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By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By R. L. Slobod, C. Gatlin

This .study defines the basic mechanism of the mis-cible displacerrzent of oil and writer from porous Medici by various water-driven alcohol .slugs. Three distinct alcohol slug processes were .studied. Considerable data concerning the quanity of alcohol required for oil recovery were also obtained. All data were obtained in a 1-in. diameter, 100-ft long, unconsolidated core. The porosity of this system was 35 per cent. and the permeability was approxitrlately 4 darcies. Total core pore volume wax 5,716 cc. All displacements were conducted at a constant injection rate of 5 to 6 cc//min, which corresponds to a frontal advance of 5 ro 6 ft/hr. The first portion of this paper is concerned with 111 use of one alcohol—isopropyl—a\. the slug material. Isopropyl alcohol (IPA) is completely miscible with both oil rind water; however, miscibility of the threc-component systems, oil-water-IPA, requires a relutively. high concentration of IPA. Hence, the displocement is not of the misoible type unless the IPA concentration is maintained above some critical value. A slug of IPA equal to only 13.5 per cent of the pore volume was jound to be sufficient to obtain complete recover?, of residua1 naphtha. In later studies two distinct process variations were developed. The firsr of these utilized methyl alcohol (MA) and IPA as slug materials. It was shown that methyl alcohol may he substituted for IPA at the front and rear of the slug with no loss of oil recovery. A .slug of 4 per cent MA-4 per cent IPA-4 per cent MA was sufficient for complere oil recovery. Because MA is considerably cheaper than IPA, this represents an important step toward economic application. A .second process variation used normal butyl alcohol (nBA) and MA as the composite slug, the nBA segnzent being injected first. This technique requires the smallest total slug size (approximately 10 per cent) of all processes studied. The high cost of nBA, however, precludes commercial application. It is possible that this basic process, subject to changes of alcohol type, may lead to a commrercicil process. INTRODUCTION Within the last 10 years, considerable study has been devoted to the general mechanics of miscible phase dis- placements in porous media. These studies have. in general, dealt with two-component displacernent. All reported field trials to date have been modified gas drives of one type or another. These utilize either lean gas at high pressure, rich gas at lower pressure or an LPG slug. The irreducible water content of the reservoir remains immobile during these processes. Although these techniques hold great promise. certain drawbacks do exist. Poor areal sweep efficiency, inherent in any displacement having a highly unfavorable mobility ratio, is one disadvantage. Furthermore, the miscibility of all processes which use gas is dependent on pressure. These pressure limitations may prohibit application to shallow reservoirs. There are also many areas where large quantities of LPG and natural gas are not readily available. These factors emphasize the need for improved techniques. The alcohol slug process is also a miscible-phase displacement process. It differs from the previously mentioned two-component techniques, however, in that both the reservoir oil and water are displaced by the slug. This behavior is a consequence of the miscibility of certain oil-water-alcohol systems. In the simplest case, a relatively small volume (slug) of an alcohol (such as isopropyl) is injected into the system. Water is then used to drive the slug through the medium. Thus. three components—-alcohol. oil and connate water-—exist at the front side of the slug. Miscibility is obtained at some alcohol concentration, this being dependent on the solubility of the particular system. Miscibility is maintained within the slug until the alcohol concentration falls below that value required to maintain miscibility. When miscibility is lost, the process reverts to a water flood. Certain inherent benefits of this technique are apparent. High pressures are not necessary to obtain miscibility in these liquid systems. Furthermore, water is a more desirable driving agent than gas because of the improved mobility ratio and the attendant improvement in areal sweep efficiency. The main disadvantage is, of course, the relatively high cost of alcohols. The use of an alcohol slug to recover reservoir oil is not a new idea." ' However, this process has received only limited study, presumably due to the lack of industrial interest caused by the seemingly prohibitive cost of alcohols. The main purpose of this study was to investigate the mechanism of the displacement of oil and water by various alcohol slugs and to develop process modifications aimed toward possible commercial application.

