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By Joseph Singewald

I. THE GENESIS OF THE DEPOSITS THE ore deposits at Firmeza have been worked continuously since 1884; those at Daiquiri since 1895. It is surprising, therefore, that they have not been the object of careful geologic study until quite recently. It is true that considerable attention was paid to these deposits by A. C. Spencer, in 1901, in the report on the geology of Cuba, by Hayes, Vaughan, and Spencer,1 but this was only incidental to a hasty general reconnaissance of the Island. As far as the Daiquiri deposits are concerned, this gap has been filled by the appearance of the two papers by Prof. James F. Kemp2 and by Prof. Waldemar Lindgren and Clyde P. Ross respectively.3 Max Roesler, first holder of the Emmons fellowship, made a detailed study of the Firmeza deposits during the past summer, so that soon we can expect a full description of them. Consequently, there is no. demand at the present time for a description of the deposits from other sources, rind that is not the purpose of this paper. The papers on Daiquiri, however, leave unsolved problems in regard to the age of the rocks of the district and certain phases of the genesis of the deposits, and it is with the. hope of aiding in the solution of some of these problems that this contribution is offered. Kemp, and Lindgren and Ross agree in assigning these deposits to the type of contact metamorphic deposits. They disagree in part on the question of their localization. The deposits occur in an extensive area of diorite which includes numerous blocks of limestone, and some-

Jan 3, 1916

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969

By M. H. Caron

THE most outstanding property of ammonia liquors, used in the ammonia leaching process is their very limited ability to dissolve all compounds present in reduced ore except nickel and cobalt. Although they do have such a high degree of purity, even the smallest amounts of impurities contaminate the precipitate of basic nickel carbonate that may be obtained from pregnant liquors by straight distillation. Figures have been given in a separate paper regarding the extent of such contamination. The product of straight distillation is likely to contain small amounts of Fe, Mn, MgO and SiO2 as well as some sulphate and sulphide. The sulphur can be readily eliminated by calcination of the product at the proper temperature and MgO and SiO2 by reduction and melting of the metal with a suitable flux. After such treatment the metal is relatively pure, and the iron and manganese content will be very small. The cobalt content, however, may vary considerably, depending upon the ore treated. The metal obtained from pure true garni-erite ores usually has only a small cobalt content of less than 1 pct. Metal obtained from medium grade iron-rich nickel ores may show cobalt values from 2 to 3 pct, and the alloy obtained from laterite is likely to contain as much as 10 pct cobalt. By proper treatment a good deal of cobalt may be recovered from lateritic nickeliferous iron ores, and cobalt will become the major constituent of the pregnant liquor if asbolan ores or similar products are treated. The pregnant liquor of "run of mine" nickel ores may have a pinkish shade, indicating the presence of cobalt. It is evident that from such liquors the metals should be recovered separately. Even if cobalt is present in only very small amounts, it would probably be economically justifiable to recover both metals as pure as possible if a suitable process could be devised. The author has made investigations along this line and has patented some processes adapted to the treatment of this type of solutions. Selective Dissolution of Nickel from Basic Nickel Carbonate Containing Some Cobalt: Basic nickel carbonate obtained from true garnierite ores by straight distillation of the pregnant liquors, always contains some cobalt as well as the normal impurities. In. order to improve the quality of the nickel product and to recover most of the cobalt, the following process has been devised. By using liquors with a low CO2 to NH3 ratio, nickel can be redis-solved preferentially to cobalt. It is not a sharp and clean separation but a selective one, for the bulk of the nickel may be redissolved with a small amount of cobalt, and a small residue may hold the bulk of the cobalt. The greatly increased cobalt content of the residue is indicated by a pronounced olive green color, in contrast with the light green color of pure basic nickel carbonate. The following example is given from Dutch patent No. 52788, Klasse 40a. 43 granted June 17, 1942: The original precipitate contained about 0.55 pct cobalt calculated on total nickel + cobalt. Eight hundred and fifty grams of the basic nickel carbonate were redissolved in leach liquor containing 7.12 pct NH3 and 2.12 pct CO2. The weight of the dry residue was about 3.5 pct of the original weight. By analysis it was found that the residue contained: Fe 1.93 pct, Co 6.01 pct, Ni 34.87 pct and also a certain amount of silica. The clear filtered blue liquor was distilled and the precipitate of basic nickel carbonate from this analyzed: Fe 0.008 pct, Co 0.0146 pct, Ni 42.37 pct. It is obvious that this product is considerably more pure, since calculation shows that about 94 pct of the original cobalt remained in the residue. Cobalt and nickel can be recovered by further

