Search Documents

By David L. Holt

It is well-established that hydrostatic pressure distribution is hardly achieved during uniaxial compaction of powders. All the previous investigations1-4 give consistent results and this variation is attributed to the die-wall friction. The conclusions are based on measurements of the density of very small portions of the compact. Although the analysis of the density or the strain distribution in the compact is very helpful in obtaining information about the stress distribution within a powder compact, it does not describe the problem from a more fundamental point of view. The densification in metal powder compacts takes place chiefly by plastic deformation (ignoring particle rearrangement) at the points of contact of the powder particles. The onset of yielding and subsequent growth of the contact areas (for spherical powders) take place fixed by a constant stress equal to three times the yield stress in tension or compression,5-7 assuming little or no work hardening. Therefore, by deforming spherical powders in the die and measuring the contact areas on each particle, the load at each contact point can be determined. In the present investigation, this was done by hot-pressing uniform spheres of lead, K-Monel, and sapphire. The details of the experiment have been described elsewhere.' The spheres were studied for the size and the number of contact points on each particle using a specially designed goniometer. It was found that the deformed faces that were approximately normal to the direction of pressing were about 2.2 times larger than those parallel to the direction of pressing. Fig. 1 shows the typical deformed sphere. A detailed study showed that the mean value of the contact areas on each sphere was within 5 pct for all the spheres in the die (ignoring those touching the die walls and the top and bottom of the die).' The spheres touching the die walls and the top and bottom of the die were found to have larger contact areas (8 to 10 pct) which indicates higher pressures in these regions of the compact and thus higher compact densities in these regions. These results show that density distribution calculated from such an experiment will give results consistent with the previous investigators. It is concluded, therefore, that the pressure distribution in the die is better understood by studying contact areas on each particle. 'R. Kamm, M. A. Steinberg, and J. Wulff: Trans. TMS-AIME, 1947, vol. 171, p. 439. 'Pol Duwez and Leo Zwell: I. Metals, 1949, vol. 1, p. 137. 'G. C. Kucynski and I. Zaplatynskyj: Trans. TMS-AIIME, 1956, vol. 206, p. 215. 'R. P. Seelig and J. Wulff: Trans. TMS-AIME, 1946, vol. 166, p. 492. 'H. Hencky: Z. Angew. Math. Mech., 1923, vol. 3, p. 241. "J. Ishlinsky: I. Appl. Math. Mech. USSR, 1944, vol. 8, p. 233. 'D. Tabor: Proc. Roy. Soc. (London), Ser. A, 1948, vol. 192, p. 247. 'Ashok K. Kakar and A. C. D. Chaklader: 1. Appl. Phys., 1967, vol. 38, p. 3223. Superplasticity in 60Zn-40Al David L. Holt THE occurrence of superplasticity in Al-Zn alloys is of interest because of its possible industrial exploitation.' The eutectoid composition (78Zn-22A1) has been the most extensively studied;'-= neck resistant flow and high strain rate sensitivity of flow stress (characteristic of superplasticity) are associated with a micron-size grain conferred on the alloy by an homo-genization and quench.5'6 Compositions away from the eutectoid have received comparatively little attention, especially from the viewpoint of relating the structural

