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By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By D. L. Marshall, O. F. Thornton

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R' cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"'. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.' The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.' It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

A knowledge of the principles of punctuation is essential to effective and intelligible writing, for the ease and pleasure of the reader, and even his understanding, may depend upon the choice and the placing of punctuation marks. To 'punctuate' is to mark with stops or points; the word comes from the medieval Latin punctuare (punctuatus), which in turn is derived from the Latin punctum, a point. The purpose of punctuation is to show the manner in which the writing is to be understood; to indicate the relations between parts of a sentence and between successive sentences. To some extent "it does for the eye what vocal stress does for the ear", but especially it marks logical relations. Some punctuation marks, such as those indicating admiration, exclamation, and interrogation, are rhetorical as well as grammatical, but most of the common ones are logical or grammatical. My discussion will be confined to grammatical punctuation in ordinary writing. "The problem of punctuation in text matter", as George Summey * says, "is to employ words, points, and paragraph breaks in such a way as to achieve at the same time clearness, proper distribution of emphasis, and the desired kind of movement." The criticism of the punctuation of a sentence or of a group of sentences is not final until the context, within the paragraph, is read. A paragraph is a sentence or a group of' sentences forming an independent unit of the composition; it represents a unit of thought. A multiplicity of paragraphs produces a choppy effect; on the other hand, paragraphs of excessive length are tiresome, because the belaboring of one unit of thought wearies the reader. The aim should be to

Jan 1, 1931

By M. G. Nicholas

The influence of deformation, relative movement and surface cleanliness on the strength of room -temperature "interparticle" bonds between copper surfaces has been studied. No bonding resulted when clean surfaces were merely pressed together, even under pressures of 50,000 psi. Bonding resulted, however, when clean surfaces were simultaneously pressed and moved relative to each other, some bonding occurring no matter how small the pressure or relative movement. Exposure of the clean surfaces to various chemicals inhibited bonding, none at all being produced by small relative movements. The size of the movements which first produce bonding between exposed surfaces depends on the nature of the chemical, being less than 0.002 in. for cleansing reagents and greater than 0.004 in. for lubricants, water and hydrogen sulfide. It is concluded from the experimental data that the prime requirement for bonding is the dispersal of surface films such as oxides and adsorbed contaminants. THE formation of interparticle bonds during the room-temperature compaction of powder metallurgy components greatly increases the ease of handling in subsequent production operations prior to sintering. The strength of unsintered compacts follows the same general trends as their density and hardness, but quantitative data are extremely Scarce. Quantitative correlation of the data on the overall strength of a compact with that of the individual interparticle bonds is virtually impossible due to the extremely complex geometry of powder compacts. Qualitatively, however, the strengths of unsintered compacts can be correlated with variations in parameters known to influence the extent of cold bonding, and hence interparticle bonding, such as surface cleanliness, relative movement, and deformation of the mating surfaces. Kuzmic and seelig4 found that contamination of powder particle surfaces with lubricants reduced the strength of unsintered iron and copper compacts. Interparticle shear has been shown to promote bonding by Train and Hersey7 while Gregory has shown that die rotation is beneficial. Eilender and schwalbe6 concluded that most bonding occurred during the early stages of pressing iron powder compacts when interparticle shear is one of the principal processes occurring. mile there can be little doubt that these and other factors, such as particle size and shape, affect the extent of interparticle bonding produced by compaction, evaluation of the influence of individual factors is not easy. Particle deformation and relative movement, for example, occur simultaneously during compaction, making any precise measurement of their relative influences difficult. Because of these and other difficulties encountered in studying interparticle bonding in actual powder compacts, the approach adopted in this study was to

Jan 1, 1963

By R. H. Hawkins

An investigation of the applicability of geophyiical methods to northern Ontario lignite deposits was undertaken early in 1930 by the Ontario Research Foundation at the request of the Ontario Department of Mines Pre-Cambrian ... Syenite, granite gnciss, etc. Igneous intrusivcs . Lamprophyre dikes cut the Abitibi River and lover formntions. (Permission of Ontario Dept. of Mines) and was financed in part from a research grant made by the latter organization. The work to date has included gravitational, magnetic and electrical resistivity studies. The gravitational and magnetic measure-

Jan 1, 1934

By Benjamin N. Webber

The peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guana-caste, which is the northern. of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guay-jiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. Physiography In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active; (2) the Atlantic lowlands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low- lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from 0 to 800 ft. Topography is of the mature type of wide valleys and low hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. History and Production The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1949