Jan 1, 1951

By Richard H. Hopkins, R. W. Kraft

A new technique facilitating the rapid determination of the three-dimensional morphology of phases suspended in an opaque matrix is described. The vapidity of the technique is based upon continuous cinephotomicrographic recording of specimen microstructure as the specimen surface is removed under controlled conditions in an electrolytic cell. The advantages of the technique for determining spatial morphologies in opaque materials are illustrated by application of this method to the study of the configuration of faults in a specimen of directionally solidified CuAl2-Al eutectic alloy. A spatial model of the eutectic fault network deduced in this manner has substantiated the facts that faults in this alloy tend to lie parallel to one another in a direction close to that of the specimen growth axis and that the majority of faults tend to bridge lamellae rather than run parallel to them as growth proceeds. For the specimen studied fault density decreased as growth proceeded. ALTHOUGH metallographic observation is a powerful tool for investigating the correlation between structure and properties in metallic alloys, ordinary metallographic methods suffer the fundamental limitation that any conclusions concerning the three-dimensional structure of these opaque materials must rely upon inference from two-dimensional microsections. For this reason it is frequently impossible to make valid judgments regarding the true spatial distribution of the micro-constituents in specimens under investigation. Several techniques have been devised to circumvent the basic limitation of planar microsec-tioning and employed with varying success. These include construction of three-dimensional models of alloy microstructure from sequences of photomicrographs,1-3 quantitative deduction of spatial features based upon statistical studies of data from random and/or selected plane microsections,4-6 and selective dissolution of one phase in a two-phase alloy to reveal the topography of the phase remaining.' However these techniques also have certain obvious disadvantages. Construction of three-dimensional models is a very time-con- suming procedure due to the tedious polish-etch-photograph cycle needed to obtain the necessary photomicrographs to portray the spatial microstructure. Statistical methods by their very nature give only average values of the quantities being studied and cannot therefore give a detailed physical picture of the microstructure to be observed. Finally, the technique of selective dissolution is only applicable in systems where the phases are of vastly different chemical reactivity; it is of little use in the study of single-phase alloys. Since the determination of the three-dimensional structure of opaque materials is hindered by two facts—the materials are opaque to radiation in the visible spectrum and construction of spatial models of microstructure is quite laborious—two solutions to the problem suggest themselves: 1) use radiation of energy great enough to render the alloy transparent, i.e., some microradio-graphic method, or, 2) devise a rapid means to section and record alloy microstructure. Stereomicroradiography has indeed been used to study internal arrangements of phases in several materials8,9 but the method, in general, is limited to very thin specimens (due to X-ray absorption) and simple microstructures. It would seem then that development of a rapid, simple, and generally applicable technique for studying the details of alloy microstructures in three dimensions can best be undertaken by following the second approach above. Using this idea a new technique for rapid evaluation of spatial microstructures was developed based upon cinephotomicrographic recording of the micro-structure of a specimen undergoing controlled electrolytic dissolution. It was further felt that application of this technique to the careful study of the spatial configuration of faults in a CuAl2-Al eutectic alloy would yield information that could be correlated with the extensive data3,6,10-12 already compiled concerning the solidification and crystallography of this eutectic. The practicality and usefulness of similar methods for studying three-dimensional features in alloys has recently been illustrated by the study of dislocation loops in zinc13 and spheroidized structure in steel.14