Jan 1, 1969

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By R. T. DeHoff

Saltykov's meihod for the determination of the size distribution of spherical particles from measurements made on random plane sections is extended to particle shapes which are not equiaxed. The analysis permits the deterrrzination of the size distribution of aggregates of ellipsoidol particles provided all particles have tlze same shape. V ARIOUS solutions to the problem of the determination of the size distribution of spherical particles from measurements made on random plane sections have appeared in the literature since the original solution was first published by Scheill in 1934. Solutions have been offered utilizing measurements of the diameter1y2 or area3'4 of circular sections that result when a test plane is passed through an aggregate of spherical particles, and the length of intercept5y6 that results when a test line is passed through the aggregate. To the best of the knowledge of the author, no method has been proposed which permits the determination of the size distribution of particles that are not equiaxed. The purpose of this paper is to develop a method which permits the determination of the size distribution for a specific class of particle shapes which cover awide range of axial ratios; namely, ellipsoids of revolution. In the interests of simplicity, it is necessary to limit consideration to aggregates of particles which are all similar in shape; that is, the ellipses which, by rotation about one of their axes, generate the particles, all have the same axial ratio. The size distribution, which is to be determined by the analysis, is arbitrary. It is also assumed that the section, or sections, upon which the measurements are made represent the average of all possible sections through the structure. This ideal condition can be approached as nearly as may be desired by observing a sufficient area of sections taken at random positions in a randomly oriented aggregate, and in random positions and orientations in an aggregate that has one or more axes of orientation. SIZE DISTRIBUTION FOR PROLATE ELLIPSOIDS Consider an aggregate of cigar shaped, geometrically similar particles (prolate ellipsoids), dispersed in an opaque matrix. Let the size of each particle be specified by the length of its minor axis, By Fig. 1, and the shape, q, be defined by the ratio of its minor to its major axis, B/A. Let the index, j, refer to dimensions of ellipsoids in a particular size class, and the index, i, to dimensions of an ellipse resulting from the intersection of a test plane and a particle. The size of such a section is specified by the length of its minor axis, b. Let the particles be arbitrarily divided into k size classes, and let the increment of size between each class be A, where A = &,$, B,,,being the minor axis of the ellipsoids in the largest size class. Since all sections are represented on the test plane, the minor axis of the largest of the sections observed, results from the intersection of the test plane with an ellipsoid in the largest size class at its center, and is therefore equal to Bmax Thus the increment, A = The final result will consist of the k numbers which represent the number of particles in each size class per unit volume of aggregate:

Jan 1, 1962

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968

By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

By G. Y. Chin, A. R. Von Neida

The relationship between crystalline texture and magnetic anisotropy in a Co-10 pct Fe alloy has been investigated by means of X-ray pole .figures, hysteresis-loop tracings, and magnetic-torque measurements. The cold-rolled texture of a sample after 95 pct thickness reduction is of the "brass-type", that is, (110)[112/. At 500°C the cold-rolled material recrystallizes fo a (311)[112] orientation, plus a minor (210) [001] component. This texture persists up to 1400°C, at which point it is replaced by a secondary recrystallization texture, (111)[112]. Magnetic-torque measurements show that the easy axis of magnetization lies along the transverse direction in the cold-rolled material and changes to the rolling direction after primary recrystallization. This change is also reflected in the hysteresis characteristic; whereas the B-H loop along the rolling direction is nonsqunre with a low value of residual induction (750 vs 19,000 gauss at saturation) for the cold-rolled material, the annealed sample exhibits a very square loop with a large value of residual induction (16,000 gauss). Theoretical torque curves calculated from the texture data on the basis of magnetocystalline anisotropy energy compare favorably with the observed torque curves. Values of the crystal anisotropy constant, K1, obbained from these comparisons are in good quantitative agreement with single-crystal data. Furthermore, both the torque amplitude of the poly crystalline material and the magnitude of K1 obtained with a single crystal show an identical temperature dependence over the range from —195° 10 +220°C. It is thus conclzided that the magnetocrystalline anisotrpopy erlergy is chiefly I-esponsible. for the nzagnetic allisotropy of textured Co-10 pct Fe alloy. THE results of a study on the relationship between crystalline texture and magnetic anisotropy of an alloy containing 90 pct Co and 10 pct Fe by weight are reported in this paper. The alloy has an fcc structure: a saturation magnetization of about 19,000 gauss,2 and a nearly zero value of magnetoatriction.3 puzey4 has reported a large crystalline anisotropy constant of -7.4 X 105 ergs per cu cm, indicating the (111) directions as the easy axes of magnetization. Hence, texture variations resulting from cold work and annealing are expected to introduce a magnetic anisotropy in the polycrystalline material through the alignment of these (111) easy directions. In the present study, magnetic anisotropy of both rolled and annealed strips was determined by magnetic-torque measurements and hysteresis-loop tracings The results were correlated quantitatively with calculations based on texture data obtained by the X-ray pole-figure technique. It is established that the magnetocrystalline anisotropy energy is indeed chiefly responsible for the magnetic anisotropy of textured Co-10 pct Fe alloy. EXPERIMENTAL Material Preparation. The alloy nominally contained 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn by weight, the chief impurities being nickel, carbon, and silicon (less than 0.5 pct total). The cast ingot was rolled to strips 10 mils thick and slit to 1 in. in width. After strand annealing at 900°C in a hydrogen atmosphere, these strips were further cold-rolled to various thicknesses down to 0.25 mil (97.5 pct reduction), with samples collected for study of the development of texture and magnetic anisotropy as a function of thickness reduction. subsequently, samples cold-rolled from 100 mils to 0.25 mil were obtained, thus extending the thickness reduction range to 99.75 pct. In addition, 0.5-mil samples cold-rolled from 10 mils were selected

