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By R. W. Smith

The Bureau of Mines is engaged in systematic evaluation of the thermodynamic properties of combustion gases. These studies are designed to provide basic thermodynamic information of high accuracy that will facilitate the theoretical study of flame and combustion phenomena. This report is the second of a series3/ presenting results of the study for particular fuel-oxidant sys tans. These calculations had as their objective evaluation of the constant pressure flame temperatures of methane-air and propane-air flames at atmospheric pressure as functions of the mixture ratio and inlet temperature of the fuel-air stream.

Jan 1, 1953

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By Ruddle R. W.

Although copper has been smelted for many years, relatively small attempt has been made in the past to examine the fundamental physical chemistry of the processes involved. Therefore, technological developments apart, slow progress has been made with the development of improved or new principles of smelting. The methods at present in use in the majority of the world’s smelters are essentially those employed at the beginning of the present century; it is significant that many of the textbooks on copper smelting, written some 50 years ago, are still regarded as standard works. The book is divided into seven chapters. In the first the fundamentals of modern smelting processes are briefly outlined for easy understanding of the subsequent sections, while the next two chapters are confined to the more theoretical aspects of the constitution of mattes and slags. Some problems of considerable practical importance are discussed in the remaining four chapters; these are (1) magnetite formation, (2) copper losses during smelting, (3) the recovery of sulphur from the smokes produced during smelting, and (4) the elimination of impurities. A collection of thermodynamic data relevant to copper pyrometallurgy is presented in an appendix, and, for the convenience of readers not well acquainted with thermodynamics, a brief explanation of the thermodynamic terms and methods employed is given in a second appendix

Jan 1, 1953

Jan 1, 1953

By Walter C. Smith, O. J. Seeds

METALLIC bismuth was known in the Middle Ages and the name is supposed to come from the German Wismut. The origin of the German name is uncertain. References to bismuth are found in the writings of Valentine, Paracelsus, and Agricola between 1450 and 1550. Early specimens of bismuth were very impure and often were confused with antimony, tin, and zinc. About the middle of the eighteenth century, J. H. Pott, C. J. Geoffroy, and Torbern Bergman succeeded in producing fairly pure bismuth and showed it to be an elementary metal similar in many respects to lead. H. S. Washington has estimated that bismuth occurs in the earth's crust about as abundantly as tungsten and silver; i.e., to the extent of 10-6 or 10-7 pct. It is found as native metal, both alone and associated with tin, copper, and other metals, and in a large variety of ores. The important ores are the sulfide (bismuthinite), the oxide (bismite), and the carbonates (bismutite and bismutosphaerite) . Other occurrences of bismuth are in the vanadate (pucherite), the selenide (guanajuatite), the telluride (tetradymite), and in many complex sulfides, arsenides, and antimonides. Bismuth minerals have been found in many parts of the world but very few of the bismuth deposits have been of economic value, the oxide ores from parts of China being the exception. The major portion of the bismuth production of today is the so-called by- product bismuth. Bismuth often occurs in ores mined and treated primarily for other metals, and during the treatment of these ores

Jan 1, 1953

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By John B. Gayle

The probable inadequacy of physical tests of coke for the purposes for which they are made has been a subject for discussion for many years. However, little has been published in this connection, even though most workers in the field believe that the physical properties of coke are of major importance in its utilization in the steel and allied industries. In fact, the reproducibility of the recognized tests is largely unknown or can only be approximated. This situation occasions many difficulties when attempts are made to judge the coke-production qualities of various coals or coal blends. During World War II the Coke Production Committee, composed of representatives from industry and the Solid Fuels Administration, concluded that study of existing testing methods and possible improvements would be of material assistance in answering questions relating to coke quality. Since that time the Bureau of Mines has taken samples of coke produced in industrial slot-type coke ovens in connection with studies aimed at extending coking-coal reserves by adding to the list of sources known to be suitable for this purpose. Testing procedures on these cokes were arranged so that the data obtained would yield information on (1) the degree of precision of tests commonly used in the industry, (2) the causes of the known poor reproducibility in several of the physical tests, and (3) possible improvements or modifications of existing physical testing procedures.