By F. M. Lewis, J. F. Meyers

This second progress report of grinding presents comments regarding ball consumption and data pertaining to the hydroscillator, which is closed circuited with the tricone mill. A study and postulate of how balls function is presented. The paper summarizes cost reduction obtained by the method of "grinding for the tail race" rather than for "mesh tons." AT the Regional meeting in Columbus, Ohio, in September 1949, the authors presented a progress report of the first year's operation with a Hardinge tricone mill in closed circuit with a Dorr hydroscillator. The present report covers our findings on this grinding circuit to January, 1950. In order to clarify our position, the authors wish to state that no invention or discovery is claimed. The Tennessee grinding circuit is simply an engineered arrangement of known equipment arranged to incorporate all of the recognized efficiency factors of comminution as they are known today. As we concluded our first report, it was not clear how effective the Tennessee mode of operation would be on harder ores. The only information we had at that time was that the Bond grindability test at 48-mesh gave 6.04 g of undersize per revolution. A later test on the same sample at 100-mesh reduced this to 2.04 g, which is definitely in the harder ore class, and which makes the reported 8.80 kw-hr per ton of —200-mesh produced a very creditable figure. Hydroscillator Operation The machine as now developed has proved dependable and easy to operate. It starts easily under full load and responds quickly to operating adjustments. The hydraulic holes in the oscillating plate do not plug when shut down under full load. Absolutely clean hydraulic water is essential. An Elliott water screen or similar device should be an essential part of the machine to keep all scale and trash of all kinds from the hydraulic compartment. The shift operators have expressed approval of the machine. In table I we show a typical screen analysis of the hydroscillator rake sand as compared to conventional classifier rake sand on our ore. We have previously reported that of the 28.7 pct reduction in power, the hydroscillator contributed 6 pct, on a —200-mesh basis. This is a conservative figure. Some of our test runs indicated that the saving was as high as 10 pct. Laboratory studies by the Dorr Co. engineers indicate that still greater efficiency is possible. Nevertheless, the 10-ft plate is overflowing 2100 tons per day at 3 to 4 pct + 65-mesh, which is a very creditable performance by

Jan 1, 1951

By Peter F. Weiss

INTRODUCTION Austro-American Magnesite Co. of Radenthein, Carinthia, Austria, is a wholly owned subsidiary of General Refractories Company, Bala Cynwyd, USA, and has been incorporated since 1908. The raw material basis is the magnesite mine on Millstatt Alp, located in the mountains near Radenthein at an altitude of 1500 m above sea level. The mined crude magnesite is crushed in a surface crushing plant to minus 35 mm and consequently hauled to the processing plant in the valley by means of a cable conveyor of 7.5 km length. The annual production of 350,000 mt is accomplished with 20 supervisors and 122 workers (of those 60 are in the mine). The labor requirement for block caving is 0.2 man hr/mt, corresponding to an output of 40 mt/man/ shift. GEOLOGY The rock in this area mainly consists of crystalline type schist. There are mostly coarse crystalline garnet mica schists with varying mineral concentrations, and to a lesser degree, some deposits of amphibolite and marble. This petrographically rather homogeneous rock is divided into numerous different tectonic units (covers and scales). The magnesite deposit itself is a foreign body that also has been tectonically inserted. The ore body has a length of 600 m, is 450 m deep, and has a thickness of 60 m on average, varying substantially however, The contact with the accessory rock is very precise. The deposit 1 = ore body, 2 = previous open pit, 3 = caved in area, 4 = block under excavation, 5 = land slide consists of coarse crystalline magnesite in excess of 90 per cent. The few impurities consist of dolomite and talc. The lower part of the deposit is inclined parallel with the schists at approx. 40 degrees. In profile it can be seen, however, that the upper part of the deposit has been tilted over. This is a result of a post-glacial land slide reaching from the bottom of the valley at 1400 m above sea level to the peak of the mountain at 2100 m above sea level. Due to this land slide, with horizontal movements of up to 100 meters, as well as older tectonic events, the rock was crushed to a vast extent. Through mining, the land slide was reactivated; about 40 million cubic meters of rock slowly flow downhill almost like a plasticized mass. Near the surface, the rock is completely crushed and resembles a glacier rupture zone. This renders the originally impermeable rock completely water permeable so that practically all of the annual quantity of 1000 to 1100 mm of precipitation permeates the rock and flows down into the mine. The carbonate rock turns into the preferred aquifer. From 1700 to 2600 cubic meters of water have to be pumped from the mine daily. On one hand, additional problems are caused by the water in the mine, on the other hand we have learned to make use of the down- hill pressure forces to improve the crushing process during block caving. The boundary of the downhill shearing zone moves downward as mining goes deeper.

