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By C. Feng, I. R. Kramer

A study was conducted to determine the influence of the surface on the yield point of fcc metals and high-purity iron. For the high-purity fcc metals, the yield Point produced by restraining a specimen may be eliminated by removing a sufficient amount of the layer. A yield point similar to that in fcc metals was found when iron specimens were pre-strained after a prior deformation. This yield point is not due to an aging effect but is associated with the surface layer. The yield points in age-hardenable aluminum alloy and those connected with "work softening" are not affected by a surface-removal treatment and are, therefore, caused by bulk-type dislocation reactions. The yield point which appears in previously strained fcc metals has been the subject of numerous studies. Several theories have been advanced to explain this "unloading-reloading" yield point. Cottrell and stokes,' from their study on the effect of temperature on plastic properties of high-purity aluminum, considered that it was the result of an avalanche "breakdown" of Lomer-Cottrell sessile dislocations. Haasen and Kelly2 extended this concept of dislocation-dislocation interaction to account for the yield point when unloading and reloading was carried out at the same temperature. On the other hand, strain aging was found to be responsible for the yield point in A1-Mg alloy by Westwood and Broom,3 and in aluminum alloys containing various amounts of alloying elements by Smallman, Williamson, and Ardley.4 In these cases, the yield point is considered to be associated with the locking of dislocations by impurity atoms. Birn-baum and filer5,6 and Takamura and muira7 reported that, when a high-purity copper specimen was prestrained, then held at a lower stress, and finally reloaded at the prestrain temperature, a larger yield point was observed. Such an increase was attributed to the locking of dislocations by point defects. In addition, Bolling8 suggested that both mechanisms, i.e., dislocation-dislocation interaction and strain aging, are responsible for the yield phenomenon, at least in a brass. Thus, there appears to be experimental evidence for both the strain aging and dislocation-dislocation interaction theories to explain the yield point in the fcc metals and alloys. In a previous article,9 one of the authors observed that, if sufficient amounts of metal were electrolti-cally removed after deformation of a high-purity aluminum single crystal, the yield point did not appear upon reloading. Continued pursuit in this area revealed that the effect of the surface on the yield-point phenomenon is not limited to one metal but affects a variety of metals of different lattice structures. Nor is the effect limited to the yield points produced by simple unloading-reloading at constant temperature; the surface exerts an important role on the yield point even when the temperature is changed at some stage during the test. It is the intent of the present article to give additional information regarding the effect of the surface on the yield-point phenomenon and to show the association between the yield point in both fcc and bcc metals and the existence of a heavy concentration of dislocation in the region near the surface of a deformed specimen.10 EXPERIMENTAL Materials. The single crystals used in this study had a nominal cross section of 0.125 by 0.125 in. and a 3-in. gage length and were prepared by a modified Bridgman technique. The initial purity for the metals was 99.997, 99.999, and 99.999 pct for aluminum, copper, and gold, respectively. Bar stock of these same materials was used in the preparation of the polycrystalline specimens of aluminum and copper. The iron specimens were machined from rods of "ferrovac", reported to have a purity of 99.98 pct. In addition, a precipitation-hardening aluminum alloy, containing 1.5 pct Cu, 2.5 pct Mg, and 5.5 pct Zn, was used. The polycrystalline specimens of iron, copper, and the aluminum alloy had a diameter of 0.17 in. and a gage length of 2 in. while the high-purity aluminum specimen had a nominal rec-