Jan 1, 1965

By H. Guyod

The response of the Guard Electrode sonde (LL3) and the Laterolog (LL7) can be mathematically computed only for cases that do not represent realistic conditions. A resistance network analogue that simulates a number of typical—although idealized—formations was used instead to obtain, for both devices, a large number of resistivity logs and current distribution maps. From these data, charts were prepared for estimating true resistivities under a number of conditions. Some of these charts and current distribution maps are presented. INTRODUCTION Two main benefits are expected from a resistivity log: (1) obtaining geological information for mapping and other purposes, and (2) obtaining petrophysical data, based on true rock resistivity. The geological information can be derived from any resistivity curve having sufficient vertical detail, but true rock resistivities frequently are difficult to determine with desired accuracy because we do not have sufficient interpretation data. This is particularly true for the records given by the Laterolog tools. The object of this paper is to throw some light on the factors affecting the responses of these tools so that better resistivity data can be obtained from Laterologs. LATEROLOGS Laterolog measuring systems are of two types: the LL3 sonde, frequently called "Guard", and the LL7 sonde. Both measure the resistance between a single exploring electrode placed in the borehole and a faraway return electrode whose influence will be assumed here to be negligible. Although the principles of these tools have already been outlined,1-3 it is desirable to review them briefly in this article. LL3 Fig. 1, left side, represents a long cylindrical, vertical current electrode placed in a medium of uniform resistivity. The current leaving the center section of the electrode flows essentially along horizontal lines, delineating a surface having the shape of a biconcave lens. It is the elec- trical resistance offered to this particular group of current lines that is measured by the Guard tool. This is done in practice by having a long cylindrical electrode consisting of three sections physically and electrically separated by thin insulating washers, as shown in the center of the figure, and keeping the three sections at the same potential. It is obvious, for all practical purposes, that the current and potential distributions about this electrode are the same, as if we had a continuous electrode of same dimensions. Because the three sections are electrically separated, the resistance seen by the center section E can be independently measured. This section will be called the exploring electrbde, or E electrode. Its height generally is from a few inches to 1 ft. The outer sections are the guards G, which are several feet long. The combined length of the three sections is from 10 to 12 ft for the tools currently used in the petroleum industry. Let V denote the potential difference between E and the faraway return electrode, and I be the current flowing between these two electrodes. The resistance (Re) seen by the exploring electrode is VII, and the corresponding apparent resistivity is Ra = k(Re),............(1) where k is the tool calibration factor. The previous description establishes that the Guard tool uses that central portion of the sonde from which, in a uniform medium, the current follows essentially horizontal paths. When the formation being logged is fairly uniform, and when its resistivity is of the same order as

Jan 1, 1965

By A. E. Dwight, A. F. Berndt

ThE published U-Ru equilibrium diagram indicates the existence of six intermetallic compounds in this system.' The structure of only two of the compounds, u2Ru2,3 and URU3,4 have been identified. This communication reports on the crystal structure and density of Uau3, which is formed by a peritectoid transformation at 1025° ± 5°C: U3Ru4 + U3Ru5 = U2Ru3. An alloy with the stoichiometric formula U2Ru3 was prepared by arc melting electrolytic uranium and ruthenium of 99.9 pct purity on a water-cooled copper hearth under an argon atmosphere. After homo-genization at 1000°C for 3 days, a metallographic examination revealed that the peritectoid transformation was complete and less than 5 pct of a second phase was present. A powdered sample, obtained by crushing the brittle compound, was annealed for 1 hr at 1000°C and air-cooled. Debye-Scherrer patterns were obtained with filtered CrKa, FeKa, CoKa, or CuKa radiation. The X-ray patterns of U2Ru3 weFe indexed as an fcc structure with a. = 12.895 0.00lA. The unit-cell constant and its standard deviation were calculated by a computer program described by Mueller, Heaton, and Miller.5 The density, measured by an immersion method, was 14.45 g cm-3. A calculated density of 14.48 g cm-3 was obtained on the assumption that twenty-four formula units (120 atoms) comprise a unit cell. The space group is either oh7 Fd3m, or the less symmetric, T4h, Fd3, since reflections indexed as hk0 with h + k + 4n are absent. All values of h2 + k2 + 12 permitted by both space groups are listed in Table I together with dc, do, and I. values. The calculated d spacings were obtained by the computer program of Mueller, Meyer, and simonsen.6 The observed d spacings above 0.77A were obtained from X-ray" patterns prepared with CuKa radiation, above 0.90A with CoKa radiaaion, above 0.98A with FeKa radiation, and above 1.16A with CrKa radiation. An attempt was made to identify the crystal structure of U2Ru3 by comparison with published data on other A2B3 compounds. A recent compilation7 of intermetallic compounds lists thirty-two structure types with the A2B3 stoichiometry. Only two of the structure types are fcc and they are Sb2O3(r), senarmontite, with 16 Sb2O3 per unit cell, and In2Te3 for which several structures have been proposed.8 However, the two cases cited do not have twenty-four formula units in the unit cell. We therefore, cannot identify UPRU3 with any of the other known A2B3 compounds. Ternary alloys were made in which 5 at. pct Os, Rh, or A1 were substituted for 5 pct of the Ru in U2Ru3. The osmium substitution increased the unit cell constant to 12.899 * .001A, which is to be expected since the atomic volume of osmium is slightly larger than