Jan 1, 1953

By M. A. Elliott

Diesel-powered haulage equipment has recently been tested and approved for permissibility by the Bureau of Mines for use in mining in the United States. Achievement of this advance in safety involved extensive studies, both in the testing station (2, 3, 20, 21, 22, 23, 24, 25, 26, 27)3/ and in the field 1, 4, 13, 30), of the operating characteristics of diesel engines in relation to the toe of such engines underground. The results of these studies formed the basis for establishing the requirements that should be met by diesel-powered haulage equipment approved for permissibility. Considerable interest has been manifested in the development of diesel-powered haulage equipment fur mines. The purpose of this paper is to retrace briefly the course of this development and to answer such questions as: What is the history of the use of diesel engines underground? Why has the Bureau of Mines been interested in the development of diesel-powered haulage equipment for use in mines?

Jan 1, 1953

By Robert I. Jaffee, Walter L. Finlay

IN the broad survey of the nonferrous' metallic elements contained in this book, the reader may well be impressed by the wide range of property combinations offered by the many metals and alloys the metallurgist has prepared since before Kubla Khan. The diversity is great and the overlap is considerable. It is particularly surprising, then, to find the latest structural metal new- comer designated by such extravagant terms as "Cinderella Metal," "Wonder Metal," "Miracle Metal," "The Metal of Tomorrow," "Dream Metal or Nightmare?" and "The Middleweight Champion of the Structural Metals." Of these and others, the most appropriate designation for the metal involved, titanium, appears to be that of The Middleweight Champion. Its intermediate density of 4.5 and elastic modulus of 16 million is a unique combination between the lower density and modulus of magnesium and aluminum and the higher density and modulus of copper, nickel, and iron. It is light, strong, ductile, and corrosion resistant. A chemical neighbor in group IV of the Periodic Table, zirconium, is similar to titanium in many respects but is appreciably denser, 6.5 instead of 4.5, less stiff and relatively much less abundant. On the other hand, the resistance of zirconium to acids and alkalies is better than that of titanium. Also, compensating for its higher density, lower stiffness, and somewhat lower strength level compared with titanium, zirconium has much better permeability to slow neutrons and is much more suitable as a material of construction for nuclear reactors.

Jan 1, 1953

For the convenience of those who are unfamilar with thermodynamics, the following brief description and explanation is given of the thermodynamical terms and methods used in this book. It must, however, be strongly emphasized that the account given below is not an introduction to chemical thermodynamics; its sole purpose is to give the reader a rough understanding of the methods used in the earlier chapters. For further information, reference must be made to the standard textbooks on chemical thermodynamics by Glasstone.

Jan 1, 1953

By Donald Carlisle

"IntroductionTHE OPINION is held by many persons outside the mining industry, and by some within it, that mine •operators customarily find it advantageous to mine •only the richer parts of orebodies and to leave behind, perhaps permanently, leaner material which could be mined only at a lesser profit. This opinion and the inference which might be drawn from it that 'gutting' of mineral resources is a common feruture• of the mining industry are prejudicial to the intertsts of the industry and deserve careful scrutiny. Oddly enough, a theory of mine economics which gives much support for the opinion was advanced first by members of the mining profession itself, has been repeated •several times in mining literature, and to my knowledge has never been adequately refoted.According to the theory, selective mining of the rich ore first on a large scale will yield substantial gains and these gains do not merely reflect the desire of 'money minded investors' for a quick return but derive from the logical application of compound interest rates and the concept of ;present value. W. O. Hotchkiss and R. D. Parks (1) illustrate the reasoning with a hypothetical example in which an orebody of 4,000,000 tons may be mined either in its entirety in forty years at $1.00 per ton profit or selectively with the recovery of only the richest half in twenty years at $1.50 per ton profit. They show that, with Hoskold rates of 4 and 8 per cent, the present value of profits from mining only the richer 2,000,000 tons exceeds the present value of profits :from mining the whole orebody by about 20 per cent."

Jan 1, 1953

By John V. Beall

IKE'S amiable expression and apparent sincerity impressed AIME members as did the theme of his talk. Cautioning against the gradually increasing power of the federal government, he said: . . . "freedom as we know it is in no greater danger from without than it is from our own lack of understanding of this creeping paralysis from within." Next February, it will be three years since he uttered these words at Annual Meeting welcoming ceremonies, but the theme was oft repeated in his winning campaign. This brush with the exalted, brief though it was, makes Washington look friendlier to many AIME members than it has for years.