By C. J. Guntner, R. P. Reed

A commercial 18Cr-8Ni iron alloy (AISI 304L) was examined in tension at 300°, 76°, 20°, and 4°K. Continuous stress-strain recordings were made, X-ray analyses at periodic stress (strain) intervals were obtained, and the magnetic measurements were taken. From this data the percentage of martensitic products [bcc(a) and hcp (E)] was computed as a function of stress (strain). It was found thatup to 15 pct E phase forms at low temperntures. The amount of E formed increases to a maximum at about 5 pct strain, then decreases. This decrease indicates the additional transformation of E to a'. The total amount of E and a' was suppressed at constant stress (strain) at 4°K as compared to 76°K. It is proposed that the suppression of E and a' is associated with the decreased mobility of extended dislocations at very low temperatures. The yield strength decreased as the temperature was depressed below room temperature and then increased rapidly near 4°K. SOME ferrous alloys which are austenitic (fcc ?) at room temperature appear to be unique in that two martensitic products (hcp e and bcc a') may form on cooling to lower temperatures or on application of mechanical stress. The most common room-temperature austenitic ferrous alloys are 18Cr, 8Ni stainless steels. Most aspects of the spontaneous transformations have been previously described for these steels.' Several previous papers have described special aspects of the stress-induced transformations at low temperatures for the stainless steels, such as the existence of the hcp phase (c) after straining at 76oK,2-7 the morphology after straining using electron microscopy,7 and the decrease in E at higher strains at 76oK.4 However, for a complete representation, one must know the stress-strain characteristics and the dependence of both martensitic products on applied stress and temperature. It is the intention of this paper to provide that documentation. To accomplish this, continuous stress vs strain recordings were made at four temperatures: 300°, 76", 20°, and 4°K for annealed AISI 304L (a commercial 18Cr-8Ni alloy). At periodic stress intervals at each temperature the integrated X-ray line intensity of a selected peak for each phase (y, E, and a') was measured. In addition, photomicrographs of the strained surfaces were taken and magnetic measurements were made. The magnetic readings can be directly converted into percent a'.',e With these measurements the percentage of each phase may be plotted as a function of stress (or strain) and test temperature. It was found that up to 15 pct E phase forms upon stressing the AISI 304L alloy at low temperatures. The E percentage increases abruptly after the alloy yields, but then decreases gradually at higher stresses. The rapid increase in e at 76°K is associated with an "easy-glide" portion of the stress-strain curve. The total amount of a' + .G is suppressed below 76°K at a constant stress or strain. The yield strength decreases down to 76°K but increases rapidly below 20°K. EXPERIMENTAL PROCEDURE Tensile test specimens were cut parallel to the rolling direction from 0.1-in.-thick sheet. Continuous stress vs strain recordings were obtained at each test temperature (300°, 76o, 20°, and 4°K) using equipment and methods described elsewhere.' The specimens which were used in the X-ray analysis were stressed to successive increments of strain at each temperature, analyzed at room temperature, then restressed at the test temperature. This procedure was repeated until approximately ten X-ray analyses had been performed with approximately 1.0 pct strain increments. The specimens had a reduced section 1 in. long, 1.2 in. wide, and 0.1 in. thick. They were electro polished prior to testing and after each strain increment. Table I lists the chemical composition, grain size, and hardness for the alloy which was used. This is the same alloy for which extensive mechanical-property tests3 and morphological studies of the spontaneous transformations' have previously been made. For the low-temperature tests (76o and 4°K) below the Ms temperature the specimens were initially cooled to the test temperature, held for 1/2 hr, then warmed and X-rayed at room temperature. The results are listed in Table 11. From earlier work8 it was known that additional transformation on the second cycle would be considerably less (-0.1 pct

Jan 1, 1964

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By T. K. Perkins, R. N. Hoffman, O. C. Johnston

