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By M. F. Burr, F. V. Lenel, G. S. Ansell

The mechanism of materials transport was studied in a model experiment in which a silver sphere was sintered to a silver plate under an applied external stress near 800° C. For this purpose the rate of growth of the neck between the sphere and the plate which is proportional to the strain rate of the creep process involved in a neck growth was determined by measuring the change in electrical resistance of the away. This rate of neck growth will depend upon the magnitude of the applied external stress. By measuring the rate just before and just after a change in the external load and therefore the applied stress, the relationship between strain rate and stress can be derived. For material transport by slip in a pure metal it is expected that the strain rate should be proportional to the 4.5th power of the stress, while for transport by diffusional flow the strain rate should be proportional to the first power of the stress. It was found that for stresses above 5 X 10' dynes per sq cm (70 psi) the exponent in the stvain rate-stress relationship was near 4.5 while for a stress of 0.7 x 108 dynes per sq cm (10 psi) an exponent of 1.8 was determined indicating that under the conditions of the experiment the transport mechanism for creep in silver shifts from diffusional flow to slip in the region of 0.7 x 106 dynes per sq cm (10 psi). The importance of these findings for an understanding of the mechanism of material transport in conventional sintering (without an external load) is pointed out. In a paper by Early et al.,' the mechanism of material transport during sintering was treated as a creep process. It was pointed out that two possible types of creep processes could operate during sintering. In one of these material transport takes place by vacancy diffusion due to a gradient in chemical potential. The vacancy sinks in this diffusion process may be either grain boundaries, as in Herring-Nabarro microcreep, or regions beneath a surface of small radius of curvature. The diffusive transport may be by volume, grain boundary, or surface diffusion. In the other mechanism, creep takes place by slip, i.e., dislocation motion with its rate generally controlled by dislocation climb. One method of distinguishing between these two modes of materials transport is to investigate the creep rate, i.e., the rate of material transport as a function of stress. For material transport by vacancy diffusion, the creep rate is proportional to the stress.' For creep by slip, controlled by dislocation climb, the creep rate is proportional to a power of the stress. For pure metals this power is 4.5;374 for dispersion-strengthened material a fourth power relationship can be derived.5 This difference in the stress dependence of the strain rate is illustrated schematically in Fig. 1, in which the logarithm of strain rate is plotted vs the logarithm of the stress for material transport in a pure metal by vacancy flux and by dislocation climb. The stress range in which the two types of material transport overlap would be expected to be relatively small. In the experiments described by Early and coworkers compacts pressed from spherical copper powder were sintered isothermally under an applied axial external load in a dilatometer. During sintering the magnitude of the applied external load was changed and the rate of axial shrinkage of the compact before and after the load change determined. In order to find the stress dependence of the strain rate the magnitude of the stress acting on the neck area between the spherical particles before and after the load change had to be calculated. This stress is the resultant of the stresses due both to the externally applied load and to surface tension. The stress due to surface tension is a function of the geometry of the powder compacts. It can be determined, at least for simple geometrical arrays,'76 but it is difficult to obtain exact values of the stresses for actual powder compacts when only average values of particle diameters and of neck diameters between particles are available. The calculation of stress and the strain rate-stress relationship is therefore only very approximate.

Jan 1, 1968

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By J. L. Huitt, B. B. McGlothlin, D. K. Lowe