Jan 1, 1969

By W. Rostoker, R. P. Elliott, B. W. Levinger

Phase equilibria in the Ti-Mn-Mo system have been investigated in the composition range 100 to 60 pct Ti and in the temperature range 550 to 1150°C. Three out of ten isothermal sections are presented as well as seven vertical sections, projections of the beta space and the surface of incipient melting. A STUDY of the system Ti-Mn-Mo was undertaken as part of a program to aid in the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range 100 to 60 wt pct Ti (all compositions refer to weight percentages) and the temperature range 550" to 1150°C. A surface of incipient melting was constructed from measurements of a large number of alloys. In the binary system Ti-Mo,' the high temperature modification of titanium generally spoken of as the p phase is stabilized to successively lower temperatures with increasing alloy content. There are no known intermediate phases, and complete miscibility exists between body-centered cubic titanium and molybdenum. The u solid solution is limited to less than 0.8 pct Mo at temperatures between 885" and 600°C. An equilibrium diagram for the binary system Ti-Mn has been published.' Manganese behaves as a p stabilizer but undergoes a eutectoid transformation at about 20 pct Mn and 550°C to a plus an intermediate phase. The structure of this phase has been found to be isomorphous with the a phase FeCr." Accordingly, the phase is assigned the formula TiMn, although its actual location on the composition scale has not been determined and may well be not exactly at the equiatomic composition. In disagreement with ref. 2, the origin of the TiMn phase has been shown' to be a peritectoid transformation at a temperature between 900" and 1000°C. A second intermediate phase occurs at the atomic proportions TiMn,. The structure of this phase was originally established by Wallbaum" as having a hexagonal lattice (C 14 type, 12 atoms per unit cell) isomorphous with MgZn,. In this work, the structure determination was confirmed and lattice parameters determined to be: a = 4.815 kX, c - 7.901 kX. Because of the extensive range of the P phase, the ternary system was suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." During the course of the investigation, this method was found applicable only to the P/a+P boundaries but not to P/P+ compound boundaries. Metallographic methods were used alternatively for delineating these phase boundaries. Preparation and Treatment of Alloys Over 70 alloys were prepared for the study of this system. Ten gram alloy buttons were arc melted in a nonconsumable electrode furnace using inert atmosphere protection, and a water cooled copper crucible. The construction and operation of this type of melting unit has been described.' To insure complete solution of alloy additions, especially molybdenum, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" the ingots over. It was very difficult to obtain homogeneous melts in the region of less than 75 pct Ti because of the very high melting point of molybdenum and Ti-Mo master alloys and the comparatively low boiling point of manganese. Thus, the arc conditions for insuring complete solution of molybdenum were incompatible with the prevention of heavy losses of