A simplified theory of viscous fingering in miscible systems has been developed. It predicts the correct functional relationship between pertinent variables and permits the calculation of the order of magnitude of fingering behavior for simple systems, such as linear or radial. The theory is based on the following four observations: (1) cross-flow takes place only near the ends of fingers; (2) the relative finger width is about 0.5; (3) fingers can be suppressed by transverse dispersion, the suppression being quantitatively described by a critical ratio of dispersion times; and (4) the widths of extending fingers are close to the minimum size finger that can grow at any stage of displacement. Fingering is studied in two-dimensional linear and diverging radial systems, both theoretically and experimentally. For linear systems, the length of the fingered region is proportional to mean displacement; the finger width is proportional to square root of mean displacement; and there is a small initial region void of fingers because of suppression by longitudinal dispersion. For the radial system, two limiting conditions are recognized. If the mean displacement is small compared with the wellbore radius, the length of the fingered region is proportional to the mean displacement. The width is proportional to the square root of mean displacement. If the mean displacement is large compared with wellbore radius, length of the fingered region is proportional to mean displacement, but the number of fingers approaches a constant value. Also, in the radial case there is a small initial region void of fingers because of longitudinal dispersion. INTRODUCTION The behavior of viscous fingers in miscible systems has been of interest to the oil industry for many years. Previous studies have clearly shown the existence and nature of fingers in small models.1,2,3,4 Engineering techniques for extrapolating to reservoir situations have been proposed. 5,6 Still, because of the lack of a real understanding of the mechanics of fingering, there remains uncertainty and disagreement as to the best way to scale or calculate fingering behavior in the reservoir. In this paper we discuss a study of the mechanics of fingering in miscible systems (i.e., why do fingers behave as they do?). A simplified theory is developed which we believe will (1) predict the correct functional relationship between pertinent variables, (2) permit us to calculate the order of magnitude of fingering behavior for simple systems such as linear and radial, and (3) give further insight into the problem of scaling or otherwise extending the results to more complicated reservoir conditions. The paper includes the following sections: (1) brief summary of the mixing behavior of miscible fluids in linear and radial systems; (2) four fundamental observations of fluid flow (under fingering conditions); (3) based on these four observations, a simplified theory of fingering in linear and radial systems is developed; and (4) the theoretical equations are compared with experimental fingering data measured in laboratory models. A REVIEW OF DIFFUSION AND DISPERSION As will be shown later, the behavior of viscous fingers in miscible systems is controlled in large degree by the mixing between the two fluids. A quantitative description of fingers will first require a quantitative description of mixing. Fortunately, much work has been done to clarify this subject; a fairly comprehensive review has been presented in a previous paper. 7 For present purposes let us (1) briefly summarize the quantitative description of diffusion and dispersion (both longitudinal and transverse) within a differential element; (2) present a simplification of the "width of mixed zone"; and (3) describe the effect of geometry on width of mixed zone. If one fluid is displaced from a porous medium by another miscible fluid (in the absence of fingers)

Jan 1, 1966

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000&apos; and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,&apos; and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"&apos;" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,&apos;&apos; and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By K. M. Rolls, F. W. Reuter, J. Wulff