Published correlations for the principal aspects of hydraulic fracturing were combined into a digital computer program to facilitate the study of interrelated variables. The computer program includes individual relationships for fracture width during pumping, fracture area generated, propping agent embedment, flow capacities of propped fractures and transport of propping agents in horizontal fractures. The effects of more than 20 treatment and formation parameters on the predicted results of hydraulic fracturing treatments were studied. The effects of these parameters were determined for (I) fracture width during injection, (2) fracture width after the overburden comes to rest on the propping agents, assumed not to be crushed, (3) generated and propped fracture area, (4) location and concentration of propping agents in the fracture when injection ceases, (5) flow capacities of the various propped sections of the fracture and (6) expected increase in the well productivity. The effects of propping agent, formation and fracturing fluid parameters on well productivity are discussed. The parameters that were found to have the most pronounced effects on hydraulic fracturing treat~nents are injection rate, treatment volume, fracturing fluid coefficient, size and amount of propping agent, spearhead volume, well drainage radius and formation capacity. INTRODUCTION Many correlations have been published for predicting effects of various parameters that are considered in the design of hydraulic fracturing treatments. The Carter equation' can be used to predict generated fracture radius as a function of fracture width, fracturing fluid leakoff and other parameters. Fracture width can be determined by use of the Perkins and Kern correlation' in which the fracture width is related to the fracture radius, fluid injection rate and certain formation and fracturing fluid parameters. Wahl and Lowe et aL4 have reported methods of predicting the location of propping agents in fractures when pumping ceases. The former study is applicable to the case where the ratio of propping agent diameter to fracture width is less than 0.1. The latter is applicable when this ratio is greater than 0.1. These studies showed that the propping agent placement in horizontal-radial fractures depends principally on how the individual particles are transported in the fracture by the carrying fluid. Particle transport in fractures is determined by local fluid velocity in the fracture, fluid and particle properties, and the size of the particle relative to the fracture width. The distribution of propping agents, effective overburden pressure and formation rock strength control the propped fracture width6 by controlling the extent to which the propping agent particles embed into the fracture faces. From the distribution of propping agents and the propped fracture width, fracture flow capacities can be calculated or the various regions of the fracture. The flow capacities and the radial extent of these regions can be combined with reservoir information to predict the productivity increases for fractured wells. In all these studies, the effects of certain treatment and/ or reservoir parameters on one facet of fracturing can be predicted only if other facets which the parameters affect are fixed. For instance, fracture width and radius are interrelated; that is, to calculate the value of one, the value of the other must be known. Also, some parameters influence more than one aspect of fracturing. For example, prop-pant transport is a function of both fracture width and fluid viscosity. but fracture width is itself a function of fluid viscosity. Since these calculations are complex and the parameters interrelated, it is not possible to write an equation with which the over-all effects of treatment parameters can be solved explicitly. For these reasons, the correlations for determining the effects of the parameters which are most significant in hydraulic fracturing treatments have been incorporated into a digital computer program. COMPUTER PROGRAM The program, which was written for an IBM 7094 computer, can be used to predict results of most of the combinations and values for the treatment parameters that are ordinarily considered for fracturing treatments. A spearhead of fracturing fluid and a propping agent-carrying fluid with different fluid properties can be taken into account. Also, the total volumes and relative amounts of the spearhead and carrying fluids can be varied. Two different propping agents (as used in tail-in operations) and a wide range of formation properties and injection rates are considered. The computer program (Fig. 12) consists of several sets of calculations. First, the final flooded fracture radius and average fracture width at the cessation of pumping are calculated. This is done by simultaneous solution of the Perkins and Kern fracture width equation and the Carter equation for flooded fracture radius (equations used in the computer program appear in the Appendix). The next step is to determine local fluid velocity in the fracture as a function of time and radius. Since it is not possible to write this function in closed form expression, a table of velocity values is generated by the program and stored for subsequent use. The time span from the beginning of