Jan 1, 1965

By H. E. Lee, P. C. Feddersen

Greenockite is the only known cadmium mineral of importance. It occurs rather universally, in minor concentrations, as a secondary mineral in sphalerite deposits. The world's cadmium output is obtained through the processing of metallurgical by-products, largely from the treatment of residues from electrolytic zinc, retort zinc and lithopone plants. These sources are supplemented by the processing of fumes from lead and copper smelting operations. The development of modern selective flotation practice in the decade 1920-1930, which permitted the economical mining of complex lead-zinc ores, resulted in significant increases in the quantities of cadmium entering lead smelting systems. Being closely related to zinc as to occurrence, properties and production, most detailed description of cadmium recovery methods are to be found recorded in connection with zinc metallurgy. Other than occasional articles pertaining to particular operational procedures, literature offers but little in the nature of a balanced survey of lead smelter cadmium recovery practices. While many of the basic operations described for the recovery of cadmium from zinc by-products are applicable to the treatment of lead plant products, the inherent problems involved differ widely. In general the cadmium content of related by-products from routine lead smelting operations is present in lower concentrations, exists in a less soluble state and is associated with both a greater quantity and a greater variety of detrimental impurities. To cope with these problems, lead smelter practices are found to follow the general outline: Preparatory Processing 1. Concentration operations 2. Sulphation operations Cadmium Plant Processing 1. Leaching operations 2. Purification operations 3. Sponge precipitation operations 4. Metal recovery operations 5. Refining and casting operations As in the case of related zinc plant operations, cadmium recovery practices at lead smelters are not standardized. They not only vary as to type, but also extent. Depending upon prevailing conditions, lead smelter cadmium operations range from simple concentration campaigns, for the purpose of sufficiently "up-grading" products for shipment elsewhere, to complete processing steps for the production of refined metal. Preparatory Processing The cadmium content of lead smelter receipts is low and, as a rule, proportionate to the zinc content; the usual range of cadmium contained being of the order of 0.01-0.05 pct. Were it not for the low boiling point of cadmium, such small concentrations would, no doubt, be lost in the large tonnages of slag, metal and other smelter end products. However, the ready volatility of cadmium and its compounds at prevailing lead smelting temperatures results in its concentration in fractional portions of fume collected. This collected fume comprises a circulating load within the smelter system. Thus, the cadmium content of blast furnace fume* increases with each successive circulation until an equilibrium value is reached when the sum of the cadmium losses, due to handling and in slag, waste gases and other end products, becomes equal to the intake as ore. With ore receipts averaging, say 0.03 pct cadmium, the concentration value obtainable, through fume circulation in a routine manner, approaches 10-12 pct. In such operations, cadmium concentrations in blast furnace fume of from 3-5 pct are readily .attainable. However, the concentration gain beyond this range, with each additional circulation, is progressively decreased as a result of mounting losses occurring through handling and in end products. Therefore, to avoid excessive cadmium loss and to enhance the ultimate concentration anttainable, it is customary practice to isolate blast furnace fume at some intermediate cadmium content for special concentration procedure. The most common type cadmium concentration "campaign" involves special smelting operations wherein a relatively high portion of blast furnace fume at 3—6 pct cadmium is incorporated into the sinter charge. This type practice is roughly illustrated by the diagram on p. 111. Cadmium fume collected from lead blast furnace operations is not amen-

