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By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By P. A. Laxen, H. R. Spedden

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

By P. A. Laxen, H. R. Spedden

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By J. L. Gissy, G. H. Schippereit, J. B. Schroder

THE existence of mechanical anisotropy in hexagonal metals is well known.&apos; One possible method of measuring the degree of anisotropy in a metal is to make hardness measurements on the different planes of a single crystal. So far as is known, no single-crystal hardness data have been reported in the literature for alpha titanium. To obtain an estimate of the variation in hardness with crystallographic direction in titanium, Knoop hardness measurements were made on single crystals of electrorefined alpha titanium obtained from the Bureau of Mines, Boulder City, Nev. The hardness of arc-melted ingots prepared from this material was 64 Bhn (1000-kg load, 30 sec). Crystals of sufficient size were mounted in epoxy resin with the basal plane exposed. They were then polished and etched to remove excess plastic resin and work-hardened surface material. The crystals were then examined by x-ray diffraction, using the back-reflection Laue technique to insure that the crystals were properly oriented and strain free. After Knoop hardness readings (100 or 200-g load) were taken on the exposed surface, the crystals were remounted to expose a prismatic face and the foregoing procedure was repeated. Hardness values for various orientations are listed in Table I. The data show a difference between the hardness of the basal planes and that of the prismatic planes, as anticipated. More striking is the hardness difference observed between different orientations of the indentor on the prismatic planes as shown in Table I and Fig. 1. All of the indentations shown in Fig. 1 were made with a 100-g load. The long axis of indentation A is parallel to the unique (c) axis of the crystal. The deformation marks visible around indentations A and C of Fig. 1 are probably slip traces of the (10.0) system reported by Rosi, et al. The greater hardness observed when the long axis of the indentor was perpendicular to the unique axis of the crystal (indention B) is probably caused by the opera-

Jan 1, 1959

NORTH AMERICA ALASKA Anchorage.-Ames, M. B. Culver, H. W. Fiedler, H. L. Geehan, R. V. Langneas, O. O. Layfield, R. A. Parent, A. Saarela, L. H. Strandberg, H. Candle.-Robbins, J. S. Chichagof.-Russell, J. C. College.-Fox, E. F. Joesting, H. R. Lyman, R. F. Smith, M. C. -Wilcox, H. G. Douglas.-Cahill, W. E. Fairbanks.-Adams, J. M. CANADA Canadian Army Overseas.¬Ball, H. D. Bridges, O. Butterill, H. J. M. Lane, H. C. Millar, W. A.

Jan 1, 1942

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth 12 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939 3 Two types of process were described (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures, and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth Both cases are met in the formation of pearlite from austenite (Fig 1),2,3 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near AeI, has been named "group-nodule transformation " In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important&apos;&apos;&apos; to obtain data on the rate of nucleation and the rate of growth of pearlite Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the actors that affect hardenability, when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite 2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature,, and the degree of homogeneity of the parent austenite The studies are restricted chiefly to plain carbon commercial steels PREVIOUS DATA ON RAID OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan22 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc ), austenite grain size, and mode of formation of pearlite at the temperatures given

