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By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.''~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.' Around room temperature, however, slip on all known systems provides only four.' In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.'?' Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

By B. Habermann

Artificially consolidated sand models, representing one-quarter of a five-spot, have been developed and used to study factors aflecting misciblt. displacrmenr. Sweep efficiency at breakthrough, size of the mixing zone between two miscible liquids and per cent area contacted by drive after breakthrough were determined tor the high mobility ratios encountered in actual resvrvoirs. Quantitative relationships between the degree of viscous fingering and mobility ratio were obtained by measuring the length of the fluid interface. Scaled miscible-slug experiments, supported by field evidence reported in the literature, have shown that when the slug is followed by dry gas the process is less efficient than expected. In addition to low areal sweep efficiencies encountered for high mobility ratio displacements, the effectiveness of a miscible slug is greatly reduced. This is caused by an accelerated growth of the mixing zone between the driving and the displacing fluids. INTRODUCTION Considerable interest in miscible displacement as a secondary recovery process has been shown by the oil industry in recent years. In addition to extensive laboratory investigations, numerous field operations have been initiated so that 39 miscible displacement projects had been reported' in the United States by early 1959. By far the most popular approach in these projects is the use of an LPG slug followed by dry gas. Laboratory tests have indicated that with a small miscible slug, amounting to several per cent of the hydrocarbon pore volume, practically 100 per cent recovery of the oil in place can be achieved and that all of the slug material can be recovered by a subsequellt gas drive. However, these experiments were conducted on small-diameter long cores that can be considered as essentially uni-dimensional reservoirs that do not represent actual field conditions. It soon became apparent that the inherently adverse mobility ratios existing in the reservoir cannot be ignored in any miscible displacement field project. When a less viscous fiuid such as an LPG slug drives a more viscous reservoir oil, fingers develop that reduce the areal sweep efficiency. The slze of the miscible slug to be used is a subject of some controversy. It has been proposed that the size of siug needed be calculated by setting lengths of the mixing zone proportional to the square root of the distance traveled. This proposal is based on experimental evidence' and theoretical considerations"' in which fingering was not a factor. A prerequisite for successful application of the miscible displacement process to field operations is a better understanding of the following factors. L What is the effect of mobility ratio on the rate of deterioration of a miscible slug? 2. How large a slug should be used for given reservoir conditions? 3. What is the sweep efficiency? The purpose of this investigation was to provide some additional laboratory data that should help to answer these questions. More specifically, it was intended to study more quantitatively the effect of viscous fiinger-ing, mobility ratio and slug size on the efficiency of this relatively new secondary recovery process by means of experiments on thin, horizontal, porous medium models.

By Clarence Zener

THE heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an under- standing will involve two distinct types of inquiry: (I) the direction of the trans- formation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed here in steel such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron- alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data being obtained from the simple binary and ternary equilibrium diagrams. FUNDAMENTAL EQUATIONS In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body- centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may be regarded as filling all the lattice positions of a given type. The introduction of the fundamental equations of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1946

By L. H. Levenson, Charles S. Barrett

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-' mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz' for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By W. L. Fink, R. S. Archer

This paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent, beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium docs not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. Commercial Possibilities of Beryllium Alloys Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to thc strength and corrosion resistance of thc aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

By Charles S. Barrett, L. H. Levenson

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By Roger L. Beals, George A. Tweedy

The results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time; hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data : Pan-Amalgamation. Cyanidation. 1905. 1905. " 1908. Tons treated,.... 51,387 58,983 69,200 Value per ton (U. S. currency),. $ 10.78 $8.39 $8.28 Extraction, per cent.,.. 65.00 88.56 87.45 Extraction, per ton,.. $7.00 $7.43 $7.24 Total cost, per ton treated, . 6.50 4.36 4.01 Profit, per ton treated,.. 0.50 3.07 3.23