The superconducting behavior and microstructural characteristics of a nominal Nb-40 wt pct Ti-0.239 wt pct O alloy were studied as a function of ther mo -mechanical processing treatment. Critical current density us applied transverse magnetic field was obtained for 0.010-in.-diam wires at 4.2°Kin steady fields 14 to 110 kG. Both optical metallogvaphy and transmission electron microscopy were used to delineate the micros tructures of the same wires. It wan found that a 1-hr 500°C precipitation heat treatment after cold drawing to final size led to the highest critical current density. Heat treatment at 600°C also led to a high critical current density, but the precipitate differs in kind and form from that at 500°C. The resistire critical field was also found to be sensitive to precipitation heat treatment since the effective composition of the superconducting phase changes. This is discussed in terms of the oxygen in interstitial solid solution. Two types of high-field superconducting wire are at present used in the construction of high-field superconducting solenoids. These types are solid-solution alloy wire such as Nb-Zr and Nb-Ti and composites of the brittle inter metallic compound Nb3Sn. The latter generally have a high super cur rent-carry ing capacity which is difficult to vary if properly made. The supercur rent- carry ing capacity of the former can be varied drastically and often predictably by suitable thermomechanical processing treatments. In general, the critical current density Jc of the solid-solution type of alloy is increased by cold work and by additions of interstitial elements along with aging heat treatments. The imperfections which result are be-iieved to be responsible for the observed increase in Jc. In 1962 Kneip and coworkers1 found that the critical faurrent density of Nb-Zr alloys could be increased by proper heat treatment preceded and followed by cold work. Betterton and coworkers2 using a Nb-25 at. pct Zr alloy found that small additions of oxygen or carbon enhanced the effect of this heat treatment. They suggested that the interstitials present aided precipitation in the alloy, leading to a filamentary structure with superior properties. If the precipitation heat treatment was omitted, interstitial additions had a negligible effect on Jc. wong3 showed that higher heat-treatment temperatures lowered Jc. Walker and co-workers,4 who studied microstructure (by transmission electron microscopy) as well as superconductivity, found that the Jc anisotropy introduced by cold rolling was itself affected by heat treatment. They were unable to clarify the relation between microstructure and critical current density, although evidence of precipitation was indicated. More recent investigation of Nb-Zr alloys,5,6 besides showing that structural defects and fiber ing due to cold work and precipitation serve to raise Jc, also elucidate important optically observable microstructural changes which occur upon precipitation. In these reports, coarsening of the microstructural features was found to decrease Jc. Vetrano and Boom,7 who studied Ti-20.7 at. pct Nb, found that Jc was increased to a maximum by a 415°C, 3-hr heat treatment following quenching from 800°C and cold working. Heat treatments can also affect the resistive critical field Hr. Final-size heat treatments of Nb-Zr wire can lower Hr drastically if gross phase decomposition occurs5&apos;* or moderately if the effects of cold work are eliminated without changing significantly the composition of the phase of interest.3,5,6,8 The percentage of oxygen which can be added to Nb-Zr alloys to enhance Jc is limited by the difficulty of subsequent cold drawing. Since Nb-Ti and Ta-Ti alloys in contrast can tolerate appreciably higher percentages of oxygen, it was decided to investigate the superconducting behavior of various alloys in these systems. The present paper describes the results of adding oxygen to a nominal 40 wt pct Nb alloy as a function of thermomechanical treatment. I) EXPERIMENTAL PROCEDURE A small alloy ingot was prepared from high-purity niobium, iodide, crystal-bar titanium, and Nb2O5 powder by arc melting on a water-cooled copper hearth in a gettered argon atmosphere. The ingot was turned and remelted fourteen times to insure homogeneity. After final melting and rapid cooling, it was machined round to 0.415 in. diam, jacketed in stainless steel, and cold-swaged to 0.117 in. diam. The jacket was removed and swaging continued to 0.051 in. diam followed by wire drawing in carbide dies to 0.010 in. diam. Although it was intended that about 1500 ppm O (by weight) be added, inert gas fusion analysis indicated a 2390 ppm 0 content, apparently due to additional oxygen pickup in the arc furnace. Even so, the alloy was sufficiently ductile to be cold-worked to greater than 99.9 pct reduction

Jan 1, 1967

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum&apos;s data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster&apos;s4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960

By AIME AIME

EVEN in the choice of his birthplace and parents, Donald B. Gillies indicated clearly the trend of his professional career. He was born on Nov. 4, 1872, at Bruce Mines, in Ontario. His father and mother came from the Isle of Skye, Scotland, to Nova Scotia, moved from there to Canada, and finally settled in the copper country in the northern peninsula of Michigan, where the senior Mr. Gillies followed mining as an occupation. Donald&apos;s early education was in the public schools and he graduated from Linden Lake (Mich.) high school in 1890. Following the family interest in mining he entered the Michigan Mining School, now Michigan College of Mining and Technology. There he was the rare student who excelled both in athletics and scholastic work. On the athletic field he was a crack football player and track roan. As early as 1890 lie established a record of 10 sec-

Jan 1, 1938

By S. A. Swensrud

REPORTS from smelters show that all were so occupied with the in- creased production called for during the first half of the year that little time was devoted to metallurgical developments. Improvements which have been made such as gas-firing and other alterations ill the reconstructed Hayden smelter, will require time for reporting. The labor situation at all plants held the most prominent place and put all other problems in the background. Coming events of considerable importance concerti the construction of two new smelters. The Chino unit of Nevada Consolidated which has long had its concentrate smelted at the El Paso plant of the American Smelting and Refining Co. is constructing its own smelter at the property in New Mexico. The newest Phelps Dodge development of the Clay ore body at Morenci, Ariz., will call for another new smelter.