Jan 1, 1953

By W. L. Crentz

Before Korea was partitioned along the 38th parallel following World War II, the coal fields of South Korea, with the possible exception of the Samchok area, were not considered important to the industrial needs or Japan or Korea. Much of the demand for electric power in South Korea was met by hydroelectric installations north of the 38th parallel. Following cessation of hostilities between Japan and the' Allied nations in 1945, hydroelectric power continued to flow into South Korea from the north until 1949, when the North Koreans severed the power lines into South Korea, thereby forcing that section of the country to depend almost entirely upon coal to generate electric power.

Jan 1, 1953

By Wilhelm Flesch

THE object of development work in the field of gasification is to find a process by which all' fuels, regardless of their individual properties, can be gasified economically. This paper describes the development of the Winkler process. The economy of the gasification process depends not only on the degree of the gasification effect but also, to a decisive extent, on the costs of fuel, production, and installations. Fig 1 shows the relation between fuel costs and gasification efficiency for various types of fuels. Since the fuel cost in the gasification of coke amounts to two thirds of the price of gas, and the thermal unit in brown coal costs only one third of what it costs in coke, it is easily seen how profitably cheap fuels can be gasified, especially if these fuels require minimum preparation and gasification is done in the vicinity of the mines. These possibilities were a great advantage of the Winkler generators, which were installed 20 years ago in the central German brown-coal fields and, at that time, were without rival for the gasification of finely divided fuels. In the Winkler generator (Fig 2), crushed and ground solid fuels were, for the first time, successfully gasified with oxygen and steam on an industrial scale. Unlike the usual processes formerly employed on an industrial scale, this gasification, which proceeds continuously in the glowing, seething fuel bed, makes only extremely low demands on the fuel. The fuel no longer has to be in lumps and abrasion-resistant, but must be capable of reaction and must be fed into the generator in a grain size of 0 to 8 mm. Brown coal or bituminous coal, or their low-temperature cokes, can be gasified in the Winkler generator. Large plants using fuels are operating on an industrial scale in Europe and in Japan. Table 1 shows the results obtained by gasifying these, fuels in Winkler generators. The thermal efficiency of gasification, which is the relation between the calorific value obtained in the gas produced and that of the fuel consumed, gives no indication of the quantity of steam generated in gasification. The generation of steam in the waste-heat boiler of the Winkler generator adequately-covers the steam consumed in gasification. To obtain effective gasification in the Winkler process, combustible mate-

Jan 1, 1953

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By C. E. Wyndham

The occurrences of manganese In Alabama were reported to be widely scattered over the northeastern section of the State, and these were examined before a development project was started.2/ The most promising and available showings were chosen for further investigation, which include 1 deposit in Goshen Valley, 6 in the Rock Run area, and 2 in the northern section of Calhoun County. The work was performed by the Bureau of Mines from July 29, 1949, to February 17, 1950. The work consisted of power auger drilling 69 holes 3-1/2 inches in diameter and totaling 2,548.4 linear feet. The accuracy of samples from auger drill holes in this type of deposit was determined by sinking two shafts a total depth of 68.17 feet, from which channel samples were cut. Sixteen rotary core holes totaling 1,048.7 linear feet were drilled with a 3-inch, double-tube core barrel. Twenty-two diamond core holes were drilled with a 2-1/8-inch, double-tube core barrel and NX diamond bit. In addition to the above drilling 220.8 cubic yards of soil and rock was excavated by hand from 403.9 linear feet of trenches and 69.7 feet of test pita. A total of 206 samples were taken and analyzed for manganese, iron, cobalt, nickel, and insoluble.