Jan 1, 1911

By J. O. Nelson, C. J. Altstetter

Single crystals of hcp cobalt, 3 mm in diameter and up to 35 cm long, were grown using an electron-beam, zone-melting technique. The martensitic-phase transformation was studied in single-crystalline and polycrystalline specimens by making length-change measurements as a function of temperature under various elastic compressive stresses. Upon thermal cycling, single-crystalline or polycrystalline specimens repeatedly transformed almost entirely on the same variant of close-packed plane provided the maximum temperature did not exceed 600°C. Cycling to 1000°C resulted in transformation on more than one {111} variant. This behavior is termed multivariance. The multivariant transformation occurred very rapidly at an M, temperature 2° to 6°C lower than the M, of a transformation which would result in a single-crystal product. Elastic compressive stresses (up to 253 g per sq mm) tended to lower the A, and raise the M, temperatures, decreasing the width of the temperature vs dilatation hysteresis loop. The transformation habit plane and transformation shear direction of an as-grown single crystal were not grossly affected by elastic compressi?ie stress. This was evidenced by similar dilatations on the temperature us dilatation loops joy specimens with and without compressive stress. A dislocation mechanism is proposed to explain the observed results. IT has been shown that, on heating, cobalt transforms martensitically from the hcp to the fcc phase.' The transformation habit plane is (0001)hcp || (lll)fcc and the transformation shear direction is (1010)hcp || (112)fcc. The transformation involves a shear of 1g°28', which may be achieved by a shearing of a/6(112) of every two planes with respect to the plane beneath, thus changing the ABABAB stacking of hcp to the ABCABC stacking of fcc. Associated with the phase change is a 0.3 x 10"3 contraction in the habit plane and a 4.2 X 10"3 expansion perpendicular to the habit plane resulting in a 3.6 x X volume increase on heating.' On cooling, an identical volume decrease takes place. The temperature at which the fcc phase begins to form on heating (A,) is reported as 430°C, and the temperature at which the hcp phase begins to form on cooling from an elevated temperature (A&) is reported as 390oC1,3 Consequently, temperature vs dilatation plots have the form of a hysteresis loop. If heating or cooling is reversed during a transformation, a smaller hysteresis loop results. Upon heating, the transformation is always complete; whereas, fcc is often retained at room temperature as a metastable phase entrapped in the polycrystal-line hexagonal matrix.1,4,5 Two obstacles in the theory of the allotropic-phase transformation of cobalt have been: 1) a detailed knowledge of the product nucleus, and 2) a plausible method of propagation of the transformation. Bilby,8 christian, 7 and seeger 8,9 have suggested a "pole mechanism" as a means of propagation of partiai dislocations from plane to plane. A pole dislocation and a Shockley partial come together at a node. The a/6(112) Shockley partial rotates about the pole dislocation effecting the transformation shear. The pole dislocation must have a 2a/3(111) screw component which causes extension of the transformed region by two atomic planes with each full rotation of the Shockley partial. Bollmannl0 suggested, on the other hand, that transformation propagation occurs due to the stress fields of intersecting (111)-type stacking faults. As faults intersect, a stress distribution is set up about their intersection which is in turn reduced by the emergence of another fault on the second nearest plane. This process continues with the final result of a complete phase transformation. In view of the similarities between deformation and transformation in cobalt, the effect of stress on the transformation would, hopefully, yield valuable information concerning nucleation and propagation. In the present work single-crystalline and polycrystalline specimen length changes were measured as a function of temperature at various compressive loads. PROCEDURE Several orientations of single crystals of hcp cobalt in lengths up to 25 cm were grown by electron-beam floating zone melting from 99.95 and 99.999 pct, 3-mm-diam cobalt rod as supplied by Johnson

Jan 1, 1964

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10&apos;a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann&apos; in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5&apos;6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1&apos;-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1&apos; ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury&apos;s3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell&apos;s rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