Jan 1, 1955

By R. Shuttleworth, R. Smith

A Knudsen effusion tnethod I~as been used lo measure the vapor pressure of pure iron in the temperature range 1000° to 1500°C. Neutron-irradiated , natural iron was used and the Mn'~proclzdced by the (n, p) reaction removed by evaporation at high temperature. The results can be represented by the equation: where pM - 1.088 x 107 atm and T, = 20,890°K. A value of 100.2 kcal per g- atom was obtained for AH;. THE vapor pressure of pure iron in the temperature range 1000" to 1500°C has been measured. Radioactive iron and a Knudsen cell technique were used and the Mn' produced by an (n, p) reaction removed by evaporation at high temperature. From the variation of vapor pressure with temperature values of the enthalpy and entropy of solid iron have been found. Previous workers2 used a Lang-muir method and measurements were made over a smaller temperature range than that in this work. EXPERIMENTAL The apparatus used was similar to that of Pyle and Shuttleworth, and McLellan and Shuttle worth. However, because of the higher temperatures the Knudsen cell was machined from tungsten bar and the flanged furnace tube was beryllia. Heating was by passing a high current (70 amp at 7 v for 1500°K) through a strip of tantalum foil laid across the top of the cell and through a turn of molybdenum wire around the furnace tube. This method of heating ensured that the top of the cell was slightly hotter than the base and prevented condensation and re-evaporation from the orifice. The temperature was measured by means of a pt/Pt 13 pct Rh thermocouple spot-welded to the base of the crucible. To ensure accurate temperature measurement the iron was in the form of a thin disc (0.75 cm diam by 0.075 cm) which lay on the base of the cell. The high-purity iron was irradiated in the Harwell pile for a week at a neutron flux of 1.2 X 10" neutrons per sq cm per sec. The isotopes fe'~ and Fe" are produced by (n! y) reactions but only Fe", half-life 45.1 days, is a emitter; Mn which is also a y emitter, half-life 300 days, is produced simultaneously by an (n,p) reaction.' Immediately after irradiation of natural iron the ratio of ~e" to Mn y activity was 100:l. However, manganese is very much more volatile than iron and almost all the y activity of the condensate is due to Mn'~. Thus it was essential to eliminate all the manganeses before any measurement of the vapor pressure of iron was made and this was done by preliminary heating for 20 hr at 1400°C. For each determination the iron was dissolved from the target with acid and the y activity compared to a known weight of iron. By means of a y-ray spectrometer the y-activity measurements were made at the 1.09-mev peak of the 17e5' spectrum where the background was of the order of 3 cpm. Despite the low specific activity of ~e" a mass of 10- " g of iron could be determined corresponding to a vapor pressure of about l0-'' atm. RESULTS The vapor pressures were calculated from the equation: Where m is the mass of iron effusing in a time t through an orifice of area a2, r is the radius of the target, Z is the distance from the orifice to the

Jan 1, 1965

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965

By M. W. Hayward

THE object of this paper is to record and tabulate the data and field observations obtained by the writers and their associates during 10 years of intensive study of lead-zinc deposits in the Cretaceous limestone areas in Northern Mexico, particularly in mines owned by the Cia. Minera de Peñoles, S. A. At the El Paso meeting of the Institute in October, 1930, J. G. Barry made the suggestion that a committee be appointed to correlate the ideas and theories which have been put forth by the numerous engineers and geologists who, during recent years, have made a study of the ore deposits in the area under consideration. The first step in a work of this nature would be to record all of the observed facts, and these facts would have to be accepted by those who attempted to formulate a theory of ore deposition. It is with this idea in mind that the writers have described as accurately as possible the actual, observed facts pertaining to the occurrence of the lead-zinc ores in dolomites or dolomitic horizons. By most writers the term "dolomite," is loosely used to designate magnesium-bearing limestones, regardless of the percentage of MgO present. Since no, true dolomites exist in the areas to be described, we shall also loosely use the terms dolomite or dolomitic limestone to designate those beds having a magnesia content of 5 per cent MgO or more. For a number of years the writers have been impressed with the fact that in areas where dolomite beds occur a large percentage of the lead ore is found in these beds, in spite of the fact that such beds may be overlain or underlain by pure limestone, which one would assume to be just as favorable for replacement as the dolomite, if not more 'so on account of its being more soluble in acid solutions than the dolomite. It is true that in some limestone areas, such as the Erupcion-Ahumada districts, Chihuahua, and Providencia, Zacatecas, where no dolomite beds have been found, large tonnages of lead ores have been mined. We venture to predict, however, that had there been dolomitic beds in these areas, the

Jan 1, 1931

By J. E. Nelson, R. J. Bonnis

Recent completion of Cyprus Bagdad's $240-million modernization and expansion program has registered a 700% increase in ore production with only a 50% increase in labor. Elements of this remarkable achievement include the application of large-scale mining equipment as well as the selection of the latest in processing hardware. Most important, however, was the early recognition that Bagdad's labor personnel is its most important asset.