Jan 1, 1950

By A. Styka, G. Fischer, S. Tour

Described herein are the results obtained during research work involving coating titanium alloys with molybdenum by vapor-deposition methods. Results show that the method can be used successfully to deposit hard adherent wear-resistant coating of methodmetallic molybdenum on titanium or titanium alloys without changing the microstructure of the titanium base. PRODUCTION and use of titanium and its alloys have increased tremendously in the past few years. The physical, mechanical, and chemical properties of this engineering metal have caused considerable enthusiasm among metallurgists and engineers. However, as with all materials, there are some drawbacks. For example, titanium is susceptible to seizing and galling on wearing surfaces. In order to produce a good wear-resistant surface, many investigations have been conducted evaluating oxidizing, carburizing, nitriding, carbonitriding, sili-conizing, and chromizing of titanium. All of these processes require high temperatures for rather extensive periods of time. It has been possible to produce hard surfaces on titanium and its alloys by a number of these processes at the expense of a deterioration of the physical properties of the base material. A practical solution to the problem of providing titanium and titanium alloy parts with a satisfactory wear-resistant nongalling surface must be one that does not involve excessive temperatures for long periods of time. Sam Tour & Co. Inc. has completed a research and development contract for the United States Army Ordnance Corps on vapor deposition of molybdenum on titanium and titanium alloys. On the basis of results obtained from the research program, titanium alloys can be coated successfully with molybdenum to provide a hard wear-resistant surface without harm to their base mechanical properties. The remainder of this article is a description of the techniques used to apply the coating and the results obtained from wear tests on molybdenum-coated titanium. Theory Basically, the technique used was the application of molybdenum by a vapor-deposition method, thermal decomposition of molybdenum hexacarbonyl [Mo(CO)] with hydrogen as the carrier gas. The selection of this method was based chiefly on the following considerations: 1—low plating temperature which would minimize excessive grain growth, 2— low decomposition temperature of the carbonyl, 3— possibilities of controlling the hardness of the plate by adjusting the carbon content using the plating temperature and pressure as the primary variables, 4—use of high vacuum, thereby avoiding unnecessary oxidation and other complex reactions with the atmosphere. Free energy data1 show the strong tendency for titanium to combine with O2 N2 or carbon from normal temperatures to temperatures above its melting point. To maintain the titanium in a film free condition, the use of as high a vacuum as possible is indicated. The literature' indicates that the reaction product of hydrogen with titanium is unstable in vacuum at around 400°C. 5—Although it is indicated from the thermodynamic standpoint that there is little possibility of removing carbon from either titanium or molybdenum, the work of Lander and Germer -ndicates that the use of a suitable H,/CO ratio is somewhat effective in minimizing carbon deposition. 6—Availability of molybdenum carbonyl. In the simplest form, the conditions of equilibrium3 in chemical reactions involving decomposition of carbonyl are as follows: Mo (CO) ? Mo + 6CO 2CO * C + CO,. The plating rate is proportional to the rate of evolution of CO from the decomposed carbonyl, i.e., it is proportional to the pressure of the gaseous decomposition products. Carbon released from CO gas is the significant constituent for the variability of the physical properties of the product. High carbon deposition is favored by increasing pressure. Limitations are imposed in the selection of plating temperature and pressure. Excessive temperature re-

Jan 1, 1956

By C. A. Hope, H. B. Wishart

THE number and severity of surface imperfections on rolled slabs, assuming the reception of uniformly good quality heats from the open hearths, depend upon a number of conditions associated with heating and rolling of steel in the primary mills. While there are other elements that have an effect on surface quality, rather than make this paper too lengthy the discussion of mill processing variables will be limited to three factors in order to illustrate their effect on slab surface quality: 1—amount of reduction between ingot and slab, 2—slab finishing temperatures, and 3—influence of roll changes. Measurement of the percentage of surface removed by scarfing on the flat surfaces of the slabs was used for evaluating quality in this study. A study of this nature must be made on slabs that are inspected and conditioned under uniform conditions and standards. In order to be certain that steel of the best possible steelmaking quality was received at the rolling mills, a low carbon deep drawing grade of rimmed steel, made for sheet mill application and manufactured under carefully controlled open hearth practices, was selected. Use of this particular steel thereby reduced the steel quality factor as a possible source of variation. The measure of slab surface quality is the amount of surface removed by scarfing during yard conditioning and is expressed as percentage of surface removal. This percentage was estimated by experienced personnel to uniform standards and it should be noted that these percentage figures are representative only for the grade selected and under the rigid inspection standards to which the slabs were subjected. Surface removal is a matter of concern because the imperfections, if undetected, often are the cause of poor surface quality in the finished product and their removal, by conditioning, add to the total plant costs. The data was collected at various times over a period of six months and, with normal weekly fluctuation in the level of quality, it is to be expected that for any period of sampling there will be some variation in the plotted results. The type of defect that is responsible for most slab conditioning at Gary Steel Works is a light angular surface break. This defect is usually interconnected to form large defective areas and occurs mainly on the bottom half of the slab on both sides. This type of defect is illustrated in Fig. 1, showing a bottom portion of a slab; while a close-up of an area of the same slab where the surface breaks were found is given in Fig. 2. The large dark areas are heat patterns, results of hot stacking and cooling. Independent of these light breaks, but sometimes associated with them, are larger and deeper isolated breaks. However, most of the surface removal occurs from conditioning the large areas of small breaks. There are also occasional scabs of varying degrees of severity but these are relatively infrequent. The slabs are generally free of rolled-in scale. Ingot to Slab Reduction vs Quality Some ten years ago at Gary Steel Works, the minimum slab ingot thickness was 30 in. Subsequent operating and other quality features indicated the desirability of using an ingot of reduced thickness with the result that a series of molds that would produce a 22 in. thick ingot with various widths was adopted as standard. A minimum number of the thicker mold sets are still used. From the standpoint of quality difficulties from pipe and segregation, the smaller ingots are an improvement. From a quality surface viewpoint, the slab product from the thin molds requires approximately twice the surface removal as the slab product from the thick molds. This is shown in Fig. 3 where the percentage of surface removal is plotted against slab product rolled from

