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By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

By E. F. Poncelet

Forty years ago A. A. Griffith developed a theory explaining why brittle materials displayed such low tensile strengths.' He based his views on two points. First, he found himself compelled to assume that all brittle materials are replete with flaws, cracks, and other defects that act, although quite invisible, as large stress raisers. Second, he applied the "theorem of minimum potential energy," which says that the total potential energy of a system must pass from the unbroken to the broken condition by a process involving a continuous decrease in potential energy. By this means he satisfactorily accounted for the noted low strength of such solids and also for the wide spread obtained in experimental measurement of these strengths. So successful has the theory been that it is favored by some to this day. Unfortunately this theory is of limited use beyond the explanation of these two noted phenomena and it is keenly felt that a better theoretical insight into the physics of the fracturing process is needed as the volume of experimental evidence accumulates. The author proposes in the following to build on the fundamentally sound concepts of Griffith and, with the help of increased theoretical knowledge over that available to Griffith, develop a mechanism for frac-ture which will provide far greater understanding of the experimental evidence accumulated to date than is possible from the original Griffith idea. THE GRlFFlTH THEORY Very little progress indeed can be made without accepting the first postulate of Griffith which supposes all brittle solids to be full of microcracks. It would be difficult indeed to find a better mechanism for the small strength of such brittle materials, in conjunction with the fact that the energy that must be expended for comminution is by no means small. The postulate of the existence of the microcracks permits the breakup of the various bonds a few at a time by concentrating the stress at the tip of the progressing crack, while the total energy expended is the same as if they all had been ruptured simultaneously. The only flaw in the argument is that no reasonable explanation has been proposed to account for the genesis of such cracks. Indeed their very presence is in violation of the Griffith second postulate, the potential energy theorem. This theorem is straightforward for isothermal processes, and, in spite of Griffith, there is some doubt that treating the problem isothermally is legitimate. The surface energy of bodies is a free energy, not a potential energy as stated by Griffith, and the production of new surface free energies is not necessarily an isothermal process. There is ample evidence to the contrary. Generally speaking, if heating a body increases its surface area, then, by virtue of Le Chatelier's principle, any increase of that area by other means will tend to lower its surface temperature. Lord Kelvin calculated the actual cooling that resulted in drawing out a film of liquid.2 R. A. Houston calculated the surface cooling that resulted in stretching a metal wire.3 These calculations were made by applying the Carnot cycle to the process and evaluating the thermodynamics thereof. IRREVERSIBILITY OF THE FRACTURING PROCESS While Griffith was very careful not to say so, the impression gained from studying his papers is that he considered the fracturing process as reversible, that is, a succession of quasi-equilibrium states. There is ample evidence that it is not. The indication that the new surfaces produced by the propagation of a crack are cooler than the original body points to an irreversible heat flow from the interior to the new surfaces to equalize the temperatures. If the process be reversible, any crack accidentally formed should immediately close up as, in the absence of any strain energy, the potential energy would thereby be lowered. The fact that they do not, constitutes a paradox. Such paradoxes are nothing new where certain phenomena that propagate from minuscule nuclei are assumed to be reversible. Such is, for instance, the condensation of a pure saturated vapor that is suddenly chilled by adiabatic expansion. At the beginning the tiny droplets that are formed should be only a few angstroms in size, but the vapor pressure at such droplets is so high that they should evaporate at once. A similar situation arises if a saturated pure solution becomes super-saturated upon cooling; the first tiny crystal nuclei should dissolve as fast as