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951

By Katherine Mather

This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. Results of the properties of these rocks on their performance as concrete aggregates are discussed. CRUSHED stone classified as limestone comprises about 70 pct of the crushed concrete aggregate and roadstone produced in this country, and the product has amounted in the recent past to about 97 million tons per year, valued at more than $123,-000,000.' Therefore an evaluation of the properties of rocks classified in these statistics as limestones and an ability to predict their behavior as aggregate in portland cement concrete are matters of considerable economic consequence to producers and consumers of aggregate. This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. It also points out certain results of the properties of these rocks on their performance as concrete aggregates. The problems encountered in efforts to explain the behavior of limestones, dolomites, and related rocks as concrete aggregate lie on the frontiers between the ignorance of the geologists and the ignorance of the engineers. The mineral composition and textures of the rocks have not been adequately explored and described, and the effects of mineral composition and texture on the performance of aggregates have been worked out in only a few cases. There are instances of unsatisfactory performance and some generalizations of those experiences. There are many more examples of satisfactory performance than of unsatisfactory, but there is practically no published information as to why a particular aggregate was satisfactory in a specific use. There are all too few investigations of undeteriorated concrete; more is known about the pathology of concrete than about its normal structure and aspect. As part of the investigation of aggregates, the classification of rocks is not an end in itself, but is a step toward recognition of properties expected to influence the behavior of aggregates in their intended use. Rock of any type may perform well or poorly as concrete aggregate, depending on the physical condition of the rock, its physical and chemical properties as compared to those of the matrix in which it is placed, and the circumstances under which the concrete is exposed. Some classification and descrip- tion of the limestones is necessary to distinguish subgroups whose members will probably behave in similar ways and to evaluate the group as a whole. The group name, limestone, includes and tends to conceal the identity of rocks that have a very great range in chemical and mineralogical composition, structure and texture, conditions of deposition, subsequent history, and suitability for use as concrete aggregate. All the rocks classified as limestones include one or both of the most abundant rock-form-ing carbonate minerals, calcite and dolomite, as major constituents. Carbonate rocks is a more descriptive and more accurate group name than limestone, which has generally been used to include dol-omitic or magnesian limestones and dolomites as well as calcitic limestones. Classification and Description of the Carbonate Rocks The question of names to be applied to the carbonate rocks may appear academic, but it is of practical importance as long as there are specifications for aggregate that result in acceptance or rejection of rocks by name and as long as failure to make distinctions among the carbonate rocks leads to misunderstandings of their properties and of what may be expected of them in performance. Materials included in production statistics as limestone and tested for concrete aggregate as limestone range in fact from calcareous shale and calcareous or dolomitic sandstone and argillaceous limestone and dolomite to calcitic limestone and pure dolomite and to rocks close to calcitic and dolomitic marble. To take a simple example: consider two manufactured coarse aggregates, both dense and unweathered, one composed principally of crystalline calcite and the other of crystalline dolomite, but both known as limestone. If each is used as coarse aggregate in a standardized concrete mixture with the same fine aggregate used in both cases, made into concrete specimens, and tested in accelerated freezing-and-thaw-ing, the test results will probably be quite different, because of the differences in internal bond and thermal properties between the two aggregates. As long as both aggregates are called limestone, the test results cannot be explained, or used except in a very limited way; if the aggregates are distinguished as limestone and dolomite and the consequent differences in texture and thermal properties are recognized, the results are reasonable. Classification of the carbonate rocks used as aggregate should be based on structure and on composi-

Jan 1, 1954

By Frank H. Macpherson

FEW people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war. The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,725 2 tons in the period 1931 to 1941. It became apparent early in the year 1941 that the United States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. As more than 95 per cent of the known bauxite reserves of the United States was in Arkansas, careful preliminary studies were made in that state by representatives of the United States Bureau of Mines, the United States Geological Survey and the War Production Board in the summer of 1941. Reserves in other states also Were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite-producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry Weight) set for Arkansas by the War Production Board Was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted, the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place

Jan 1, 1945

By E. S. Machlin, Morris Cohen

The isothermal formation of martensite in a 71 pct Fe, 29 pct Ni alloy is found to take place mainly by the nucleation of new plates rather than by the growth of existing ones, and is dependent on the temperature and time of the isothermal hold, the amount of atherrnal martensite present, the state of internal strain, and the application of tensile stress. The conclusion is reached that the isothermal nucleation is activated by thermal fluctuations superimposed on localized regions of very high strain. The reaction-path concept, involving martensite nucleation at strain embryos by athermal activation on cooling, or by thermal fluctuations on holding, reconciles the athermal and isothermal modes of transformation, and offers a unified picture of the kinetics of martensite formation. THE phenomenon of isothermal martensite formation has been the subject of considerable study lately,'-' and its reality has been thoroughly established. The existence of such isothermal transformation has been claimed to confirm the nucleation and growth hypothesis as applied to the martensitic reaction.1 " However, the isothermal formation of a martensitic phase is also compatible with the reaction-pathw escription of the transformation. The purpose of this investigation is to examine the isothermal mode of the martensitic reaction, both theoretically and experimentally, in order to test the likelihood of the above two mechanisms. Material and Methods The alloy used in this study contained about 71 pct Fe and 29 pct Ni. The complete analysis was 29.5 ± 0.2 pct Ni, 0.036 pct C, 0.02 pct N, 0.19 pct Mn, 0.09 pct Si, 0.008 pct P, and 0.006 pct S. The amount of isothermal transformation was determined by electrical resistance measurements using a Kelvin double bridge. The specimens were in the form of rods 1/16 in. diam x 4 in. long. Aus-tenitizing was performed at 1095°C for % hr either in a pre-purified nitrogen atmosphere or in an evacuated Vycor tube, followed by oil quenching to room temperature. After this treatment, the samples were completely austenitic, and the transformation studies were conducted at subatmospheric tempera- tures. Lineal analysis and X-ray determinations of retained austenite were used to calibrate the electrical resistance changes in terms of the percentage of martensite. The martensite range curve for this alloy is given in Fig. 9 of ref. 6. The M, temperature occurs at about -18°C (255°K). Reaction-Path Theory The nucleation and growth description of the martensitic transformation that occurs isothermally has already been given by Kurdjumow.','2 However, no comparable treatment exists using the reaction-path concept." Consequently this section presents the reaction-path description of the isothermal mode of the martensitic transformation. According to the latter theory, there is a reaction path (a strain) which describes the relative motion of the atoms during their transference from the austenitic to the martensitic state. The possibility exists, therefore, that the nucleation of a martensitic plate is accomplished by an embryo that comprises a state intermediate between that of austenite and martensite. This state may be attained within a finite volume by means of a homogeneous strain of the austenitic matrix. There is a free-energy barrier (F.) along the reaction path, corresponding to a critical strain in a critical volume. When activation is achieved, a spontaneous increase in strain and volume of the embryo takes place to generate the full-size martensitic plate. This mode of nucleation is to be distinguished from the more conventional mode involving embryos of the martensitic phase that merely grow in size by an interface motion. There are two ways whereby embryos in the austenitic phase can achieve the critical state of strain for isothermal nucleation: 1—through the formation of internal strains by plastic deformation or by stress; and 2—through thermal fluctuations, preferably superimposed upon existing internal strains. The activation free energy F,, must be supplied either mechanically by internal strains or thermally by energy fluctuations, or by a combination of both.