Jan 1, 1956

By Howard E. McKinney

A high-pressure wellhead lubricator has been developed to facilitate telemetering electrical measurements from subsurface reservoirs to the surface with the well under normal flowing conditions. The field unit in use at the present time employs a 5/16-in diameter, single-conductor armored cable and is to be used in wells with surface pressures up to 5,000 psi. It has a pressure sealing element that maintains a continuous and absolute seal around the cable as it enters or leaves the tubing at speeds up to 175 ft per minute. A cable injecting device is used which obviates sinker bars or weight sections on the instrument. INTRODUCTION The development of instruments for securing physical measurements in pressure wells has been confined in the past to those instrument which would operate on a wire line and record the necessary measurements in the downhole instrument itself, or those which would operate on an electric cable in a well with the surface pressure killed by the use of weighted fluids or by the use of tubing plugs. In one case the accuracy of the measurements is questionable, and in the other the range of application is very limited. Considerable work has been done by other interests to provide effective means to accomplish the necessary telemetering. The U. S. Bureau of Mines developed a wellhead lubricator prior to 1947 which permitted a 5/16-in diameter single-conductor cable to be lowered into a well with a surface pressure of approximately 500 psi. This unit was used successfully in a number of tests in Oklahoma. A company which tests wells has recently offered on a service basis a wellhead lubricator with a 3/16-in diameter cable that reportedly operates up to 2,500 psi surface pressures. Each of the above operates on a staging principle to effect a seal. In both of these units some leakage of well fluid occurs when the cable is moved. SPECIFICATIONS FOR DESIGN In order to provide the maximum flexibility in its use, the following parameters were established for the design of our high-pressure wellhead lubricator: L An absolute well fluid seal up to 5,000 psi surface pressures. 2. Means for raising and lowering the instrument at speeds of at least 100 ft per minute. 3. Provision for the instrument to enter and leave the well without disturbing the well flow or the reservoir conditions. 4. A cable large enough to provide suitable electrical characteristics and suitable mechanical properties. 5. A method of operation that will not damage the well in any way. The present high-pressure wellhead lubricator field unit fulfills the above requirements. DESCRIPTION OF THE UNIT AND ITS OPERATION The cable selected for this use is the standard Amergraph 1H2 as manufactured by the American Steel and Wire Co. This particular cable is normally used by the Halliburton Oil Well Cementing Co. in their conventional well logging operations. Although the cable presents a noncircular cross-section (Fig. l), its diameter is very consistent; lor example, maximum diameter is 0.325 in., minimum diameter 0.314 in. This [actor permits the use of the sealing element, as later described. Early in the development of the high-pressure wellhead lubricator it was apparent that we could not effect a direct gas seal around a moving 1H2 cable. This becomes evident when an examination of the cable cross-section is made. The voids between the strands of the outer armor provide natural channels lor the flow and escape in large quantities of a low-viscosity fluid such as gas. However, it is relatively simple to