Jan 1, 1965

By H. H. Rachford

This work presents a first-order analysis of the instability underlying viscous fingering in adverse viscosity-ratio water floods. It extends previous analyses of frontal instabilities, which were carried out with equations for parallel plate models, by including effects of the saturation transition zone observed behind the front in water floods in water wet systems. This zone tends to insulate incipient fingers from the high-mobility watet;. thus conditions for the onset of fingering differ from those in the parallel plate theory. Finite-difference solutions of the two-dimensional equations of displacement in porous media exhibited the predicted stability characteristics in six hypothetical field- and laboratory-scale floods in rectangular reservoirs. In contrast to results with parallel plate systems, this paper concludes that for waterwet reservoirs, laboratory models scaled by the usual criteria are also correctly scaled for frontal instability. Further, fingering in the systems studied can occur in any saturation range behind the front, and may occur at an intermediate saturation even though stability obtains both at the saturation corresponding to the Buckley-Leverett front and near residual oil saturation. Other points of contrast are that the likelihood of occurrence of fingering may not increase as flow rate or viscosity difference increases, but my be sensitive to changes in he relative permealdlity and capillary pressure functions. INTRODUCTION The recovery of oil by water flooding frequently involves displacing the oil by water of a lower viscosity. Displacement of a fluid by a less viscous one may lead to gross channeling or fingering like that observed in solvent floods, in which it severely lowers recovery efficiency.1 In addition to adverse effects on recovery, it has been suggested that the unstable move- ment causing fingering may interfere with interpretation of scaled model studies of proposed water floods, since the instability in the model might not be faithfully scaled to that in the reservoir prototype. In view of the serious implications of this possible breakdown of widely used scaled model techniques4-6 it is the purpose of this paper to examine the question further. Instabilities in the solutions of systems of differential equations imply a loss of smooth dependence on initial and boundary conditions. Thus, the possibility exists that in using models whose scaling is based on the differential system there may arise size- and rate-dependent factors which are not properly scaled. This possibility was examined in detail by Chouke et al., who analyzed the instability of frontal advance in a related problem, water-oil displacement in parallel plate models,2 in which a moving interface separates two regions of constant, unequal mobilities. First-order perturbation theory predicts the existence of a critical wave length for the growth of perturbations: and a wave length of maximum instability of A, = The interpretation is that wave lengths in a perturbation which are longer than A, will grow. Thus, if the width of a two-dimensional channel is greater than A,, fingers will grow, and the spacing of the fingers which grow at the maximum rate will be approximately It is important that the higher the velocity and/or the difference in flow resistance, the lower is A,, and thus the greater the number of fingers that can grow in a given model. In applying these conclusions to porous media, a pseudo-interfacial tension, , was assumed for the invasion front. Since this would not necessarily be equal to the liquid-liquid interfacial tension, an unknown constant was substituted for the foregoing expression for A, This was determined

Jan 1, 1965

By R P. Douglas

During 1955, Cominco commenced an exploration pro-gram in northern New Brunswick; in the following year, what is now the Wedge mine was discovered. The mineralization is mainly pyrite, with associated chalcopyrite and minor amounts of sphalerite and galena. The property was brought into production at 750 tons per day in early 1962. The ore is trucked 10 miles to the Heath Steele concentrator, where a copper concentrate grading about 19.5 per cent is produced and shipped to the Japanese markets through the port of Dalhousie, New Brunswick. Introduction THE Wedge mine, owned by The Consolidated Mining and Smelting Company of Canada Limited (Cominco), is located in the Newcastle-Bathurst area of New Brunswick. It is 42 miles by road northwest of Newcastle and 37 miles southwest of Bathurst (Figure 1). The mine is located on the north side of the Nipisiquit river in one of the more mountainous areas of the Province, the local relief rising to 1,500 feet above sea level. There is an almost complete forest cover of mixed hardwoods and conifers -the val-leys and hillsides being covered by balsam, spruce and pine, the swamps by cedars and black spruce and the highlands by mixed hardwoods.

Jan 1, 1965

By J. D. Spagnola

The Bureau of Mines conducted research to obtain comparative data on the extent of reduction of galena and sphalerite with molecular hydrogen and with hydrogen from the thermal cracking of ammonia and methane at various time intervals. Galena reductions of 95 to 99 percent were obtained with H2 and with decomposed NH3 while reductions of 70 to 80 percent were obtained with cracked CH4? Sphalerite reductions of 99 percent were obtained at 1,000° C with Hz and with decomposed NBs; however, complete volatilization of the free zinc from the remaining concentrate and the subsequent recombination of zinc and sulfur vapors resulted. A promoted iron catalyst brought about a decrease of 100° C in the temperature required for complete decomposition of ammonia. It was found that H2S retards NB3 decomposition and that nitrogen retards the reduction of galena by H2? A mixture of N2 and He in about the same ratio as that obtained by the thermal cracking of NBs gave about 15 percent less reduction of galena than was obtained with decomposed NB3; this indicates that a portion of the hydrogen obtained by NBs decomposition is in an active form.

Jan 1, 1965

Reaction between xanthate ions in solution and oxidized compounds present on the surface of galena to form lead xanthate is considered to be a side reaction not contributing to flotation, although accounting for some consumption of reagent. The direct reaction of lead sulphide with xanthate and oxygen to form lead xanthate is the most significant to flotation. Coadsorntion of dixanthogen is also involved. Previous work has shown lead recovery in lead rougher flotation to be a function of m [H+] where: m = concentration of xanthate in solution rHl = hydrogen ion concentration. A plausible explanation for this relationship is suggest-ed. Likewise, the experimental findings that the amount of xanthate adsorbed under certain conditions is a function of m'[H+] are explained in terms of reaction between xanthate ions and soluble basic lead salts such as PbO.PbS04? It is also shown that m[H+] should have a constant value in lead cleaners operating at a higher pH than the roughers. This conclusion is confirmed by plant data, and the value of the constant agrees well with the calculated value. The finding is useful in mill control.