Jan 1, 1981

By Leonard Obert

The structural stability of any mine or under- ground opening in rock is dependent on the stress field, that is, the state of stress in rock before mining, the stress distribution in the rock created by the opening, and the in situ strength of the rock. In the past mine design problems have been considered by assuming that the stress field is due only to the weight of the overlying rock, the stress around the opening can be calculated from elastic theory using laboratory-determined elastic constants, and the in situ strength of the rock can be determined from laboratory tests on small specimens. Solutions to hypothetical problems using this procedure are given in a report by Obert, Duvall, and Merrill.' Because of the uncertainties of these assumptions, this method can give only a rough approximation to the solution of actual structural problems. Obviously, this approach to determining the stability of underground openings would be greatly improved if the rock stress could be measured in situ, and it is undoubtedly for this reason that in recent years many investigators have spent considerable effort on the development of procedures for measuring rock stress. In this report a method is described for determining in situ the absolute stress in rock. The method requires the measurement of the deformation of a borehole before and after the rock is stress-relieved. The magnitude and direction of the applied stresses are calculated from the borehole deformation and modulus of elasticity of the rock. Also, the results of absolute stress determination made in the walls and pillars of underground openings in five rock types are presented. From these results a number of conclusions are drawn regarding the accuracy and limitations of this method and the problem of stress measurements in general.

Jan 8, 1962

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By D. E. Swets, R. C. Frank

It is well known that hydrogen is introduced into iron or steel as a result of many chemical processes (acid pickling, electrolytic cleaning, plating, etc.). One of the reactions that has been of recent interest1 is the reaction between an iron surface and water vapor. It was shown a few years ago2-4 that hydrogen can be introduced into steel at an accelerated rate during abrasion as a result of this reaction. Grun-berg and Scott have also observed that water in mineral oil lubricants increases pitting failure in ball bearings5 and they have suggested that hydrogen from the water is the primary cause of this effect.' In this laboratory, the question was raised as to whether or not hydrogen is also introduced into the metal surface of a bearing as a result of the decomposition of the hydrocarbon lubricant itself, and an experiment was performed to try to find a satisfactory answer. All steel parts contain some residual hydrogen. Therefore, it appeared that the best way to carry out this experiment without the need for highly accurate quantitative analyses was to use deuterium as a tracer. The natural abundance of deuterium in H2 is only 0.015 pct. The tracer was obtained in the form of deuteroparaffin (CD,(CDJ, CD,) and 0.25 g were dissolved in 20 cc of mineral oil to form the lubricant to be used in the tests. The bearings used were New Departure Type QOLOO ball bearings with a ball diam of 0.187 in. Prior to adding the mineral oil-deuteroparaffin lubricant, the bearings were cleaned in warm trichloroethylene to remove the packing grease. After packing with the new deuterated lubricant, the bearings were operated in a bearing fatigue test machine under a radial load of 190 lb and a thrust load of 190 lb at a speed of 3800 rpm. The expected life under these conditions is about 500 hr. Two tests were made; one for a period of 27 hr and the other for a period of 102 hr. The bearings achieved a temperature of 120o F during the tests. When the tests were stopped the balls were mechanically removed from the bearings and were immediately placed in liquid nitrogen to reduce degassing until the analysis for deuterium could be made. Before analyzing, the balls were warmed to room temperature and scrubbed with several degreasing agents to remove all traces of the deuteroparaffin mixture. This cleaning procedure was shown to be satisfactory by running a control test in which one ball bearing was subjected to all parts of the test except running in the fatigue machine. The hydrogen and deuterium were removed from the balls using a hot extraction apparatus attached to a mass spectrometer. Four balls from each bearing were analyzed. Each one was analyzed separately by removing it from a cold storage volume of the hot extraction apparatus and transferring it to the oven tube with a magnet. As the gases were evolved they were analyzed with the mass spectrometer. Since the hydrogen and deuterium pass through steel in the atomic form and since there are many more hydrogen atoms than deuterium atoms in the sample, the probability of forming an HD molecule is greater than forming a D2 molecule. For this reason the evolution of HD and H was followed as each ball was placed in the oven. The results showed that as each ball from the test bearing was dropped into the oven, the mass spectrometer recording of the HD evolution increased by about ten divisions. When balls from the control test bearing were dropped into the oven, the increase was about one division or less. The hydrocarbon background in the mass spectrometer was also monitored to see if hydrocarbons or deuterocarbons were given off when the balls were dropped into the oven, but no change in the hydrocarbon peaks was observed. Since the balls contained a fair amount of residual hydrogen, isotope ratio measurements were made on the gas obtained from each ball. The D/H value found for those balls which had been operated in the fatigue testing machine was consistently about 0.3

Jan 1, 1962

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

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

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

Jan 1, 1968

By S. S. Clarke

LATE in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls Were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1947