 6 phases, are presented for the uranium-molybdenum-titanium system. In the compositional range investigated, a y-ura-nium solid solution exists at elevated temperatures. At about 900°C the 6-U2Ti phase, with limited molybdenum solubility, forms. Epsilon, a molybdenum-titanium-rich solid solution appears at the same temperature and appears in all phase regions that exist below this temperature except in the terminal 6-phase regions. The y phase is stable to approximately 660°C in titanium-rich alloys; the y and 6-U,Ti phases decompose at this temperature to a uranium in a peritectoid reaction. The y phase in molybdenum-rich alloys of the ternary cut studied decomposes in an apparent eutectoid reaction, at about 593°C, to the 6-uranium-molyb-denum and a-uranium phases. The e phase while present, presumably plays a negligible role in these reactions. Titanium was found to markedly decrease the stability of retained y in these alloys. Age-hardening characteristics developed in titanium-contain ing uranium-molybdenum alloys quenched from 900°C and aged at 500°C are ascribed to decomposition of Y to the a and E phases. INTRODUCTION Alloys of uranium with molybdenum, titanium, and zirconium, respectively, are of great interest because of their potential use as reactor fuels. As a result, this interest extends to the constitution of these alloys, particularly in view of their uniqueness of constitution. In these systems, alone, among known uranium-alloy systems, an intermediate phase forms by direct decomposition of the high-temperature y-uranium phase. As a prelude to possible future alloy development, an investigation has been undertaken of the phase relationships that occur between the intermediate phases of these systems. These phase relationships have already been reported for the intermediate 6 phases of the uranium-zirconium and uranium-titanium systems.' The results of an investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems are reported here. The phase relationships that occur in the binary systems pertinent to this investigation are shown in Fig. 1. Phase nomenclature appearing throughout this report is as shown in these diagrams; the crystal structure of the phase is given in Table I. EXPERIMENTAL PROCEDURE Alloys were cast and fabricated to flat plate. Specimens were heat treated and examined metal-

Jan 1, 1959

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By A. E. Jenkins, A. Jostsons

Isothermal sections of the Ti-0-H phase diagvam at 600°, 700°, and 800°C have been constructed from equilibrium hydrogen pressure measurements over a range of Ti-0-H alloys containing up to 34 at. pct 0. Oxygen reduces the hydrogen solubility at fixed hydrogen pressure but increases the terminal solubility in the a solid solutions at the a/(a + P) phase boundary. Metal-lographic studies of alloys annealed below the eutectoid temperature show that oxygen also increases the ter-ninal solubility of hydrogen in the a solid solution in equilibrium with the hydride phase. The effect of oxygen on hydrogen solubility is discussed in terms of the electronic and geometric structure of interstitial solid solutions. THE isothermal solubility of hydrogen in a Ti-0 alloys at 800°C has been measured by Hepworth and ~chuhmann&apos; who subsequently used ternary Gibbs-Duhem integrations to calculate oxygen activities in binary Ti-0 alloys. The present study aims to extend Hepworth and Schuhmann&apos;s measurements to alloys richer in oxygen and to a range of temperatures. This paper presents the results of hydrogen equilibrium pressure/concentration measurements in Ti-0 alloys as well as observations on the effect of oxygen on the terminal solubility of hydrogen in a titanium. The thermodynamic properties of binary Ti-0 alloys, derived from these measurements, will be published separately.&apos; EXPERIMENTAL METHODS Specimen Preparation. Ti-0 alloys were prepared from iodide-refined titanium and titanium dioxide obtained by hydrolysis of redistilled titanium tetrachlo- ride. Specimens containing up to 16 at. pct 0 were prepared by electromagnetic levitation3 whereas a conventional tungsten arc furnace with a water-cooled copper hearth was used to melt oxygen-rich alloys. The specimen homogeneity was indicated by the constancy of lattice parameters of samples from various parts of the ingot as well as by the sharpness of the reflections on X-ray powder patterns. Oxygen-rich specimens in the composition range (20 to 34 at. pct), where ordering has been ~bserved,~ were annealed for 300 hr at 600°C prior to use in hydrogen solubility measurements. Apparatus. The hydrogen pressure/concentration measurements were made with a modified Sieverts apparatus shown diagrammatically in Fig. 1. Specimens were placed in a clear silica tube and impurity pickup by direct reaction with silica was prevented by lining the heated end of the silica tube with thin molybdenum sheet. A double silica tube was required to eliminate loss of hydrogen by diffusion through silica at high temperatures and high hydrogen pressures, the space between the tubes being maintained at a hydrogen pressure equal to that above the specimen. Hydrogen was purified by diffusion through a Ag-Pd tube.= Hydrogen pressures were measured with a mercury McLeod gage in the range 0.001 to 4 Torr

Jan 1, 1968

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8&apos;7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By J. W. Goss, M. J. Coolbaugh

A survey of literature published in the U.S. on grouting indicates that most such work has been done to stop water flow in mines and for stabilizing foundations of various man-made structures. Apparently San Manuel is one of the first mines in this country to use grout extensively underground for the strengthening and stabilizing of ground about drifts, shafts, and stations.

Jan 3, 1961

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

THERE has been little investigation of the gold-germanium binary alloys. Haughton1 does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least o.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at 12,0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke&apos;s value, was found to have a few gold dendrites in it. The eutectic temperature has been determined as 356.0 ± 0.5°C., slightly less than the temperature of 359°C reported by Einecke. The liquidus curves and the solid solubility of germanium in gold have been determined, and are shown in Fig. I. MATERIALS AND ALLOYING The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050° to 1100°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hypereutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be off composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallographic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By E. Brunner, E. S. Mardock

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By E. S. Mardock, E. Brunner

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By John N. Hobstetter

IT is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spontaneous diffusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow,&apos; Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Becker1 in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r. beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration, The increase in free energy per mole accompanying the formation of a nucleus which is just stable, ?fe, is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. THE NATURE OF THE NUCLEUS It is necessary to have rather detailed knowledge of the nature of a nucleus if ?Fe is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown3

Jan 1, 1948

By W. R. Hibbard

Although extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110) , [111] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wasserman11 reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. Preparation OF Specimens Crampton&apos;s5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5, 10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. Determination of Pole Figures A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.&apos; The three general types of pole figures

Jan 1, 1949