Jan 4, 1978

By HUNTINGTON ADANS

(Wilkes-Barre Meeting, June, 1911.) THE arrangement of a flow of cyanide-pulp through Pachuca tanks in agitation, so as to permit a continuous process, instead of alternate filling, agitation, and emptying, has been proposed by various writers within the last two years, and more particularly by A. T. Grothe, agent for the Brown patents on Pachuca tanks in Mexico. It was first put into practice, I believe, by M. H. Kuryla at the Esperanza mine in El Oro, Mexico. The starting of agitation in Pachuca tanks after filling may offer no serious difficulties with ores which do not settle rapidly in such tall tanks; and the adaptation of the tanks to continuous agitation under such conditions may give simply a somewhat more convenient method of treatment and greater agitation-capacity for a given number of tanks, because of the saving -of time lost in filling and discharging. But in the treatment .of pulp which tends to settle rapidly, as in the cyaniding of concentrates or of the whole pulp of ores containing heavy sulphides, the packing of the slime at the bottom may, cause much trouble. The use of the radial air-pipe attachments near the top of the cone and of the air-valve outside of the air-lift .tube at the bottom may obviate the difficulty to some extent; but the action of the radial air-pipes on the cone-sides is that -of a sand-blast, and their continuous use cuts through the tanks. Moreover, even when these pipes are used, some pulps will pack tightly below them in the cones. Under such conditions the use of Pachuca tanks with intermittent filling and discharging becomes a troublesome process. Time is lost in ,starting agitation; large quantities of compressed air are wasted; pulp is blown over the tank-tops; and not infrequently it may be necessary to dig out the bottoms of tanks by hand. This trouble is the only important one occurring in the use of Pachuca tanks; and, since it is caused by intermittent filling, the .arrangement of a continuous flow of pulp from tank to tank,

Aug 1, 1911

By Paul Billingsley

The Asientos-Tepezala district is in the north of the State of Aguasca-lientes, about 30 miles north of the city of Aguascalientes, the capital. The district is reached by a standard-gage railway on the west side through the junction, Rincon de Romos, which is on the main line of the National Railways of Mexico from El Paso to Aguscalientes. The terminal is Tepezala. On the east side a narrow gage connects Asientos with the junction, San Gil, on the main line, Asientos to San Luis Potosi. Tepezala on the west side of the Asientos hills is about 2 miles from Asientos on the east side. The area between the two mining centers is separated by a low subdued divide which forms the central part of the hills. The district is in a group of isolated hills surrounded by characteristic bolsón plains. The hills rise above the surrounding plains about 6500 to 10,000 ft.; the highest peak is Alta Mira. The two mining districts lie somewhat upon the flanks of the hills at about the same elevation, 7200 ft. The district is an old one and has been known since early in the 17th Century when the mines were worked by the Franciscan Monks. Their mining operations, which were limited to the oxidized ore above the water level, consisted chiefly in extracting silver from the Santa Francisca vein. To judge from the old workings and the remains of surface plant, the operations were on a large scale. By modern mining operations since about 1900, the various mines of the district have been one of the principal sourees of ore for the smelter located at Aguascalientes. Topography The topographic features of the Asientos hills are largely controlled by the character of the underlying rocks. During the Tertiary period, the entire group of hills was probably covered by extrusive volcanic material in the form of cones and lava flows. The central part of these have since been carried away by erosion, so that remnants have been left along the borders of the hills. These remnants form rather conspicuous peaks,