Jan 1, 1964

By O. B. Buchlen, J. W. Smith

The Coal Research Bureau of the School of Mines at West Virginia University, using an experimental flotation cell designated an airlift-cyclone was able to obtain a clean coal product containing 7.64% ash with 94% yield and 97% coal recovery. This favorable performance was obtained with the experimental flotation cell operating as a simulated three-stage unit on slurry taken from the fine coal circuit of a coal preparation plant. This experimental device, consisting of a sheet metal cyclone-like unit mounted on a U-shaped uplift pipe, uses a combined flotation and cyclone action to beneficiate the minus 14 mesh partially cleaned feed product. In addition to providing comparable analytical results, the airlift-cyclone possesses other attractive features among them being a low capital expenditure, utilization of moderate plant floor space, efficient operation on high density feed slurry, and absence of moving parts. The primary shortcoming of the experimental cell is its limited capacity. The Coal Research Bureau presently has under construction a larger unit which, it is hoped, will provide the capacity and quality to establish the airlift-cyclone as a commercially feasible unit. Froth flotation of fine coal is a practice which has only recently gained wide acceptance in this country. Various explanations can be put forth for this delayed acceptance of a very selective and efficient system of coal preparation. Among these reasons would be the advent of continuous mining machines resulting in the increased production of coal fines, the change in market patterns from domestic and rail consumers who did not want fines to a predominantly utility market which normally consumes fines, and also the imposition of legal restrictions in regard to stream pollution. However, the major detriment is probably the high cost involved both in installation and operation of the flo- tation unit and auxiliary systems. These facts assume greater emphasis when considering that froth flotation installations normally process a low quality feed product. A recent estimate' of installation costs including dryers, filters, and other auxiliary equipment for a flotation system was $5000 to $7000 per ton of capacity while the operating costs, exclusive of auxiliary equipment, were estimated at 10 to 306 per ton of feed. The Coal Research Bureau of the School of Mines at West Virginia University is currently developing a simplified froth flotation cell, designated an airlift-cyclone, which may provide considerable savings in capital and operating costs without sacrificing product quality or recovery. This experimental cell consists of three primary components: 1) a vertically mounted U-shaped pipe; 2) an air injector device; and 3) an integrally mounted cyclone-like unit (Fig. 1). A feed slurry is introduced at the top of one leg of the U-pipe while compressed air is injected near the base of the other leg. The air serves both to aerate the pulp and to cause it to flow upward into the base of the cyclone unit where the floated clean coal is separated from the reject material and unfloated coal which remains in slurry. The Coal Research Bureau's experimental airlift-cyclone is somewhat similar in principle to a flotation device developed by Russian engineers in the late 1950's. In tests upon a two-stage pilot-size device, the Russians obtained very favorable cleaning efficiencies.' However, later experience with production models demonstrated that rated capacities and acceptable product quality could not always be maintained.3 Because of these limitations, Russian engineers subsequently recommended that conventional, mechanical cells be used when cleaning difficult to float slurries. Engineers at the Coal Research Bureau felt that such a device utilizing the combined actions of a cyclone and a froth flotation machine offered numerous attractive features and merited investigation. Accordingly, a small capacity experimental airlift-cyclone was designed and, with the permission of the Christopher Coal Company Div. of Consolidation Coal Co., installed in Christopher's Humphrey preparation plant near Morgantown, West Virginia.

Jan 1, 1964

By Charles T. Baroch, Charles J. Baroch

Nuclear energy probably has greater potentialities for changing the world's way of life than any other recent discovery. The atomic-bomb bursts over Hiroshima and Nagasaki suddenly changed the concepts of war. Peaceful uses of nuclear energy are advancing so rapidly that no study of economic trends is complete without giving them consideration. The minerals specialist, especially, must be aware of this new force in our lives, as minerals and metals are essential in harnessing the new force, and atomic energy itself is rapidly improving its competitive position in the energy field. Future historians may chronicle December 2, 1942, as the beginning of the Atomic Age. On that day Enrico Fermi and his co-workers at the University of Chicago produced and controlled the first self-sustaining nuclear chain reaction. Lie many inventions, the first application of nuclear energy was as a weapon of war. However, its potential usefulness in man's work and welfare far outweighs in economic importance its destructive use in war, unless its military effect would be considered so great and all-embracing that no major power will hereafter chance a world conflict. Recognition of this potential has generated a vast international effort to exploit the atom for peaceful beneficent purposes. Like its physical manifestation, the advent of nuclear energy has unleashed chain reactions that have pervaded the political, social, and economic environments of the world. The impact of nuclear developments in one of many fields is exemplified by the uranium mining industry. Uranium was discovered in 1789 and in the next century and a half it found only an insignificant use as a ceramic coloring agent; in fact, in the latter part of that period, it was a largely unsalable by-product of the radium and vanadium industries. Up to 1940 the total quantity of uranium metal produced was not more than a few grams, of doubtful purity. Thus the production of 12,400 pounds of pure