Jan 1, 1938

By K. Harms, T. D. Jones

TO unload large tonnages of lead bullion cast in 100-lb. bars is a problem which has confronted the lead refineries for many years. The bars, on arrival, must be restacked for unloading by truck or hand-charged to charging machines. Selected crews of labor, capable of working at sustained speeds for five- or six-hour periods, are required for this exhausting task. Due to the fatigue involved crew personnel changes rapidly. During the war it became increasingly difficult to maintain crews, especially in critical labor areas, so that the development of casting and shipping ten-ton lead blocks from the smelters to the refineries became a must in our operating program. For many years lead refineries, when making interdepartment or intradepartment transfers, have cast lead blocks weighing five or ten tons which are easily handled by crane by merely attaching the crane hook to a steel anchor embedded in the frozen lead blocks. In previous years, the practice was to use regular smelter slag pots which, due to their rounded shape, produced what were called "buttons" by the refinery personnel. The button-type blocks were unsafe as they rolled and tipped easily and were unsatisfactory for stacking since no piling pattern could be followed. To remedy this situation, flat-bottom molds came into general use and later the bottoms were made concave to prevent slipping.

Jan 1, 1946

By AIME AIME

OUT of the fabulous iron ranges of Michigan?s Upper Peninsula since Pearl Harbor have come go to the steel mills to become tanks, guns, ships, and other weapons for a United Nations&apos; victory. But the contributions to the war effort, as far as Michigan&apos;s iron country is concerned, do not stop there. The same men who mine iron ore deep inside the earth also are "mining" on top of the ground, gleaning a harvest of scrap iron and steel that is writing a big chapter in the War Production Board&apos;s salvage program. At virtually every mine over an area of a hundred square miles, everyone from the top mine official and straw boss to the man in the dippings is scrap conscious. They know the importance of the ore they mine but they are equally familiar with the importance of iron and steel scrap in war production. The successful job they are doing in salvage is a tribute to the entire Upper Michigan mining industry and to the man who marshaled them into action-John M. Bush, chief of the land department for the Cleveland- Cliffs Iron Co. at Negaunee, and for ten years an A.I.M.E. member. Also, this job should be an inspiration to 611 mining. metallurgical, and petroleum communities as to the latent possibilities of organized scrap recovery.

Jan 1, 1943

By Hugh H. Waesche

AN adequate supply of crystalline quartz of piezoelectric grade and size continues to be of fundamental importance to the U. S. Army Signal Corps. Current electronic development programs of the Armed Forces depend upon the use of quartz crystals in all applications where accurate frequency control is necessary. In peacetime this&apos; may not seem too significant, but in planning for possible national defense emergencies, an adequate supply of piezoelectric grade raw quartz is just as important as an adequate supply of some of the more publicized strategic minerals. Prior to World War II, the Signal Corps accepted the use of quartz crystals for frequency-control purposes in essentially all electronic communication, navigation, and radar equipment operating in the audio and radio frequency spectra up to and including the ultra-high-frequency channels. Over 4,000; 000 lb of radio-grade quartz was required between January 1942 and V.J Day. Use of such a large quantity of crystal units was necessary in order to establish and maintain, with a minimum of effort, clear and definite frequency channels of greater stability than could be obtained by any other means. This policy was justified on the basis that quartz was without a peer as a frequency-controlling element. Military and civilian uses of quartz in the field, as well as laboratory studies, have confirmed this premise and no means of highly stable frequency control, superior to quartz, has been discovered. It appears certain that the demand for use of quartz for frequency control purposes will continue at a high level.