Jan 1, 1942

By W. T. Swensen

The Anaconda Company, through its wholly owned subsidiary The Anaconda Company (Canada) I,td., has investigated, optioned and partially developed a large tonnage of iron ore amenable to magnetic concentration. The reserves are located in north central Ontario and occur within a twenty-two mile belt of layered and intricately folded metamorphic rocks, close to the north contact of an igneous complex of granite and pegmatite. There are two main ore deposits. Briarcliffe is a steep to vertically dipping body 100 to 500 feet wide and over a mile long. The Two Mile Lake deposit is flat dipping and confined to an open, asymmetrical syncline; it is approximately a mile wide and 250 to 4.00 feet thick. On its flat easterly plunge, it is saucer-like in shape and is amenable to open-pitting for an east-west distance of several thousand feet. Magnetometer surveys, confirmed by drilling, indicate at least a three mile eastward extension of this deposit. Location and Access: The property is located in the Kowkash Mining District of northwestern Ontario, roughly forty-four miles north of the community of Nakina on the main line of the Canadian National Railroad. (Fig. 1) Access during the exploration period was entirely by airplane from Nakina. (Fig. 2) More recently, Nakina itself was connected to the highway network in the Longlac-Geraldton area. The property is roughly 190 miles by existing and proposed railroad from the Great Lakes waterway system. The Trans-Canada pipeline moving natural gas from western to eastern Canada passes through Geraldton roughly 70 miles south of the property. Topography: The surface features in the area are typical of a sizeable portion of the Precambrian Canadian Shield area. Many lakes, low swampy areas, and glacial moraine-type features are common in this recently glaciated area. The average elevation is between 800 and 900 feet above sea level, and the relief is probably less than 100 feet with the greater portion of the area less than 50 feet. The topographic "highs" are formed either by outcrops that were resistant to glacial erosion or by moraines, eskers and drumlins which were deposited upon the recession of the glaciers. The better mineralized zones, composed chiefly of quartz and magnetite, commonly form ridges resistant to erosion and weathering. Previous Work: Because of the obvious outcrop of the magnetite-rich beds and knowledge gained from early developments within the general region, it is conceivable that the presence of the iron formations has been known for a good many years. The area is included in studies made by L. F. Kindle* in 1929 and 1930 for the Ontario Department *Kindle, L.F., Kowkash-Ogoki Gold Area, Ontario Department of Mines Annual Report, Vol. XL, Part IV, 1931; map 40f

Jan 1, 1961

By C. E. Van Orstrand

An intrusive body is a mass of igneous rock that has migrated upward, presumably from great depths. Great variations in form, composition and depth of burial occur. It is not proposed in this paper to go into all of the details of the problem. Instead, it mill be assumed here that the intrusive has the form and characteristics represented in Fig. I. According to W. 11. Emmons minerals are not deposited in appreciable quantities below the "dead line." Important amounts of ores of virtually all metals may be found around summit cupolas, but only gold, copper and zinc (in limited quantities) are usually associated with trough cupolas. Most students of ore deposits agree that temperature changes are largely instrumental in precipitating many ores in the "hood" and that the difference in temperature between the intrusive and that of the country rock may be the chief factor in determining the mineralogy of a deposit. A problem then of some interest is to correlate the principal physical features of the intrusive with the phenomena of heat conduction as evidenced by the cooling curves and the isothermal surfaces. Mathematical Theory In order to show the possible application of heat conduction to the interpretation of the processes of metalliferous deposition associated with intrusives, it will be as- sumed that the intrusive is a large par-allelopiped of dimensions, 2l, 2m, 2n. The equation that represents the flow of heat from the parallelopiped into country rock (v = o, 1 = o), which has the same thermal properties as the intrusive, is2,3 l-x v I FT 2 [2 2 — l-x m — y — m — y n — z In this equation, the origin, x = o, y = o, z = o, is at the center of the parallelopiped. v = temperature at point x, y, z, time 1. v, = initial temperature throughout the intrusive, 1 = o. k = coefficient of thermal diffusivity. a, ß, y are variables of integration. Put n = m in Eq. I, and we have v I [2/5 [2I-x 2 — l-x m — y 2 2 2 kt 2 20xt e-a2da ebrdß

Jan 1, 1946

By C. E. Van Orstrand

An intrusive body is a mass of igneous rock that has migrated upward, presumably from great depths. Great variations in form, composition and depth of burial occur. It is not proposed in this paper to go into all of the details of the problem. Instead, it mill be assumed here that the intrusive has the form and characteristics represented in Fig. I. According to W. 11. Emmons minerals are not deposited in appreciable quantities below the "dead line." Important amounts of ores of virtually all metals may be found around summit cupolas, but only gold, copper and zinc (in limited quantities) are usually associated with trough cupolas. Most students of ore deposits agree that temperature changes are largely instrumental in precipitating many ores in the "hood" and that the difference in temperature between the intrusive and that of the country rock may be the chief factor in determining the mineralogy of a deposit. A problem then of some interest is to correlate the principal physical features of the intrusive with the phenomena of heat conduction as evidenced by the cooling curves and the isothermal surfaces. Mathematical Theory In order to show the possible application of heat conduction to the interpretation of the processes of metalliferous deposition associated with intrusives, it will be as- sumed that the intrusive is a large par-allelopiped of dimensions, 2l, 2m, 2n. The equation that represents the flow of heat from the parallelopiped into country rock (v = o, 1 = o), which has the same thermal properties as the intrusive, is2,3 l-x v I FT 2 [2 2 — l-x m — y — m — y n — z In this equation, the origin, x = o, y = o, z = o, is at the center of the parallelopiped. v = temperature at point x, y, z, time 1. v, = initial temperature throughout the intrusive, 1 = o. k = coefficient of thermal diffusivity. a, ß, y are variables of integration. Put n = m in Eq. I, and we have v I [2/5 [2I-x 2 — l-x m — y 2 2 2 kt 2 20xt e-a2da ebrdß