Jan 1, 1964

THE slag performs two useful functions in open-hearth steel- making. First, it is the means of disposal of all the impurities, save carbon, which are removed from the charge materials in refining the steel, so it must be suited to receiving and retaining as much as possible of undesirable elements with minimum loss of iron and useful alloying elements. Second, the slag serves as a buffer between the flame and the bath and transfers oxygen to the metal at a measured pace contrasted with the violent and difficultly controlled oxidation of the bessemer process. At the same time, the slag is a thermal insulator that limits the rate at which heat can be delivered to the metal from the flame, and a heavy slag blanket thereby serves as a brake on production rates. It has been said with justification that the secret of good steel- making is to make a good slag and the steel will take care of itself. In a broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of: (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) Si02, MnO, MgO, and other oxides charged as such or introduced incidentally with ores or fluxes or by refractory erosion, and (3) lime charged or fed to the heat to neutralize the "acidic" oxides present (Si02 and P205). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined; and the control problem would be solved. Unfortunately, only a somewhat imperfect control over these factors is possible, so the operator must begin during the lime boil and continue through the refining period to discover and correct departures from the normal pattern of slag development. To do this as the heat progresses, the first helper must be able to make quick estimates of the composition and physical state of develop-

Jan 1, 1964

Jan 1, 1964

By B. Ramaswami, Y. Nakada, U. F. Kocks

Compression tests were performed on single crystals of aluminum, silver, gold, and a Ag-10 pet Au alloy, with height-to-width ratios from 8:1 to 1:1. As this ratio decreased, so did the amount of easy glide until, for cubic specimens of all the pure materials, it was entirely absent. Heterogeneity of deformation is proposed to he a major contribution to the explanation of easy glide in slender specimens. For comparison, one single-crystal cube of zinc was tested and showed a behavior very similar to that in tension. Beyond easy glide, tension and compression curves are very similar. It is concluded that, in this range, neither grip effects nor orientation change influence the work-hardening characteristics to any significant extent. (121) and (100) crystals of all materials had similar stress-strain curves in tension and compression, except that the stress level of the flat portion of aluminum (109 crystals at high strains mas somewhat higher in compression. These results are at variance with previously proposed mechanisms of orientation dependence by both Hosford and Kocks. The compression tests themselves are described in detail and it is shown that they are essentially frictionless and produce single slip when the crystal is suitably oriented. DEFORMATION in uniaxial compression does not necessarily give the same result as deformation in uniaxial tension, essentially because the boundary conditions chosen are practically always different. 1) The shape and size of the specimens are usually different, and any genuine effect of size on work hardening should thus influence the result. 2) The grip constraints are usually different and can vary substantially for different kinds of tests. If the compression specimen is a thin plate and the friction on the platen is large, the grip contraints are more serious than in tension and lead, in the extreme, to uniaxial strain rather than uniaxial stress. If the specimen is roughly cubical and the friction is low, the specimen is less constrained than in tension inasmuch as displacements in the contact face are allowed. 3) The orientation change of single crystals is of opposite sign in tension and in compression; it is furthermore different in detail, because the relevant orientation in a squat specimen is the normal to the contact face, whereas that in a slender specimen is the generator of the side faces.' The considerable dependence of work hardening on the initial orientation in tension would suggest that the orientation change should also be very important. 4) Finally, localized deformation instabilities found in tension tests, such as necking and Lüders band propagation, are not possible in squat specimens. This is, for some investigations, a favorable consequence of the large grip influence. Even if one is not interested in any of the effects mentioned above, compression tests are often desirable just because the specimens needed are so much smaller and sturdier. For example, they have been very helpful in the investigation of latent hardening by means of alternate longitudinal and lateral compression of cubes,* and for testing

Jan 1, 1964

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.' Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964