Jan 1, 1952

By P. R. PaeIay, A. Slibar

Using three-dimensional, stress-deformation rate equations for a Bingham plastic, an approximate solution for the laminar flow of drilling mud between the drill pipe and casing is given for the case when the velocity gradients due to axial flow are large compared to velocity gradients due to rotation. INTRODUCTION The fact that drilling mud can be treated, to a first approximation, as a Bingham plastic has been established by several investigators12,3,4,5. A Bingham plastic is a material that is rigid until a certain combination of stresses exceeds a critical value. When the stresses are sufficiently high to initiate flow, the reduced stresses have a constant ratio to the corresponding deformation rates at each point. Prediction of pressure and torque requirements to produce the desired flow of the material have been made by analytical solutions due to Bingham6, Reiner7, and Buckingham8. One part of the present means of calculation that requires clarification is the flow between the drill pipe and casing. Present methods treat the flow resulting from the rotation of the drill pipe separate from the flow produced by the axial pressure gradient. Since the non-linear behavior of a Bingham plastic implies that solutions cannot be superposed, the present analytical investigation was undertaken to obtain a solution to the problem of combined axial and tangential flow. Equations have been proposed for the three-dimensional flow of a Bingham plastic9,10,11 and it has been shown that the proposed equations lead to the usual solutions from the one-dimensional theory". Applying these equations to the flow between two concentric cylinders the problem of axial flow only13 and tangential flow only12 have been solved. In addition to the separate problems of axial and tangential flow between concentric cylinders, the authors have determined the relationship between external torque on the inside cylinder and axial pressure gradient necessary to initiate flow". The solution given in Ref. 14 points out the complexity of the present problem. The problem considered here is the case of simultaneous axial and tangential flow. The axial flow, necessary to keep the drill bit free of removed material, results from the axial pressure gradient. Tangential flow is present since the drill pipe rotates in the hole. The solution given here is valid when the shear stresses in the drilling mud due to rotation are small compared to the shear stresses resulting from the axial flow. This case for laminar flow can be encountered in oilfield drilling. STRESS-DEFORMATION RATE EQUATIONS A detailed derivation of the equations governing the behavior of a Bingham plastic is given in Ref. 10. This section briefly outlines the physical reasoning leading to this three-dimensional formulation of the stress-deforma-tion rate law. Experiments on a certain class of materials have demonstrated the following properties: (1) when a certain combination of the stresses is below a critical value no deformation of the material occurs, (2) to a first approximation this combination of stresses is independent of the hydrostatic pressure (negative average normal stress), (3) if flow occurs the ratio of the reduced stress to the corresponding deformation rate is constant at each point of the flowing material, and (4) incom-pressibility. For the one dimensional case of shear deformation, Bingham6 formulated the governing equation as dxx, = 0 for sxx < to and µdxx = s xx = to for sxx to , . where dxx is the shear deformation rate, sxx the shear stress, to the critical shear stress, and p the slope of the sxx vs dxx curve for dxx > 0. Fig. 1 shows the behavior for pure shear between two parallel plates. Taking into account the physical properties given above and assuming the critical combination of stresses to be measured by the octahedral shear stress, the fol-lowing three-dimensional equations have been proposed.

Jan 1, 1958

By Orville R. Lyons

THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,1 but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."&apos; Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."&apos; It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913,8 by the United States Bureau of Mines in 1938,4 by Hancock in 1947,3 and by the national French research agency Cerchar in recent years.2 In 1950 Anderson&apos; proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or ±0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1952