Jan 1, 1953

By D. Geoffry Minnes, Ray Blair, Stanley J. LeFond

Nepheline syenite is a silica deficient crystal-line rock consisting of albite and microcline feldspars and nepheline, together with varying but small amounts of mafic silicates and other accessory minerals. Nepheline-bearing rocks are widely distributed around the world but only in Canada, Norway, the Union of Soviet Socialist Republics, and the United States are deposits worked commercially, Because of its low melting point and fluxing ability, nepheline syenite was investigated in the early 1900s by many students of glass and ceramics. Although the nepheline syenite deposits in Methuen Township, Ont., Canada, were discovered as early as 1897 it wasn't until 1935 that the first mill was erected to produce nepheline syenite products. In Canada, nepheline syenite deposits are worked by Indusmin Ltd. and International Minerals and Chemical Corp. (Canada) Ltd. who have combined production capacity in excess of 1800 stpd. Between 1935 and 1972 seven million tons valued at $78 million were produced from the Methuen Township deposits. In Norway, the Norsk Nefelin Div. of Elkem Spigerverket has produced nepheline syenite from a deposit on Stjernöy Island in western Finland since early 1960. Production has increased from 8 kt in 1961 to over 200 kt in 1980. Nepheline syenite has been under investigation in the Union of Soviet Socialist Republics (USSR) since at least 1928. In 1951 the first commercial alumina works was brought on stream at Volkhov, near Leningrad, utilizing nepheline concentrates from the Kola peninsula as mill feed. Since then two others have been completed and more are planned. Large quantities of portland cement, sodium carbonate, and potassium carbonate are produced in conjunction with the alumina. A material called nepheline syenite, but actually a pulaskite, is produced in Pulaski County, Arkansas, by the McGeorge Construction Co. for construction aggregates and by the 3M Co. for roofing granules. The Dome Fill Co. purchases the fines and uses them in the preparation of enclosed construction fill. Production is over 2,000,000 stpy. Chap. 16 on "Feldspar, Nepheline Syenite, and Aplite" in the 3rd ed. of Industrial Minerals and Rocks (Castle and Gillson, 1960) and Nepheline Syenite Deposits of Southern Ontario (Hewitt, 1960) contain excellent accounts of earlier commercial development of nepheline syenite as a glass and ceramic material. As in the 4th ed., this chapter deals mostly with the period since 1960 and with matters not previously reported in detail. An English monograph on Nepheline-Syenite and Phonolite (Allen et al., 1968) is a complete survey, at the time, of nepheline syenite which, with its very complete list of references, is an excellent source book. End Uses Nepheline syenite from the Canadian and Norwegian producers finds use primarily in the manufacture of glass and ceramics. One producer also makes several grades of nephellne syenite that are useful as extender pigments and fillers in paint, plastics, and rubber. In the Soviet Union nepheline is used in increasing quantities in the manufacture of alumina, alkali carbonates, and portland cement and to a lesser degree it is used in the manufacture of colored container glass.