Jan 1, 1946

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick&apos;s first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank&apos; supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains&apos; Glasstone, et al&apos; treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity&apos; has shown how to convert the Onsager equations to a form very similar to Lamm&apos;s. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

By Linn M. Farish

The estimated production of petroleum in the Dominion of Canada for 1931 was 1,582,000 bbl., an increase of 60,000 bbl. over 1930. Nearly all of the production came from Alberta, with a small quantity from Ontario, and a very minor amount reported from New Brunswick. At the beginning of 1931 it was hoped, and predicted, that a substantial increase in production would be shown for that year, but such was not the case, since Alberta did not show the anticipated gain. The production from Ontario and New Brunswick has not varied more than a few thousand barrels during the past 10 years and aggregated 124,000 bbl. in 1930, with 126,600 bbl. estimated for 1931. Unless new fields are discovered, production in 1932 will decline, with Ontario and New Brunswick showing little change and Alberta declining appreciably. Canadian production by provinces during the past 10 years is given in Table 1. Furnished by the Dominion Bureau of Statistics. a Barrels of 35 Imperial gallons or 42 U. S. gallons. c Figures for Ontario and New Brunswick are estimated. The production of natural gas in Canada reached the record figure of 29,377,000,000 cu. ft. in 1930 and it is estimated at 26,874,600,000

Jan 1, 1932

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.&apos; Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy&apos;s law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f&apos;(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f&apos;(S) can be calculated. It turns out that the experimentally derived f&apos;(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By Ulrich H. Roesler

RECENTLY, C. Zener1 published a new thermo-dynamic treatment of the a/y transformation in iron alloys. His interpretation differs from the previous theories2-0 ainly through the separation of the free energy difference, Ga—G, into two additive

Jan 1, 1957

By Meredith Johnson

THE year 1924 saw little change in the production of oil and gas it either Pennsylvania or New York. In the early months of the year the price of Pennsylvania crude oil, $4.00 to $4.50 a barrel, was sufficiently high to cause operators to lay plans for rather extensive drilling opera-tions. But when, in August, the price dropped to $2.85 a barrel, there was no inducement for new work and drilling was curtailed. In spite of the curtailment, however, the combined production of the two states for the year showed a slight increase over 1923, the production being 8;859,000 bbl. in 1923, and 8,901,000 bbl.1 in 1924. The increased production was due entirely to. the continued development of flooding operations in the Bradford field, all other oilfields showing a decline for the year. TABLE 1. Production of Crude Oil in Pennsylvania and New York for the Last Ten Years a Production, Barrels Production, Barrels Year Year Pennsylvania I New York Pennsylvania I New York 1915 7,838,000 888,000 1920- 7,438,000 906,000 1916 7,593,000 874,000 1921 7,418,000 988,000 1917 7,733,000 880,000 1922 7,425,000 1;000,000 1918 7,408,000 809,000 1923 7,609,000 1,250,000 1919 8,137,000 851,000 1924 7,535,0006 1;366,0006 a U. S. Geological Survey figures. b Estimated. Much of the drilling in the southwestern part of Pennsylvania was done in search of gas. Natural gas in Pennsylvania is fast being recognized at its true worth and the increased prices allowed &apos;the gas companies for their product induced quite a bit of new work. The relative importance of natural gas compared with manufactured gas is shown in Table 2.2