Jan 1, 1965

Jan 1, 1965

By J. Richard Lucas

Today, the future of the coal industry is extremely bright because coal can be produced at a cost which makes it competitive with other energy sources. However, the industry has been forewarned that further cost reductions must be made if it expects to remain a serious contender in the growing energy market. Surface as well as underground operations must be improved. The very same elements which affected production a. few years ago still exist today and will continue to be present in the future. Improvement's in production mining equipment, mining methods, and auxiliary equipment have resulted in reduced costs over the past few years. Efforts must be continued toward further reducing costs in areas which have been improved previously, and new areas should be investigated for possible improvements. Therefore, new techniques must be developed which will enable the industry to augment its current efforts in reducing the cost of mining. The logical place to begin evaluating the factors affecting production and cost is in the immediate face area where a substantial part of the total cost of mining is incurred. The coal industry stands to gain much through the development of new techniques for analyzing the numerous variables affecting production and by establishing methods for eliminating or minimizing the adverse effect of those variables which can be controlled. Intuition and trial-and-error methods have been the standard means used to resolve many of the factors which influence production. As a result, many elements are overlooked or ignored because their effect on production is not pronounced and cannot be readily resolved. The need for a method of analyzing such factors was recognized by the Office of Coal Research. Therefore, in April 1962, under OCR sponsorship, a. research project was initiated at Virginia Polytechnic Institute (VPI). The objective of the project was to identify the factors which influence mining costs in the immediate production area, and to develop methods and techniques which will enable the coal operator to minimize production costs. The objective of the research at VPI has been successful, and techniques have been developed for establishing quantitative facts concerning the interrelationships of production activities.

Jan 1, 1965

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By A. J. McEvily, R. C. Boettner, C. Laird

The processes leading to fatigue failure in the low-cycle range were studied to obtain an understanding of the basis of Coffin's law. Particular attention was paid to the manner of mack nucleation and to the determination of the portion of the total lifetime spent in crack propagation. It was observed that cracks are nucleated at surface notches meated during reversed plastic deformation, Principally at grain boundaries, and that crack growth occupies greater than 75 pct of the fatigue life. When inclusions are present, they are often the primary sites of crack initiation. From consideration of the incremental distances advanced by a crack in each cycle and of the lifetimes of different materials, it appears that the universality of Coffin's law arises from the similarity of crack-tip strain for a given applied strain amplitude, irrespecti7:e of material. STUDIES of low-cycle fatigue have been particularly rewarding in that a simple correlation between fatigue lifetime and plastic-strain range has been shown to exist. This empirical relationship takes the forml,2 Nner=C [1] where N is the number of cycles to failure, Er is the plastic-strain range defined as the total plastic strain per cycle (the sum of the tensile plastic strain plus the compressive plastic strain), n, the exponent, is a constant independent of the material to a first-order approximation and often has a value of about 0.5, and C is a constant which for a number of ductile and metallurgically stable materials is approximately 0.65 for fully reversed strain.3 This relationship has been shown to be valid for a wide variety of metals and alloys and is often referred to as Coffin's law. However, it is yet not clear why so many different metals and alloys exhibit the same over-all behavior in the low-cycle range. Less is known about the mechanisms of fatigue failure in the low-cycle range than in the high-cycle range, but it is expected that the processes would have much in common. For example, an important characteristic common to both high-and low-cycle ranges is that fatigue crack propagation can occupy a considerable portion of the total lifetime. This has been shown by Laird and smith4 by a count of the number of ripples present on the fracture surface of copper specimens, each ripple corresponding to one cycle of load. On the other hand, some marked differences have been noted. For example, in copper,5 nickel, and aluminum4 there is a greater tendency for grain boundary cracking to occur as the strain amplitude is increased. The purpose of the present work was to study further the processes leading to fatigue failure in the low-cycle range and to obtain an understanding of the basis for the validity of Coffin's law. Particular attention has been paid to the manner of crack initiation and to the determination of the portion of total lifetime spent in crack propagation. MATERIALS A number of metals and alloys were tested, although more attention was focused on a particular few, once general trends had become apparent. Alloys were selected so as to investigate the effects of crystal structure, number of phases, stacking-fault energy, and impurity content. The materials in this grouping were: high-purity copper OFHC copper 1100 aluminum (commercially pure) 70-30 brass (Cu-30 wt pct Zn)