By Charles L. Mantell, P. P. Napolitano

High-purity tellurium oJ semiconductor grade may be prepared by a combination of electrowinning from tellurium oxide, electrorefining and controlled atmosphere melting, as detailed in the paper. SEMICONDUCTOR devices such as transistors and rectifiers depend upon extremely pure forms of silicon, germanium, and selenium. Although tellurium is chemically related to these elements, it has not been studied as a semiconductor because commercial forms are too impure. Highly purified tellurium would be an interesting starting point for a study of its solid-state characteristics. Tellurium shows a greater electrical conductivity in the direction of the helices or chains forming the crystals than at right angles to the chains, and thus is a semiconductor. Unlike selenium, the conductivity is only slightly increased by exposure to light. Impurities such as Ag, Cu, Au, Fe, Sn, As, Sb, Bi, Br, and I provide accepters and make extrinsic tellurium of the P type. So far, however, no elements have been found which, when introduced, would act as donors. Small amounts of tellurium dioxide enormously increase the thermoelectric power. Many extremely pure metals have been made by electrolytic refining or electrowinning procedures. Tellurium forms compounds in a number of valences, as indicated in Table I. The physical properties given in Table II do not show any unusual conditions which would interfere with the formation of elec- trodes, or the deposition of the metal on a cathode. Tellurium dioxide could be obtained in relatively high purities of 98 pct TeO2 or better at reasonable prices. Tellurium dioxide is soluble in caustic to form tellurites, which are conductive, ionizable, and from which tellurium metal may be deposited at a cathode. Preliminary solubility tests to saturation of tellurium dioxide in approximately 10 pct sodium hydroxide gave the results of Table III. The temperature range is a practical one for electroplating. Electrochemical test facilities were set up and these met the operating conditions of Table IV. For a determination of purity of deposits, there was available a Jarrell Ash Co. quantitative emission

Jan 1, 1964

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By F. X. Tartaron

This paper deals with basic physical phenomena, which when combined and interpreted, lead to the same mathematical equations that describe comminution phenomena. Thus, a physical model is described that corresponds to the mathematical model presented in the writer&apos;s previous papers. &apos;12 In the mathematical model, the energy consumed in breakage is related to the volume or weight of material broken and the size of particles broken. The equation E=2.303 Ck-a log x1/x2 was derived by multiplying the volume or weight of each size in an ideal Gates-Gaudin-Schumann size distribution by an energy factor. The product of these two factors gives the energy distribution among the different sizes in a single size distribution. The energy of breakage of a specific constant weight of one size distribution to another size distribution is given by the equation E = constant/kn-1. In this case, where the volume or weight is constant, the energy is proportional to the size factor 1/kn-1. In what follows, a physical theory will be presented showing that the energy consumed in comminution is proportional to the volume or weight of the material broken and to the reciprocal of the size of this material raised to a constant exponent. THE VOLUME FACTOR The atomic theory of matter reveals that in solids, atoms or ions are arranged so as to be in equilibrium at specific distances from one another. Although the atoms or ions are oscillating, there is a definite determinable mean distance between them and this distance is a balance between repulsive and attractive electrical forces. It therefore requires force to separate the atoms or ions and when an outside force is applied, it first produces strain in increasing the distance between the atoms or ions. This strain increases to the breakage limit on application of sufficient force. In brittle materials, there is negligible plasticity and when an elastic limit is exceeded, breakage takes place. The work done is the force applied per unit area times the cross sectional area of the ideal particle multiplied by the maximum strain per unit length at right angles to the area times the length of the particle. Thus the work done is proportional to the area times the length, which is equivalent to the volume of the ideal particle. If more than one feed particle is considered broken, each particle must be subjected to sufficient strain so that the breakage limit of its contained atoms or ions is reached in order for the particle to be broken. Thus, the energy of breakage is proportional to the total volume of the particles broken. If the particles are of different sizes, the size factor must be included to get a correct determination of energy of breakage. In the preceding, it has been assumed that there is a constant binding force between the atoms throughout the volume being strained. This, of course, is not true. It is known that there are many irregularities in the structure of matter and the binding force differs markedly in different portions. But the differences are only discernible by examining extremely small subdivisions of matter. In one order of magnitude of volume, cracks can be discerned separately from non-cracked neighboring material. In a smaller subdivision of volume, lattice dislocations can be isolated. When these situations are brought into focus, mechanisms of their behavior can be learned, leading to a fuller understanding of phenomena that occur in larger scale subdivisions of matter. Very often, however, the mechanisms that operate in small scale subdivisions have negligible effect in those of large scale, and there still is a place for deriving a mechanism for large scale conditions. The quantum theory is extremely valuable for use with photons and electrons, but is of negligible use with ordinary atoms and molecules. This paper deals with relatively large scale subdivisions of volume present in comminution phenomena. Hence, the effects of cracks, lattice dislocations, misplaced atoms, etc., are smoothed out in an average, constant for each relatively large subdivision of volume. This attitude is supported by experience. If two 10 cc samples of the same ore were ground identically, the same product would be obtained. However, if two samples, each a cubic micron, were conceived to be broken, then one sample might contain a crack and the other not, hence a different product would be obtained. Experience shows that ordinary samples used in comminution, behave as though no irregularity existed