Jan 3, 1925

South Dakota State Geological and Natural History Survey, State University, Vermillion, S D. A list of publications will be sent upon request Many of the publications are out of print A series of Biennial Reports of the State Geologist will be sent upon receipt of three cents for postage on each, and are available as follows: 1918-20, 1920-22, 1922-24, 1924-26, 1926-28, 1928-30 Available Bulletins of greatest interest are: Bulletin 4, Pre¬liminary report of the geology of the Rosebud Reservation (1909), 10 cents; 10, Possibilities of oil in South Dakota (1922), 10 cents A series of Circulars (5 cents each) deals with the possibilities of oil and gas in various parts of the state, as follows¬ Circular 8, Eastern Pennington County (1921), 9, Western Dewey County (1922); 10, Northern Dewey County (1922), 12, Eastern Harding County (1923), 13, Northern Ziebach County (1923); 20, Western Ziebach County (1925), 23, Northeastern Meade County (1925); 27, Western Corson County Other Circulars (5 cents each) are: Circular 16, The natural resources of South Dakota (1924), 22, Structures ,in northern Haakon County (1925); 24, The Ragged Butte structure (1925), 25, The structure of western South Dakota (1925), 28, Structures in western Haakon and eastern Pennington counties (1926)

Jan 1, 1933

By W. T. Olsen, R. Ulcer

WHEN a liquid alloy freezes, the solid first formed usually differs widely in chemical composition from that last formed, so that there is segregation in the alloy as cast. For example in the copper-nickel system (fig. 1) the first solid formed from a liquid containing 55 atomic pct Cu may contain as little as 38 pct Cu, while the last must contain well over 55 pct. Three factors may act to decrease segregation from the maximum possible. 1. Diffusion in the cooling solid tends to make the phase homogeneous, decreasing segregation. This may be important at slow rates of cooling. 2. Segregation is impossible without diffusion in the liquid. At extremely rapid rates of cooling there may not be enough time to allow maximum segregation. 3. Supercooling delays nucleation to temperatures well below the liquidus thereby decreasing segregation. Hence the first nucleus in the copper-nickel system may contain well over 38 pct Cu. At sufficient supercooling the first nucleus may form below the solidus, in which case there is no reason to expect any segregation whatever. From these considerations, we could predict that at sufficiently low rates of cooling the alloy would be unsegregated because of factor 1 and at sufficiently high rates of cooling there should also be no segregation because of factors 2 and 3. Considerable segregation should occur only at intermediate rates of cooling. We have demonstrated experimentally that segregation can be completely suppressed by rapid rates of cooling. For the alloys studied, however, these rates are too great to be attained in any commercial practice. An alloy of 55 atomic pct Cu, 45 atomic pct Ni was frozen by cooling at varying rates. The degree of segregation in the solid was determined by X-ray diffraction photographs. Slow rates were obtained by slowly cooling the furnace containing the liquid alloy; fast rates by pouring or ejecting droplets of the alloy into water or iced sodium hydroxide solutions. The cooling rate of the droplets can be cal-culated from their dimensions by assuming reason- able values of thermal conductivity.&apos; The experi-ments were repeated with an alloy of 16.5 pct Cu and 83.5 pct Au. A single experiment also showed a 50 atomic pct Bi-Sb alloy had no segregation at the most rapid quench. The position of back-reflection X-ray diffraction lines is a highly sensitive function of the lattice constant, which in turn depends on the chemical composition of the phase. A phase of varying composition will give broad diffraction lines. By measuring the edges of these lines and making suitable corrections for intrinsic line width, it is possible to determine the range of lattice constants represented. These can be converted to chemical compositions from a lattice constant vs. composition curve. Results are shown in table I. In the copper-nickel system the greatest segregation is found at the slowest cooling rates, where the lowest percentage of copper theoretically possible is found. In the copper-gold system, on the other hand, the degree of segregation is decidedly less at the slowest rates of cooling, being greatest at 11,100°C per sec. At no rate is the theoretically lowest percentage of copper (12 pct) found. At the rates of cooling found in sand and die castings the degree of segregation is large and depends little on the rate of cooling. Acknowledgment Most of the material in this paper is abstracted from a thesis presented by William T. Olsen, Jr. in 1948 in partial fulfillment of the requirements for the degree of Master of Science at the University of California.