Jan 1, 1953

By Alan U. Seybolt

UNLIKE its sister elements, columbium (niobium) and tantalum, vanadium has not been available until recently in fabricated form. While Vanadium Corporation of America has offered the metal in fairly pure form for sale for many years in small lots for research purposes, this grade of vanadium has been brittle, probably because of a high oxygen content. Hence, when in 1950 the announcement1 was made that wrought vanadium was available as a commercial material, this represented a large step forward in the metallurgy of vanadium. While vanadium is generally regarded as a rare metal, data on its occurrence in the earth's crust show it to be as abundant as copper, zinc, and lead combined. Vanadium is widely distributed, but it does not seem to occur in massive deposits except in a few localities, principally in Colorado, Utah, and Arizona, where it is found in sandstone formations, and in Mina Ragra, Peru. Only in Colorado or Peru are ores mined solely for the vanadium content. Ores in the United States are principally carnotite and roscoelite; the former is of particular interest because of its uranium content. It is a uranium-potassium vanadate containing approximately 52 pct of UO2 and 18 pct of V2O5. Production in the United States during the war years averaged around 2000 tons a year, but dropped to 636 tons in 1946. In recent years, ferrovanadium has been selling for about $2.80 per pound of contained vanadium. This suggests that the price of the pure metal will never be as low as $2.80 per pound, but it could

Jan 1, 1953

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953

By E. T. Hayes, A. H. Roberson, M. H. Davies

ZIRCONIUM has been produced on a pilot-plant scale for only a few years, but the potential uses have led a large number of research establishments to engage in a thorough study of the metal and its alloys. The work described in this paper is part of a cooperative project between the Bureau of Mines and the Air Materiel Command. The Zr-Cr system was one of the first investigated because of the possibilities of improving the properties at elevated temperatures, the chemical corrosion resistance, and the mechanical properties of zirconium in a manner similar to the enhancement of the properties of titanium by additions of chromium. There is no published work on the Zr-Cr system but from the similarity of the metals involved it was expected that it would be similar to the Zr-Fe' and Ti-Cr' systems. The materials used in this investigation were prepared in the Bureau of Mines laboratory at Albany, Ore. Zirconium was produced by magnesium reduction of zirconium tetrachloride, and a typical analysis is as follows: Fe, 0.06 pct; Ox, 0.08; N?, 0.01; C, 0.02; and other impurities such as Al, Pb, Ni, Ti, and Si less than 0.01 pct each. High purity chromium was prepared by treating crushed electrolytic chromium in a stream of dried and purified hydrogen." The resulting powder contained about 0.01 pct 0 and about 0.1 pct total metallic impurities. All alloys were prepared by arc-melting 50 g briquetted compacts of the desired composition in a Kroll-type" arc furnace using an inert atmosphere. The furnace was evacuated twice and backfilled with helium, which was gettered by melting a center zirconium button immediately before the alloys were melted. Alloys were remelted at least once to insure greater uniformity of composition and subsequently were annealed in vacuum at 1250°C for 48 hr. Fairly homogeneous alloys were obtained by this means; a slight loss of chromium from the surface by evaporation during the high temperature homogenization was noted. All alloys were analyzed for chromium and gave results in good agreement with the nominal composition. Spot checks on tungsten and nitrogen showed pick-up of these elements to be negligible. Over 70 alloys were prepared for use in this investigation; only the critical ones are shown in Table I. Alloys containing up to 10 pct Cr were amenable to hot working at 850°C and a number of these were sheath rolled to 1/16 in. thickness. Specimens were cut from the sheet for use as metallographic samples. For the thermal analysis a differential couple was used in conjunction with an X-Y recorder, the temperature of the specimen and the difference in ternperature between it and the standard nickel body were recorded simultaneously. Heating and cooling rates of 5°C per min were used. The sensitivity of the instrument was such that a difference in temperature between the specimen and standard equivalent to 0.1 mv produced a deflection of 1 in. on the recording chart. The chromel-alumel thermocouples were checked against a Bureau of Standards calibrated thermocouple. Melting-point determinations were made in a high vacuum induction furnace using an optical pyrometer. The pyrometer, calibrated against nickel, copper, and zirconium (iodide process) under near black body conditions, was focused on the base of a hole drilled in cylindrical samples. A North American Philips Geiger counter X-ray spectrometer was used for all diffraction studies. This instrument, in addition to supplying precise intensity measurements of planar reflections, has an added advantage in that metallographic specimens mounted in bakelite can be used directly, and this

Jan 1, 1953