Jan 1, 1965

By A. A. Dor

Recent developments in the design of concentration plants have reflected the increased recognition that has been given to the economic and metallurgical advantages of autogenous grinding. This has manifested itself in the increasing adoption of primary auto genous grinding in iron ore 'beneficiation plants in North America. Table 1 lists eleven major iron ore beneficiation plants which have either been put in operation since 1961 or are under construction at present. Seven out of these eleven plants have adopted primary autogenous grinding. Four of them have coarse grinding mills (8 to 14 mesh) and three have fine grinding primary circuits (48 to 65 mesh). Their nominal capacity totals 26. 2 million ltpy of concentrates or pellets, representing very nearly 75% of the aggregate capacity 135. 3 million ltpy) of the eleven concentrators listed. For a long time there was a tendency to consider that primary autogenous grinding was only applicable to suitable coarse grained ores, However, extensive testing of a very wide variety of ores, and actual operating performance in several commercial plants, seem to have established beyond reasonable doubt, that the majority of mineral ores which the beneficiation engineer may be called upon to process can be ground autogenously. The basis for the selection of autogenous or conventional grinding mills, becomes principally economic and depends on the liberation characteristics of the ores under consideration and their relative hardness and grindability.

Jan 1, 1965

By E. J. Karges

The use of pulverized coal for generating power and performing industrial processes has made an important contribution to our industrial economy during the past half century. Actually, the burning of coal in powdered form is a subject that has held the attention of engineers for a century or longer. Its widespread use, however, is comparatively recent, As early as 1866 patents were granted to Messrs. Whelpley and Storer for a method of feeding pulverized coal into a furnace as an auxiliary to the grate fuel. In the many tests made during the subsequent years with various kinds of apparatus, the experimenters were handicapped in not getting the coal fine enough to obtain complete combustion and to prevent excessive formation of slag.

Jan 1, 1965

This paper comprises a description of on-stream analysis instrumentation, including sample handling, X-ray optics and data processing. It also includes a discussion of some typical applications of an on-stream analyzer as related to the mineral processing industry. Introduction T WO automatic X-ray spectrometers have been developed for the simultaneous analysis of as many as six elements in a given sample. These instruments, namely the On-Stream Analyzer and the new Vacuum Simultaneous Spectrometer, have been designed specifically for process control in industry where large numbers of static samples or a number of flowing sample streams must be analyzed continuously with both speed and accuracy. This paper is concerned particularly with the application of these instruments for the continuous analysis of dynamic samples. The Instruments The On-Stream Analyzer and the Vacuum Simultaneous Spectrometer are intended to serve industry by offering two basic approaches to the problem of continuous sampling of flowing sample streams. The On-stream Analyzer (Figure 1) is designed for the completely automatic and unattended analysis of flowing sample streams in a programmed cycle of operation.

Jan 1, 1965

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,' which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins' calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By Albert W. Deurbrouck

Twelve samples from six Barbour County coal beds were analyzed for this report. The samples collected were generally high sulfur content coals, frequently exceeding 3 percent in the raw-coal sample. Many of them could not be upgraded to acceptable metallurgical standards even by rigorous preparation procedures. The production of coal in the county in 1963 amounted to almost 3 million tons of which 44 percent was mechanically cleaned.

Jan 1, 1965

By D D. Deacon

A brief description is given of the requirements which No. 4 Shaft has been designed to meet and of the methods by which two-stage winding of rock has been accommodated in a single shaft sunk to a depth of 7,421 ft. This is followed by a consideration of the factors which led to the decision to sink the shaft as rapidly as possible. Introduction T HE No. 4 Shaft of Hartebeest-fontein Gold Mining Company, Ltd., has been sited to serve the deep southern area of the mine, some 1,500 claims in extent, between the elevations of 6,250 and 7,300 ft. below surface. From this area, some two-thirds of the mine production will ultimately be obtained. Above the 6,-250-ft. elevation, an existing shaft hoisting system, situated adjacent to the reduction plant, is of adequate capacity to cater for all ore hoisted to surface for milling. No. 4 Shaft will therefore be required to provide downcast ventilation of 1,000,000 c.f.m., together with surface hoisting facilities for men, material and development rock and underground hoisting

Jan 1, 1965

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.' However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.' The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1'5'6'7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By C Carbonneau

In order to successfully produce columbium pyrochlore concentrates, St. Lawrence Columbium and Metals Corporation had to face two principal problems met in several new operations but possibly made more acute than usual owing to the newness of the project. 1.-The ore is particularly complex, as it is made up of an elaborate intermingling of carbonates and discontinuous ultra-alkaline rock bodies of various ages and types in which no less than seventy mineral have been re-ported. Obvious petrographic or structural controls are lacking. Ore boundaries have to be defined on the basis of assay results and the determination of several minerals which occur in trace amounts. 2.-The pyrochlore concentrates produced had to com-ply with a set of stringent specifications. This fact, combined with the low Cb205 content of the ore, necessitated the use of a beneficiation process that would have to operate at a concentration ratio greater than 100:1. A brief description of the mill circuit is given. Mill stability was obtained through extensive mineralogical study of the mill feed coupled with close geological and engineering control of the mining operations.

Jan 1, 1965

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965