By J. L. Walter

Tungsten ingots with and without small amounts of aluminum, silicon, and potassium were prepared by conventional powder-metallurgy techniques and hot-rolled to 0.001-in.-thick sheet. The ingots were rolled three different ways: I) initially cross-rolled, then straight-rolled; 2) straight-rolled, and 3) straig-ht-rolled, then cross-rolled. Total reductions were 99.8 pct. Samples of the sheet were annealed, in vacuo, at temperatures from 1200" to 2200°C. Substructures and textures were determined by transmission electron microscopy and X-ray diffraction. The doping agents were found to form particles of mullite (Al,Si,O,,) which, on rolling., appear to form strings of particles aligned parallel to the rolling direction. These strings of purticles are associated with an increase in the recrystal-lizution temperature from 1400°C for undoped sheet ThE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of drawn and recrystallized wire.&apos;" The grains generally do not occupy the entire cross section of the wire and have lengths many times the wire diameter. The grain boundaries are, in general, nearly parallel to the wire axis and have long &apos;&apos;fingers" projecting one into the other as may be seen in Fig. 1, a longitudinal section of recrystallized doped wire. When unsuitable additions or no additions are made or the wire is not sufficiently reduced during draw- to 2000°C for doped sheet. The particles also limit lateral grain growth while allowing growth parallel to the rolling direction. This results in the formation by primary re crystallization of large highly elongated grains of specific preferred orientation. The undoped sheet recrystallized to small equiaxed gains. The preferred orientations of the large grains were determined from axis density plots to be (113) (691). (0i3) (362), (116) (304) types for the initially cross-rolled then straight rolled material. These orientations are similar to the orientations of the large elongated grains in doped and heavily drawn tungsten wire. The nucleation of the large grains appears to occur by recovery of certain of the polygonized regions of specific orientation, followed by strain-induced boundary migration.

Jan 1, 1968

By J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By T. A. Rickard

RICO, in the southwestern corner of Colorado, is one of the productive mining centers of the San Juan region, so-called because its waters drain into the river of that name, which is tributary to the Colorado. The San Juan region includes the counties of Ouray, Hinsdale, San Miguel, Dolores, San Juan and Montezuma. It is traversed by a network of picturesque mountain ranges on whose lofty summits there rests perpetual snow. The region is peculiarly rugged, and, in the early days of its development, tested to the full the hardihood of the adventurers who first explored its can ions 111 search for gold and silver. A prospecting party, guided by Jim Baker, scout and trapper, penetrated in 1861 this part of the territory of Kansas. At that time the country was in the possession of the Ute Indians. In October, 1873, by the Brunot treaty, they ceded to the United States Government the richest mineral-bearing portion of their

Jan 1, 1897

By Hans S. Carlsson

Like most industrial processes, nuclear power production creates wastes, which have to be handled and ultimately disposed of in a safe manner. Some of the wastes contain very long-lived radioactive substances and have to be isolated for very long periods of time before they have decayed to harmless levels. Sweden, like many other countries with similar geology, intends to use crystalline rock for isolating the high-level nuclear waste from the biosphere. The suitability of a rock mass for a repository needs to be investigated extensively. Apart from the political and practical considerations for a site selection, a detailed study has to be performed in terms of geology, hydrogeology, geophysics, geochemistry and rock mechanics. The responsibility of the site selection studies in Sweden is entrusted to the Swedish Nuclear Fuel Supply Company, Division KBS (SKBF/KBS) . The paper gives a brief presentation of the "Standard Program" for the studies that will be carried out during 1980-1990. Modifications of the program are justified on the basis of gained experience or specific circumstances for each site. The program is compiled by the Geological Survey of Sweden (SGU) in cooperation with KBS.

Jan 1, 1982

By J. M. Avasthi

The DOE-funded (Contract No. DE-ACO3-77ET13108) Gulf Research & Development Co. (GR&DC) field tests of underground coal gasification in steeply dipping beds (UCG/SDB) were conducted in the North Knobs area, located 12.8 km (8 miles) west of Rawlins, WY. The site has a gently rolling, sparsely vegetated, semidesert terrain on the transition zone between a broad, flat basin (Great Divide Basin) to the west and the subdued mountains of the Rawlins uplift to the east. A comprehensive geotechnical program (Ahner et al., 1980) was essential to successfully complete the test program. Emphasis of the program was the subsurface characterization of the site and consisted of mapping, drilling and logging, core analyses, and hydrologic tests. The samples of lithologic units over- and underlying the G coal seam were tested in the laboratory for their modulus and strength. This program provided the required data necessary for designing surface facilities, input for permits, and ensuring correct placement of the process modules. The two UCG tests at the Rawlins site were conducted in the nominally 6.7 m (22 ft) thick G coal seam (rank-subbituminous B), dipping at 63°.

Jan 1, 1984