Jan 1, 1927

THOSE NOT MARKED ARE MEMBERS; MARKED THUS ?ARE ASSOCIATES. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP JUNIOR MEMBERS ARE MARKED ' . THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. AARONS, J. BOYD See Honor Roll. '05 ? AARONSON, ALFRED E Pres., Tuloma Oil Co., Unity Bldg., Tulsa, Okla. '18 ABADIE, EMILE R., Min. En r Box 291, Porterville, Tulare Co., Cal. '76 ABBOTT, CLARENCE E., Gen'l Supt., Iron Mines Div., Tenn. Coal, Iron & R. R. Co., 1405 Minnesota Ave., Bessemer, Ala. '04 ABBOTT, Louis BENJAMIN, Chief Engr., Consolidation Coal Co., Elkhorn Div., Jenkins, Ky. '15 ABBOTT, ROBERT R Met. Engr., Peerless Motor Car Co., Cleveland, Ohio. '12 ABE, ASAKA Fujitagumi Taiwan Office, Taipeh, Formosa, Japan. '14 ABBY, HIROSHI Min. & Met. Engr., Mitsubishi Co., Tokyo, Japan. '17 ||ABOUCHAR, S. S., Cia. de Minerales y Metales, S. A., Minas Viejas, Villaldama, N. L., Mexico. '17 ABRAHAMS, A. I 1391 Madison Ave., New York, N. Y. '14 ?ACKER, E. O'C., Met.,128 East Washington Lane, Germantown, Philadelphia, Pa. '86 ? ACKERMAN, ERNEST R., Pres., Lawrence Portland Cement Co., Plainfield, Union Co., N. J. '15 ACOSTA, J. N., Min. Engr., Cons. Engr Hotel Brewster, San Diego, Cal. '15 ADACHI, JINZOO 11 Shiba Park, Shiba-Ku, Tokyo, Japan. '88 ADAMI, CHARLES J., Min. Engr., Gen'l Supt., St. Joseph and Doe Run Lead Companies, Bonne Terre, Mo. '12 ADAMS, ARTHUR K., Min. Geol., Andes Copper Min. Co., Casilla 230, Antofagasta, Chile. '06

Jan 1, 1923

By M. W. Hayward

THE object of this paper is to record and tabulate the data and field observations obtained by the writers and their associates during 10 years of intensive study of lead-zinc deposits in the Cretaceous limestone areas in Northern Mexico, particularly in mines owned by the Cia Minera de Peñoles, S. A. At the El Paso meeting of the Institute in October, 1930, J. G. Barry made the suggestion that a committee be appointed to correlate the ideas and theories which have been put forth by the numerous engineers and geologists who, during recent years, have made a study of the ore deposits in the area under consideration. The first step in a work of this nature would be to record all of the observed facts, and these facts would have to be accepted by those who attempted to formulate a theory of ore deposition. It is with this idea in mind that the writers have described as accurately as possible the actual, observed facts pertaining to the occurrence of the lead-zinc ores in dolomites or dolomitic horizons. By most writers the term "dolomite" is loosely used to designate magnesium-bearing limestones, regardless of the percentage of MgO present. Since no true dolomites exist in the areas to be described, we shall also loosely use the terms dolomite or dolomitic limestone to desig-nate those beds having a magnesia content of 5 per cent MgO or more. For a number of years the writers have been impressed with the fact that in areas where dolomite beds occur a large percentage of the lead ore is found in these beds, in spite of the fact that such beds may be overlain or underlain by pure limestone, which one would assume to be just as favorable for replacement as the dolomite, if not more so on account of its being more soluble in acid solutions than the dolomite. It is true that in some limestone areas, such as the Erupcion-Ahumada districts, Chihuahua, and Providencia, Zacatecas, where no dolomite beds have been found, large tonnages of lead ores have been mined. We venture to predict, however, that had there been dolomitic beds in these areas, the

Jan 1, 1932

By J. L. Lytton, J. E. Dorn, L. A. Shepard

Single aluminum crystals were subjected to creep in simple shear on the (111) planes in the slip direction. The activation energies for creep were calculated from the effect of small abrupt changes in temperature on the creep rate just before and immediately following the temperature change. The results definitely establish the fact that creep of single aluminum crystals occurs by-three unique processes, characterized by thethree distinct and isolatable activation energies: The 35,-500-cal-per-mole activation energy obtained at the highest temperatures was ascribed to a dislocativationtion climb process; the 28,000-cal-per-mole activation-energy process, occurring over the intermediate-temperature range was attributed to a cross-slip mechanism; and it was suggested thot the 3400-cal-per-mole process observed below 400°K may be the Peierls energy. THE most pertinent question regarding the phenomenon of creep in crystalline materials is concerned with the identity of the crystallographic mechanisms of deformation that control the creep rate. For many years slight progress was made in uncovering the basic mechanisms for creep. Over the past 10 years, however, two parallel lines of investigations have contributed to a more definitive understanding of the processes involved in creep. The extensive development and maturing of dislocation theories for deformation of crystalline materials' proved to be of paramount importance for this progress. And second in importance was the replacement of the former prosaic methods of creep testing by new techniques'." which were especially

Jan 1, 1959