Jan 1, 1964

By J. D. Braun, C. W. Powell

Diffusion between gold and indium at two temperatures below the melting point of indium (155.4oC) was investigated. The major, component of the diffusion zone was determined to be AuIn2; the other, intermediate phases in the system occur in much narrower layers In order of decreasing layer width these are: Au9In4, AuIn, Au4In. Inter diffusion coefficients of the four intermediate phases and the terminal solid solutions lie in the range of 2.4 x 10-l3 to 1.8 x 10-11 sq cm per sec. WHEN two metals which do not form a continuous series of solid solutions interdiffuse, each phase in equilibrium at the diffusion temperature should appear as a separate layer in the diffusion zone. In the Au-In system, diffusion plays a significant part in many commercial applications, particularly where indium alloys are used as solders for electrical contacts with very fine gold wire, for estab- lishing electrical contact to thin metallic films, and for mounting metal-coated piezoelectric crystals. A knowledge of the number, extent, and type of phases which form at diffusion temperatures below the melting point of indium, 155.4oC,1 and the diffusion constants for the system would be useful for these practical applications. Of more basic significance, additional information on polyphase diffusion in a system not previously investigated would be gained. The phase relationships in the Au-In system were determined primarily by Kubaschewski and Weibke1 and are based on thermal, microscopic, and X-ray analysis, Fig. 1. There are five intermediate phases in the system having approximate compositions corresponding to the formulas: Au4ln (ß)—80.0 at. pet Au; Au3In (?)— 75.0 at. pet Au; Au9In4 (d)—69.2 at. pet Au; AuIn—50.0 at. pet Au; AuIn2—33.3 at. pet Au. Solid solubility of indium in gold at 700°C is reported as 12.64 at. pet and at 406°C as 10.36 at. pet. No solid solubility of gold in indium is reported.