By R. A. Vandermeer, J. C. Ogle

The preferred crystallographic orientations (texture) developed in randomly oriented, poly crystalline niobium during rolling were studied by means of X-ray diflraction techniques. The evolution of texture at both the surface and center regions of the rolled strip was carefully examined as a function of increasing defamation throughout the range 43 to 99.5 pct reduction in thickness. Certain aspects of the center texture development in niobium are in agreement with the predictions of a theory by Dillamore and Roberts, but others cannot be explained by the theory in its present form. Above 87 pct reduction by rolling, a distinctly different texture appeared in the surface layers which was unlike the center texture. The present results are compared with previous results obtained from other bcc metals and alloys. RANDOMLY oriented, poly crystalline metal aggregates when plastically deformed to a sufficiently large extent develop preferred orientations or textures. In a recent review article, Dillamore and Roberts1 pointed out that the nature of the developed texture may be influenced by a large number of variables. These include both material variables such as crystal structure and composition and treatment variables such as stress system, amount of deformation, deformation temperature, strain rate, prior thermal-mechanical history, and so forth. From a practical point of view, the control of preferred orientation may often be important for the successful fabrication of metals into usable components. During the past few decades many experiments have been devoted to the study of deformation textures. This work, however, has been confined in large part to metals and alloys that have an fcc crystal lattice. By comparison, bcc metals and alloys have received much less attention, and consequently our understanding of preferred orientations in these materials is only shallow. This state of affairs worsens when it is realized that almost all of our present howledge about this class of materials derives from studies on irons and steels.&apos; The bcc refractory metals, which are relative newcomers to the industrial world, have, on the other hand, been given at best only passing glances in the area of texture development. Our understanding of the evolution of preferred orientations in bcc metals can only remain fairly limited until systematic studies of metals and alloys other than the irons and steels have been carried out and the influence of the many variables has been determined. To that end a program was initiated to investigate in detail texture development in niobium. The present paper reports some of the results of this study. Textures were determined at both the center and surface of strips rolled variously to as much as 99.5 pct reduction in thickness at subzero temperatures. Emphasis in this paper is on texture description and on texture evolution during rolling to progressively heavier deformation. EXPERIMENTAL PROCEDURE The niobium was purchased from the Wah Chang Corp. as a 3-in.-diam electron-beam-melted billet. Chemical analysis indicated the impurities to be less than 300 ppm Ta, 40 ppm C, 10 ppm H, 170 ppm 0, and 110 ppm N. All other impurities were below the limits of detection by spectrochemical analysis. This large-grained billet was fabricated into specimen stock so that a fine-grained randomly oriented grain structure resulted. This was accomplished in three deformation steps alternated with recrystalli-zation anneals of 1 hr at 1200°C in a vacuum of low 10"6 Torr range after each deformation step. The first step was to alternately compress the billet 10 to 20 pct in each of three orthogonal directions. The second step was to compress in only two directions 90 deg apart to produce a 2-in.-sq bar. The final step was to roll this bar 50 pct to give a 1-in. by 2-in. cross section. After the final anneal, metallo-graphic examination showed the material to have an average grain size equivalent to ASTM No. 5 at 100 times (i.e., 0.065 in. diam). Specimens cut from the center and edges of this bar gave no indication of detectable preferred orientation when examined by X-ray diffraction. Samples 1.5 in. long, either 0.625 or 0.750 in. wide, and approximately 0.400 in. thick were machined from this fabricated ingot. The surfaces corresponding to the rolling planes were ground so as to be parallel. The samples were chemically polished in a solution of 60 pct nitric acid and 40 pct hydrofluoric acid (48 pct solution) prior to rolling to remove any cold work introduced in the machining operations. Rolling was accomplished with a 2-high hand-operated laboratory rolling mill that had 2.72-in.-diam rolls. Prior to operation, the rolls were polished with 600 grit paper, cleaned with acetone, and then soaked in a container of liquid nitrogen for several hours. The samples were also soaked in liquid nitrogen prior to rolling and were recooled between each pass. While some slight heating of the samples occurred during rolling, this procedure maintained the sample temperature well below 0°C at all times. The samples were rolled unidirectionally, and the rolling plane surfaces were not inverted during any phase of the operation. The draft per pass averaged between 0.010 to 0.012 in. After 96 or 97 pct reduction the draft was reduced to 0.001 to 0.002 in. per pass. Samples were rolled to various reductions in thickness between 43 and 99.5 pct.