Jan 1, 1983

By C. H. Li, R. J. Stokes, T. L. Johnston

Dislocation half-loops, artificially introduced by sprinkling with carborundum, were subjected to stress using three-point loading. The different stages of loop expansion and multiplication were then correlated with the macroscopic stress-deflection curve. Loop expansion started at approximately one-third of the "yield stress," defined here as the motivation stress. Above one-half of the "yield stress" simple multiplication commenced while about two-thirds of the yield stress gross multiplication developed short slip-line segments. These values were not affected by the age of surfaces exposed to both dry and wet air. Slip was not detected on unsprinkled crystals below two-thirds of the "yield stress." Thus the stress to activate intrinsic sources, defined here as the activation stress, was approximately twice the motivation stress. This relationship was independent of the strain rate used. It is concluded that lattice resistance takes the form of a viscous drag rather than a static type of force. THE importance of surface condition and environment as one of the more significant factors controlling the mechanical properties of ionic solids has recently received renewed attention.1-4 In some materials, notably the alkali halides, exposing freshly cleaved specimens to the atmosphere results in a progressive hardening and embrittlement of the crystals. This has been attributed to the surface layer becoming "aged," thereby restricting the motion of dislocations in such a way that pileup and eventually fracture results. It is necessary therefore in studying the mechanical properties of ionic crystals to inquire first into the density and distribution of dislocations in the normal cleaved surface and to understand the role these dislocations play in the onset of plastic flow. Knowledge of the effect of environment on this behavior will then assist in understanding the mechanism of embrittlement on aging. In the work reported here a method is described for studying the initiation of plastic flow from dislocation sources in the surface of magnesium oxide crystals. Preliminary results are described of the influence of surface age on this behavior. EXPERIMENTAL TECHNIQUES The magnesium oxide used in this investigation was obtained from the Norton Co. and had a nominal purity of 99.5.pct. Single-crystal specimens, having dimensions typically 1/4 by 1/8 in. cross section and 1 in. in length, were prepared by cleavage over (100) planes from the parent crystal. They were deformed under three-point loading with 3/4 in. spacing between the two end supports and a constant rate of deflection at the center of 0.001 in. per min. The maximum strain rate therefore was 1.5 X 10-5 sec-1. Reasons for choosing this particular form of loading will become apparent in a later section. In addition, a number of confirmatory type tests have been performed at higher loading rates where the maximum strain rate was increased to 1 x 10-3 sec -1. Following deformation the crystals were etched to reveal the dislocation distribution. In a previous paper5 we described a satisfactory etching solution consisting of 5 parts of saturated ammonium chloride, one part of sulfuric acid, and one part distilled water. Immersion of the crystals for 1/4 hr at room temperature developed reproducible conical etch pits at the points where dislocations emerged through the surface. It should be mentioned that dislocations freshly introduced by room temperature deformation gave sharply pointed etch pits which generally distinguished them from the almost flat-bottomed pits obtained on "grown-in" dislocations. The distinction is obvious in the photomicrograph included in Fig. 5(b). Annealing crystals at 1000°C for 12 hr on the other hand gave sharper etch pits on the grown-in dislocations and the distinction was no lower -possible; a similar observation has been reported for lithium fluoride. We have succeeded furthermore in chemically polishing magnesium-oxide crystals. Boiling in fresh 85 pct ortho-phosphoric acid for only 1 min resulted in a microscopically smooth surface which could again be etched to reexamine the dislocation distribution. This boiling time was sufficient to remove the surface damage introduced by cleavage (see next section). SURFACE DISLOCATION SOURCES There are a number of ways by which dislocations may be introduced into cleaved surfaces to act later

Jan 1, 1960

By C. E. Brown, D. C. Helms, O. W. Shimer

The early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. . The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 3½ million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20" to 90 and some are on the invert in many sharp folds and faults. Planning The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been . maintained. Locations of stripping areas are determined as follows: I. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness

Jan 1, 1944

By Kurt Stock

The war caused a demand for enormous quantities of high-grade zinc, which were not available and could not be produced from pure ores in sufficient amounts and in the time required. Redistillation of virgin spelter on a large scale was practiced to supply this demand; this paper gives a full description of the process used by the Oklahoma smelters of the Bartlesville Zinc Co. As the redistillation of zinc has become of historical interest only, having been superseded by the electrolytic process, it was deemed advisable to give expression to this phase of the metallurgy of zinc that, in the past, had never gone beyond laboratory experimentation. THE grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: TOTAL, NOT LEAD, IRON, CADMIUM, OVER. PER PER CENT. PER CENT. PER CENT. CENT. A. High grade 0.07 0.03 0.05 0.10 B. Intermediate 0.20 0.03 0.50 0.50 C. Brass special 0.75 0.04 0.75 1.20 D. Prime western 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages.

Jan 7, 1924

By E. L. Tucker

IN THE metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alka-line or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture-and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have, successfully introduced it in. the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation.. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its, application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious.

Jan 8, 1925

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 Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.&apos; The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.&apos; The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,&apos; since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By William B. Phillips

This paper was prepared at the request of Capt. A. F. Lucas, Chair man of the Institute&apos;s Committee on Petroleum and Gas; as a pre1iminary.discussion of the fuel oils which are used in the Southwest, giving their composition, uses, prices, etc. Should it afterward be found desirable, these observations may be extended over a larger area. In this connection, I suggest that samples of all kinds of fuel oils, including various tars, from all over the country, be collected and sent to some testing laboratory for examination. We would be glad to extend the facilities of the laboratory of the Bureau of Economic Geology and Technology, at the University of Texas, for this purpose, and to do the work free of all expenses. After such examinations are made and the results classified and studied, it would be possible to suggest specifications under which fuel oils should be purchased, and to arrive at some conclusions respecting the uniformity of such specifications, with due allowance for climatic and other more or less local conditions. While such specifications do not now depart from a common standard anything like as much as specifications for illuminating oils do, yet there are discrepancies which should not exist. Some of these discrepancies are of lessening importance, due to the pronounced tendency to distill every crude oil that can be distilled with profit, and to send residues into the market for fuel oil. Residues from the refineries are of a more uniform chemical composition and physical nature than many of the crude oils that go direct into the fuel market. The lower flash-point oils are disappearing from the fuel trade and in place of them we are getting oils that do not flash below 220" F., nor burn under 320" F. In the Southwest, it has not been long since we had fuel oils that flashed as low as 110" F., and the average flash point over a considerable period was 151" F. Now we are using oil that flashes at about 30" lower than the former burning point, which was 258" F. In other words, the flash point has risen, on the average, 100"; and the burning point about 75".

Jan 1, 1915

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 Warren Howes, C. O. Anderson, Robert E. Illidge, M. D. Harbaugh, S. J. Burris

The Tri-State zinc-lead mining district embraces an extensive area, including the northeastern part of Ottawa County, Oklahoma, the southeastern part of Cherokee County, Kansas, and adjacent portions of Missouri, mainly in Jasper County. The Oklahoma-Kansas portion of the district, in the vicinity of Picher, Okla., has been the principal producing area since 1917, and the present milling practice in that section is the subject of this paper. This district is the largest zinc-producing field in the United States. In 1926 it produced 55 per cent of the nation&apos;s zinc and 15 per cent of its lead, and in 1933 it produced 35 per cent of the zinc and 10 per cent of the lead. From 1842 to 1933, inclusive, the total output of the district was 18 1/2 million tons of zinc and lead concentrates valued at 818 million dollars. Of this production, the Oklahoma-Kansas, or Picher, field yielded over 9 million tons valued at over 400 million dollars. Mining operations in the Oklahoma-Kansas field near Picher and Baxter Springs began in 1915. The mills built it that time consisted merely of gravity concentration plants employing jigs and tables and the same flow sheets as had proved satisfactory with the free-milling ores such as were mined in the Joplin-Webb City fields in Missouri. The Kansas-Oklahoma ores proved to be much richer but also more refractory to treatment than those in the Joplin area, and contained a considerable percentage of zinc mineral not freed by the amount of crushing usually practiced in preparing the ores for jigging. Thus the old Joplin type of mill, with its usual two or four jigs and a few tables, proved inadequate and resulted in excessive tailings losses sometimes as high as 50 per cent

Jan 1, 1935

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers&apos;; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.&apos;.&apos; A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".&apos; This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,&apos; Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967