Jan 1, 1964

By T. D. Teimann, R. L. Stone

The rate of extraction of silica from certain Wisconsin and Minnesota taconites was investigated by autoclave digestion in sodium hydroxide solutions over the temperature range from 296° to 416°F. Rates obtained were from 7 to 254 g mol per cm2 per sec giving activation energies from 15,000 to 19.000 cal per mol. Activation energy was found to increase with increase of sodium hydroxide concentration. Digestion of different forms of quartz indicated the rate of extraction to be solely a function of surface area under similar conditions of digestion. The results of an experimental investigation on the caustic extraction of silica from certain Wisconsin and Minnesota taconites were presented in a recent publication.&apos; It was shown that residual concentrates containing as much as 65% iron can be produced by this method. The occurrence of silica as a micro-crystalline variety of quartz with high specific surface area gave correspondingly high mean rates of extraction in solutions of sodium hydroxide. The present paper extends this previous work by presenting the results of a study of the specific rates of extraction of silica from these ores as related to temperature, sodium hydroxide concentration and variety of quartz. Calculated activation energies for the dissolution of silica are presented and some possible mechanisms are discussed. TACONITES The low-grade siliceous iron ores investigated included taconite from the Wisconsin Gogebic range and a semi-taconite2 from the Minnesota Mesabi range. These are adequately described in the former paper1 and by the U. S. Bureau of Mines. The principal iron minerals are hematite (Fe2O3) and goethite (Fe2O3 . H2O), while the gangue is essentially a microcrystalline variety of quartz. Minor amounts of other minerals are present. Typical analyses show the Wisconsin taconite to contain approximately 28% Fe and 54% SiO2 and the Minnesota semi-taconite 39% Fe and 39% SiO2. Analyses of the actual samples used are given in Table I. The taconite samples were prepared for digestion by reducing the original ore to minus 200 mesh in a Braun pulverizer. QUARTZ Three varieties of quartz were studied in the investigation: Ottawa sand, chert and chalcedony. The Ottawa sand was obtained from the Ottawa Silica Co. The chert and chalcedony came from Wards Natural Science Establishment. A minus 200 plus 400 mesh fraction of the Ottawa sand, used as a surface area standard, was repeatedly washed in hot concentrated hydrochloric acid followed by distilled water before autoclaving. The other two varieties were used directly after grinding through 200 mesh in a laboratory hammer mill. Analyses of these samples appear in Table 11. Microscopic examination of the silica samples by the oil immersion method showed that the Ottawa sand consisted of clean, uniform spheres of quartz with little deviation in size from a mean diameter of 82µ determined by a distribution count. The other two varieties consisted almost entirely of microcrystalline aggregates of quartz crystals; the aggregates ranged from 10 to 70µ. The individual crystals in the chert aggregates were estimated to be of the order of

Jan 1, 1964

By T. H. Alden

A correlation has been found in rock-salt structure single crystals between the latent hardening, measured by the direct stress activation of oblique slip systems, and the stress-strain behavior in simple compression. Materials with high latent hardening, like LiF, strain-harden at a low rate (Stage I) even when severely constrained. KCl, in contrast, shows low latent hardening and a tendency to strain-harden at a high rate (Stage 11). This correlation suggests that oblique slip is essential for Stage II hardening of these materials. THE role of secondary slip in the strain hardening of metal single crystals is a topic of lively controversy. On the one hand are theories in which secondary dislocations participate directly in Stage II hardening in the fcc metals, for example through the production of sessile dislocations,1 forest intersections, or jog formation. Much of the experimental evidence on which these theories are based has been reviewed by Clarebrough and Hargreaves.~ On the other hand, a recent theory5 denies that secondary slip has an essential role in Stage II hardening or in the transition from Stage I to Stage 11. In the latter view, Stage I is not terminated by an increase in the activity of secondary systems but by the exhaustion of undeformed material.6 The experiments reported in this paper will not resolve this controversy since the materials being studied are cubic ionic crystals rather than metals. However, the results do show in an unusual way a direct connection between "secondary" (nonortho-gonal or oblique) slip and strain hardening in these materials. Specifically, a correlation has been found between two independently measured properties, first the latent hardening of oblique (110)(1i0) slip systems as measured by direct stress activation of these systems, and second the stress-strain behavior at small strains. From prior work, it was known that in most cubi-cally oriented rock-salt structure crystals, two orthogonal slip systems operate and exclude the other equally stressed pair, oblique to the first pair.7&apos;8 This observation apparently indicates that a significant interference exists between slip on oblique (110) planes and a relatively small interference between orthogonal (110) planes. The present experiments were begun with the intent of obtaining a quantitative measure of this difference by means of a study of latent hardening in these crystals. I) EXPERIMENTAL METHODS The experiments were basically of two types, first the determination of stress-strain curves by compression along a single (100) axis, and second the measurement of latent hardening by compressive prestrain along one cube axis followed by the determination of the yield stress in a second (latent) cube direction. All tests were done at room temperature in an Instron machine by compression between lapped, parallel steel faces. Three specimen shapes were used. For long crystals (nominal dimensions, 1/8 in. square by 1/2 in. long) the ends were lubricated with an oil-graphite mixture. Superior results with short crystals (about 1/8 in. cube) were obtained using 0.003-in. teflon film.&apos; Thin crystals (1/4 in. square by 3/32 in.) were used for latent-hardening measurements and similar results were obtained with either lubricant. Test specimens were cleaved from Harshaw single crystals which had been irradiated to a dose of lo8 roentgen using a cobalt-60 source. The irradiation raises the yield stress and tends to prevent plastic deformation during sample preparation.10 Prior to testing, the irradiation hardening was removed by an anneal at 400°C. Ideal compression specimens have flat, parallel faces. In short specimens particularly, satisfactory results demand a close approximation to this ideal. In the present work, cleaved surfaces were often used directly as compression faces. The degree of success using this method depends on two factors: 1) the smoothness of cleavage faces, and 2) the extent to which the crystal is deformed or crushed by the chisel during the cutting of a long crystal into short pieces. Unfortunately, only one material of those studied, LiF, was completely satisfactory. NaF, NaC1, KC1, and KBr behaved less well so that