Jan 1, 1969

By R. M. Treco

THE thermal expansion of pure beryllium was first investigated by Hidnert and Sweeneyl in 1925 on a single cast specimen stated to be of 98.9 pct purity. A study of the coefficients of expansion by X-ray methods has recently been made by P. Gordon&apos; on powder obtained from the Brush Beryllium Co. assaying 97 wt pct beryllium with about 2 wt pct oxygen as an impurity. The present work pertains to about the highest purity metal obtainable from the Brush Beryllium Co. This metal was in the form of lumps which were remelted and cast in a high-vacuum induction furnace. Expansion data in this paper deal with beryllium extruded into bars of rectangular cross-section 4x1/2 in. and the anisotropic expansivity of a large cast single crystal. Analysis of the cast metal after extrusion indicated a beryllium assay of 99.28 pct. Impurities were 0.170 pct Fe, 0.140 pct Al, 0.014 pct Mg, 0.086 pct Si, 0.020 pct Cu, 0.020 pct Mn, 0.007 pct Ni, 0.007 pct Ca, 0.080 pct C, 0.179 pct 0, (as BeO). Part I—Extruded Metal Thermal expansion measurements were obtained with a fused quartz-tube differential type dilatom-eter3 on specimens cut from the extruded sections in longitudinal and transverse directions. Specimens were machined to a diameter of 0.250 in. and a length of 3.000 in. One sample from each direction was vacuum annealed for 1 hr at 800°C. The dilatometer tube was placed in a vertical tube furnace having a uniform temperature zone which was twice the length of the sample. Average time for a complete thermal cycle to 500°C was 18 hr. Temperatures were observed with two chromel-alumel thermocouples attached to the sample about 1 M in. apart. The accuracy of temperature measure-ment was ± 0.25°C. An argon gas atmosphere sur-rounded the specimen to prevent oxidation of the beryllium. Samples were identified as shown in table I. Results - The original plan included measuring expansion up to 1000°C, but the first two runs on sample No. 5 showed that a permanent contraction occurred from

Jan 1, 1951

By J. R. Mihalisin, J. S. Iwanski

The response of Inconel "700" to heat treatment has been studied by light and electron microscopy combined with X-ray and electron diffraction techniques. A heat treatment which vesults in low ductility for this alloy appears to be associated with the formation of MC carbide in a Widmanstdtten distribution. This type of precipitation can be suppressed by suitable heat treatment with concurrent increase in ductility. Various other phases precipitated in this alloy are also identified. RECENT studies of commercial nickel base su peralloys have demonstrated the importance of the morphology of carbide phases upon physical properties.&apos; For example, empirical heat treatment studies applied to Nimonic "80" and Inconel "X" have resulted in prescribing double aging treatments for optimum physical properties. These treatments have subsequently been related micro-structurally to grain boundary carbide morphology.2 The purpose of this study was to obtain information about the morphology and identity of some of the phases precipitated in Inconel "700" after heat treatment. It was hoped that some correlation could be made of micro structure with heat treatment similar to that observed with Inconel "X" and Nimonic "80." EXPERIMENTAL PROCEDURE Specimens were obtained from a hot-rolled bar of Inconel "700" of the following composition: C Mn Fe S Si 0.10 0707 0.42 0.007 0.12 Cu Cr -A1 -Ti- Co Mo Ni 0.02 -14.90 TM 2.22 27.61 2.92-- Bal. Specimens were prepared in the following heat-treated conditions: (A) 2275°F for 2 hr WQ (B) 2275°F for 2 hr WQ + 2000°F for 1 hr (C) 2275°F for 2 hr WQ + 1600°F for 48 hr. (D) 2275°F for 2 hr WQ + 2000°F for 1 hr + 1600°F for 48 hr. Empirical stress-rupture studies had shown that treatment (D) resulted in optimum stress-rupture life and ductility. Treatment (C), although giving a good aging response, resulted in low ductility. Treatments (A) and (B), respresenting individual. steps in treatments (C) and (D) were added here for microstructural comparison studies. The procedure was to make an optical and electron microscopic investigation supplemented by X-ray diffraction analysis of electrolytically extracted residues. Electron diffraction studies were made utilizing selected area diffraction techniques with extraction

Jan 1, 1960

By Albert B. Horn, J. J. McKetta, O. L. Culberson

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry&apos;s Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- &apos;References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the

Jan 1, 1950

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-&apos;. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.&apos; The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By Leonard C. Grimshaw

The idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a composite steel. Previous Methods There are two methods in use that result in tolerably good bonds between ferrous metals: (1) the casting method, and (2) what we shall call the "heat-pressure" method. This "heat-pressure" method covers processes in which the bond is made between two prepared surfaces by heating them and then applying pressure. Usually sufficient pressure must be used to produce appreciable spread and elongation, or else we arc merely brazing and not truly welding. Casting methods for welding together ferrous metals have been used more than 74 years, and are described in the technical literature as applied

Jan 1, 1936