Jan 1, 1951

Abbott, Argyle Campbell 1209 Sherwin Ave., Chicago, Ill. Almstrom, Adne A., Student, Met. Engrg., Washington State College Pullman, Wash. Ankudinoff, N., School of Mines, Univ. of Utah Salt Lake Cite, Utah. Apter, Robert F., Student, McGill Univ Montreal, Que., Canada. Bailey, Donald G 798 Kensington Rd., Los Angeles, Cal. Baker, Kenneth B., Met., Aluminum Co. of America Pittsburgh, Pa. Barger, Thomas, Student, Univ. of North Dakota Grand Forks, N. D. Bartholomees, Geo. C Box 304, Bonne Terre, Mo. Bates, Walter, Student, Univ. of Utah, School of Mines Salt Lake Cite, Utah. Bobb, Russell V 16 College Ave., Houghton, Mich. Boswell, John C., Stripping Asst., Fairbanks Exploration Co Fairbanks, Alaska. Brandenburg, E. C., Student, Univ. of Kentucky 112 Church St., Lexington, Ky. Brannen, John, Chemist, Assay Office, Consolidated Min. & Smelt. Co. of Canada, Ltd., Tadanac, B. C., Canada. Brooker, Edgar, Jr., Student, Ferrous Met., Stanford Univ., Stanford University, Cal. Brooking, Leslie E 738 Lakoma, Norman, Okla. Clark, Martin Lester, Student, Missouri School of Mines Rolla, Mo. Collins, Edward D., Jr Box 1597, Ribbing, Minn. Comeau, Faye Bernard, Student, New Mexico State School of Mines Socorro, N. M. Conder, Henry S., Student, Pet. Engrg., College of Min., Univ. of California, Berkeley, Cal. Cotton, John Francis, Metallographist, Stealton Plant, Bethlehem Steel Corp., Steelton. Pa. Dahlgren, Elmer George, Student, Univ. of Wisconsin, Tripp Hall, Madison, Wis. Dale, James L., Student, Colorado School of Mines Golden, Colo. Dashti, Mirza Abdullah Khan, Graduate Student, Columbia School of Mines, Engrg. Chemistry, New York, N. Y. DeHuff, Gilbert L., Jr., Student, Lehigh Univ Bethlehem, Pa. de Romana, Enrique P., Jr. Engr Casilla 22, Arequipa, Peru. Oresbach, Charles Howard, Geol., Gulf Production Co Box 1428, Amarillo, Tex. Evens, Howard G., Student, Michigan College of Min. & Tech Houghton. Mich. Fassler, Glen Emerson Rodman, Inspiration, Ariz. Feight, Charles Donald, Foreman, Clairton By-Product Coke Wks., Carnegie Steel Co., 319 5th St., Wilson, Pa. Floe, Carl F., Student, State College of Washington Pullman, Wash. Fuentes, Vicente, Student, Pet. Engrg., Univ. of Oklahoma, School of Mines, Norman, Okla. Fuhrman, Carl F., Student, New Mexico School of Mines Socorro, N. M. Goergen, Gerald G., Cerro de Pasco Copper Corp Casapalca, Peru. Grove, Hubert A., Training Course, U. S. Aluminum Co New Kensington, Pa. Gastetter, Robert E 1010 N. Cherry Ave., Tucson, Ariz. Halbouty, M. T., Student, Texas Agriculturcl & Mech. College, Box 254, Faculty Exchange, College Station, Tex. Halfast, Edgar 710 E. Okmulgee Ave., Muskogee, Okla. Hall, Robert Lee 121 58th St., Niagara Falls, N. Y. Hanson, Rolf H., Student, Colorado School of Mines Golden, Colo. Hillyer. Shaler G., Student, New Mexico School of Mines Socorro, N. M. Hoertel, Frederick W., Met., R. W. Hunt Co., Engrs St. Louis, Mo. Holtz, Henry G., Student, Ohio State Univ Columbus, Ohio. Hon, Richard J Box 721, Miami, Ariz. Huffman, James O&apos;Neil, Student, College of Min., Univ. of California Berkeley, Cal.