Jan 1, 1964

By D. C. McLean

This report summarizes the work that has been done during the past several years in adapting resins for use as auxiliaries in mine roof support. The resins were applied in two ways: 1) by injection into the strata, and 2) as a bonding agent for roof bolts and reinforcing bar. The Explosives and Mining Chemicals Department of the American Cyanamid Co. has worked during this period in cooperation with the Roof Control Research Group of the U.S. Bureau of Mines, the Pattin Manufacturing Co., the J. H. Fletcher Co., the Homestake Mining Co., the U.S. Steel Corp., the National Mines Corp. and the Pocahontas Land Corp. in an effort to create resin formulations and methods for applying them as a practical and sate type of roof support for mining areas particularly where conventional support is inadequate, yet expensive. This, work has involved much pioneering in a field where theory, speculation, and pure mythology predominates, and little basic engineering data is available. It is strange butt true that, despite the importance of roof control both from an operational and safely standpoint, there is scarcely a mining&apos; company in this country that has an engineer, or anyone, assigned to the study of roof support problem, except temporarily--after a bad roof fall. The responsibility for improving roof control methods seems to have been placed entirely upon the shoulder, of the USBM, various State departments of mines, and individual roof bolt manufacturing; companies. It was in cooperation with the USBM that Cyanamid first developed resins for mining use.

Jan 1, 1964

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.&apos; The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.&apos; The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1964

By J. Mizrahi, A. Brillantshtein, A. Mitzmager, O. Schächter

The separation of synthetic mixtures of heavy minerals by hindered settling classification and jigging was comparatively tested in water and five organic heavy liquids, of various specific gravities and viscosities. It was found that in the hindered settling classification process the separation efficiency was directly proportional to the concentration criterion, the liquid viscosity being a minor factor. There is therefore a decisive advantage in using heavy liquids as classification medium. In the jigging process the advantage of using a heavy liquid is masked by the detrimental effect of a higher liquid viscosity, which, in this case constitutes an important factor. Considerable interest has been aroused lately by the development of mineral beneficiation techniques 1,2 using TBE (tetrabromoethane), a heavy liquid of specific gravity of 2.96, which has been made available for industrial use by a new process3 producing TBE directly from the Dead Sea brines at a reasonable price. Most of the applications investigated until now were based on the sink-float separation of minerals in a heavy liquid of intermediate specific gravity. The TBE can be conveniently diluted with many organic solvents, and thus sharp separations are possible in a wide range of specific gravities up to 2.96. Although this maximum specific gravity is sufficient on most cases for the elimination of the bulk of the barren gangue and the production of marketable concentrates, some practical problems came up for investigation in which the separation of two (or more) minerals, heavier than TBE, was required.* *Among the cases studied in the IMI Laboratorles which fall into this category we can mention: alluvial deposits, such as heavy minerals in sea sand, tin deposits, or ground coarse-grained rocks, such as pegmatites. In such cases where, due to the petrographic structure, further fine grinding is required in order to achieve the liberation of the heavy components, the

Jan 1, 1964

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964