Jan 1, 1948

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

George Otis Smith, Washington, D. C. (communication to the Secretary) : The somewhat exceptional features discussed by Dr. Jenncy in his paper on " The Mineral Crest" mere recognized and described by Mr. Tower in our report on the Tintic district. The general absence of surface-outcrops of important ore-bodies, and their occurrence, when present, at relatively low points, are noticeable characteristics of this district, and the statements made by Dr. Jenncy agree in general with our observations. The approximately horizontal upper limit of the Silver Gem ore-body in the Bullion-Beck mine is figured in this report, and mention made also of the horizontal pipes of ore found in several mines." In only one case," however, was any hypothesis

Jan 1, 1903

By Gerald, Sherman

INCREASED production and con¬sumption of all metals, indicate the progress of industry toward that condition formerly thought to be normal. With no market limitations on silver and gold the two new precious-metal mines, the Silver Queen (now the Golden Queen), in southern California, and the Sunshine, at Kellogg in northern Idaho have made progress toward a high routine production. The Golden Queen 300-ton mill is finished and ready. The Sunshine mill has been enlarged and production is now at the rate of 500 tons per day of high-grade silver ore. The Hecla Mining Co. is developing the Polaris vein, which should be the extension of the Sunshine to the east. Some rich ore is reported. The developments of the&apos; East African Gold Fields, Ltd., in the Lupa gold field of Tanganyika Territory, have made good progress, but operation in an isolated locality is not rapid and a large plant will be required. There have been no other discoveries reported that can be compared with the three mentioned, but production has increased, with greater capacity in dredging equipment and underground mines more adequately prepared for production.

Jan 1, 1936

By R. L. Sebastian

ALUMINUM&apos;S war history is the record of a successful race to expand facilities fast enough to meet the multiple increases in military requirements, principally for aircraft. From the beginning of the war program in 1940 through 1942, requirements estimates were repeatedly lifted to new high levels, and plans for increasing capacity had to be constantly revised. In 1943, basic metal supply caught up with and exceeded requirements, and by 1944, the surplus of primary production was large enough to force reduction in output and plant closings. In the past two years, ingot capacity has been ample, though periodic critical shortages have been experienced for a few fabricated shapes as a result of sudden shifts in demand. And now with all controls lifted we are faced with surplus capacity, surplus stocks, and surplus scrap. In 1938 the Aluminum Co. of America was the only U. S. producer of primary

Jan 1, 1946

By J. Parke Channing

THE growth of and profession depends on meeting and solving new problems. It is a continuous process. &apos;A period free from new, or hitherto unknown, questions will be a period of arrested development in the profession it affects. The present generation has witnessed a&apos; mechanical development that has been truly marvelous: Almost every day marks the advent of a new, or the improvement of an old; process, method or machine. Wonders are now commonplace. The impossible is regularly accomplished. Yet, with all our progress in every realm of science and with our development in the engineering field, advances which have made possible the marvelous growth in industry, we have not made commensurate gains in methods affecting the human factor. Without the cooperation of the worker, we shall always fall short of our goal in a mechanical or statistical sense. If we do not make the individual members of the human family strong, healthy, happy, and ambitious for better things for themselves and their children, we will have failed utterly, for that is the real reason for our existence as men and the purpose of our organized effort as an engineering group. Thomas A. Edison

Jan 1, 1921

By Dewey J. Sabin

THE Rio de Canada Honda placer property is situated at an altitude of 5500 ft. above sea level in the San Luis Mountains of the Province of San Luis, Argentina. The mine is reached by 70 km. of fair truck road, from the nearest railway station on the Ferrocarril Buenos Aires al Pacifico. The Pan-American airport at Villa Mercedes, 1.40 km. distant, serves as the most convenient point for shipment of gold. Placer mining in the Rio de Canada Honda dates from the time of the Incas and the present native population depends on the gold washed from this river and the adjacent arroyos as a means of livelihood as did the many generations before them. They dig pits to bedrock where they are not driven out by water, and mine the bedrock gravel by means of tunnels and caves. No timber is available and the ground is supported by rock cribs carefully built with the boulders encountered; or with angular blocks of slate rock taken from quarries on the surface.

Jan 1, 1936