Jan 1, 1929

By I. R. Kramer, L. J. Demer

Aluminum single crystals were pulled in an electrolytic cell allowing surface removal during the deformation. The extent of Stages I and 11 of the stress-st-aitz curve was increased and the slope decreased as the rate of metal removed from the surface was increased. An increase of the strain rate caused a decrease in the effectiveness of the metal removal. The data indicate that the work-hardening coefficient in Stage I is determined primarily by the conditions which exist on the surface of the crystal. In Stages 11 and 111, both surface effects and internal barriers are important. ALTHOUGH numerous investigations have been conducted on the plastic flow characteristics of metals in an attempt to explain the mechanism of work-hardening, relatively few studies have taken into account the influence of the surface. In all current theories of work-hardening it is assumed that the impediments to the movement of dislocations are within the crystal. The barriers due to the surface and the existence of solid and liquid films have been neglected even though it has been demonstrated that the surface exerts a large effect. A number of investigators1-l8 have shown that solid films on the surface of single crystals markedly affect their mechanical behavior. In general, the presence of a solid film tends to increase the yield stress and increase the work-hardening rate. Often, on single crystals, Stage I and, at times, Stage II regions are completely suppressed. Various mechanisms have been offered for the effects of oxide and metal films as well as the influence of electrolytes. Of these, concepts concerned with the locking of surface dislocation sources and the blocking of dislocations at the surface resulting in pileups appear to be actively considered at present. Barrett,11 Takamura,6 Gilman,19 Lipsett and King,20 Shapiro and Read,10 and Weiner and Gensamer21 are among those who have interpreted their results in terms of piled-up dislocations at the surface, while Adams.22 and Chalmers and Davis23 have explained their experimental observations in terms of locking of surface dislocation sources. In general, the change in plastic flow properties due to electrolytes has been explained in terms of the unblocking or unlocking of dislocations by the removal of the oxide films. In considering the two proposed mechanisms, it appears that the locking of sources of surface dislocations by a solid film should exert a primary influence only on the critical resolved shear stress for flow and not on the slopes of Stages I and 11. However, the blocking at the surface of dislocations from internal sources may also affect the critical resolved stress and furthermore exert an influence throughout the whole plastic range. In certain cases it does not seem feasible to explain the results of experimental observations in terms of locking of surface dislocation sources. The abnormal aftereffects found by Barrettll,12 by removing the oxide by an acid treatment are excellent evidence of the blocking of dislocations at the surface. Additional evidence in favor of a blocking due to a pileup of dislocations at the surface may be found from the observations that the critical resolved shear strength continues to increase with the thickness of the oxide layer until very heavy oxide layers are formed. If the locking of surface dislocations sources were the dominant factor, the critical resolved shear stress would not be expected to increase after all of the surface sources were locked by the formation of the oxide. This may be expected to happen after a few atomic layers of the oxide are formed. In spite of the above evidence on the strong influence of the surface on the plastic flow characteristic, this has been ignored in current theories of work-hardening. Seeger24,25 suggested that most of the dislocations may slip out of the crystal only when the specimen axis is within certain areas of the orientation triangle. In other areas the resolved shear stress in other glide systems is large enough to generate dislocations which can form Lomer-Cottrell locks, thereby decreasing the average slip distance in some directions and causing a larger hardening rate. Friede126 assumed that at the beginning of Stage 11, a large number of Lomer-Cottrell dislocations are formed by a catastrophic process which used up all the Frank-Read sources on the secondary slip-planes. In this manner a fixed number of Lomer-Cottrell locks is formed which act as barriers against which the dislocations can pile up. In Stage 111, Seeger24 and Diehl, Mader, and Seeger25 proposed that Lomer-Cottrell barriers are circumvented by the cross slip of extended screw dislocations. Cottrell and Stokes,27 Friedel,26 Cottrell,26 and stroh29 suggest that the Lomer-Cottrell dislocations collapse under the stress field of the dislocation pileup. It is the purpose of this paper to report the changes in Stages I, II,and III of the deformation process in

Jan 1, 1962

By Larry A. Shiprnan

DEMANDS upon power plants by the war program in 1941 intensified problems of coal utilization. It was an outstanding year in that field. The domestic heating stove witnessed outstanding development; the research folks progressing so rapidly that the design of the "perfect" stove is just around the corner. Use of colored motion pictures in analyzing fuel-bed performances has reached a new high with the colored pictures taken at minute intervals and projected at sixteen frames a second as shown by the Koppers Coal Co. and the Anthracite Institute (on domestic stokers) and the Consolidated Edison Co. (industrial stokers). Continued efforts of this kind will be beneficial in analyzing further some of the "Code for Testing Coal" problems confronting Subcommittee No. 2 of the Joint A. I. M. E. - A. S. M. E. Committees.

Jan 1, 1942