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By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By M. Cross

INTRODUCTION The development of refining processes involving gas injection into liquid metals has seen the evolution of a variety of designs [I]. During the last few years or so the top, bottom and side blown processes have, essentially, been combined to produce a series of mixed gas blowing schemes (eg. the LBE [2,3] and LD-OB processes [4,5]). Although, a variety of mixed gas blowing processes have been carefully engineered and recorded operational experience now attests to their effectiveness, optimising their design and operational performance is another matter. Detailed process analysis of such operations is impeded by the complex nature of the physical and chemical processes involved: . fluid flow behaviour of the liquid metal and injected gases, . chemical reactions in the vessel, . mass and heat transfer within the fluid phases in the vessel, . influence of the geometry (eg. location of the tuyeres, etc.), . monitoring the operational performance. By and large, design and operating parameters evolve from a combination of laboratory scale experiments, pilot plant work and, of course, practical engineering experience. Conventionally, the gas-liquid system used to model the industrial process is air-water, for a number of valid reasons including – . visual demonstration plus geometric and (to some extent) dynamic similarity, . the fact that the system demonstrates, at least, qualitatively many of the complex features of gas injection - interaction between the gas and the liquid - the nature of the gas flow behaviour - qualitative indications of mass transfer rates Important experimental contributions to the understanding of gas liquid systems include the work of Brimacombe [6], Wraith [7], T.Robertson [8], D.Robertson [9], Guthrie [10] and Szekely [11] (these references provide starting points to identify the major published work in this area). Although air-water systems have been instrumental in providing a great deal of qualitative insight into the fluid flow behaviour of the processes, reliable quantitative predictions are more problematic. A number of workers (notably Brimacombe and colleagues [6, 12])have demonstrated that different gas-liquid systems can lead to wide variations in behaviour. Other limitations of physical modelling include the assumptions of isothermal flow, scale- up of turbulent flow behaviour and the inability to directly include the effects of chemical reactions. The above limitations in physical modelling, therefore, yield a natural role for mathematical modelling provided that it can be made comprehensive enough whilst remaining cost-effective. The major physical processes involved in gas injection systems may be summarised as . behaviour of the gas envelope structure in moving through the liquid metal . the global movement of the liquid metal . momentum interaction between the liquid metal and the injected gas . heat transfer and mass exchange via the chemical react ions. The behaviour of gas envelopes forming at a tuyere and then moving through the liquid has been investigated thoroughly by a large number of workers. Such models are generally based upon simple physic- al concepts derived from visual observation. An early model by Davidson and Schuler (DS), based upon a force balance between the liquid inertia and a combination of the bouyancy and momentum forces on the envelope, has proved to be a useful tool in predicting bubble volumes at detachment [13]. The DS model has been successfully modified in a number of ways [14-17] to cope with heat transfer and reactive transfer rates, etc. Furthermore, the basic ideas summarised above have also been confirmed on industrial converters by both Guthrie [I8] and Brimacombe [19]. Models have also been developed to predict the behaviour of the "chemical" component of some gas-liquid systems. However, one thing is clear; all gas-liquid reactive systems are governed by the degree to which effective mixing occurs. As such, the processes are dominated by the behaviour of the heat and mass exchange of the two phase fluid flow system. It is the pattern of movement of the turbulent liquid metal plus its interaction with the injected gas which must be predicted reliably, if sufficiently comprehensive comp-

Jan 1, 1984

By I. Zaplatynskyj, G. C. Kuczynski

SINCE the excellent studies of metal powder compaction executed by Kamm, Steinberg, and Wulff, no work on the subject has appeared in the technical literature. Kamm et al. were the first to investigate quantitatively the distribution of density in a powder compact, as a function of pressure, height and diameter of the die, powder particle size, etc. For this purpose they devised a very ingenious method. They inserted a thin lead grid into a die and then filled the die with powder. During cold pressing, the lead grid -moved downward. Due to its deformability it followed closely the downward descent of the adjacent powder. The die was then radiographed and, from the deformations of the grid openings measured on the radiographs, the density in the vicinity of each opening was evaluated. Their findings led them to the conclusion that the friction on the side walls of the die is a major controlling factor of the density distribution inside the cold pressed powder compacts. However, it is difficult to conduct tests similar to those of Kamm, Steinberg, and Wulff in a processing plant laboratory, which usually lacks the necessary expensive radiographic equipment. The purpose of this note is to describe a method which makes it possible to determine the density distribution in green powder compacts with the same accuracy as the lead-grid method but which is far simpler and faster and requires only standard laboratory equipment. Instead of using a lead grid, the hardness at selected points of the sectioned compact is determined. If the relationship between hardness and density is known the density distribution is readily obtained. This relationship is easily found from measuring hardness and densities of thin compacts. In such compacts the density, for all practical purposes, is constant throughout. The method was tested on a Plast nickel powder, grade FlA-A20, kindly supplied by Plast Metals Co. Thin compacts (height to diameter ratio 0.2) were pressed in a single action cylindrica1 die at various pressures. The density of the compacts was determined by weighing and by measuring the height and diameter with a micrometer. Subsequently the Rh hardness was determined. Up to ten readings were taken on each specimen. The difference in hardness readings on each compact was never greater than three corresponding to about 0.1 g per cu cm uncertainty in density. By varying the compaction pressure of the samples, a whole scale of densities was obtained allowing construction of a set of density-hardness calibration curves. To test the method several compacts of different height were pressed under varying pressures. Die walls were always well lubricated. After pressing, the compacts were mounted in bakelite and halved by grinding, and hardness readings taken along the diameters of the specimens. The distance between adjacent indentations was about 2.5 mm. After hardness readings were translated into densities, contour maps of densities of the compacts were prepared. One of them is reproduced in Fig. 1. The areas encompassed by the curves are labeled with numbers representing the density in g per cu cm of those regions. In Fig. 2 the same results are re-plotted to emphasize the radial density changes at various depths. The results thus obtained confirm the findings of Kamm, Steinberg, and Wulff kentioned previously. They are recapitulated here briefly. 1—The densest part of a compact pressed from one side is at the outer circumference at the top and the least dense part at the bottom, at the outer circumference. Figs. 1 and 2 show this clearly. 2—The density near the cylindrical surfaces of the compact decreases uniformly with height from top to bottom. 3—The density variation increases with the height to diameter ratio. References R. Kamm, M. A. Steinberg, and J. Wulff: Trans. AIME (1941) 171,'R. p. 439 ;MetaLs Technology (February 1941). R.p. Kamm, M. A. Steinberg, and J. Wulff: Trans. AlME (1949) 180, 2R.P. 694; MetalS Technology (December 1948).

Jan 1, 1957

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By M. M. Singh, H. L. Hartman

This paper reports on the results of a fundamental investigation of the behavior of rock under impact of a chisel-shaped bit. Drop-tester studies were conducted with strain gauges attached to the rock and striking bit-edge. It was established that rock behaves viscoelastically. Little correlation was found to exist between the strain waveforms detected on the rock surface and in the bit; thus, strain-time curves obtained with transducers mounted on the bit cannot be used to explain the sequence of events in rock breakage. It is estimated that nearly 1 per cent of the total energy of the blow is expended in permanent deformation of the rock. The strain- energy distribution on a rock surface as a result of chisel impact, which follows a simple law, is presented graphically. Experiments also were conducted with gauges embedded in the rock vertically below the line of impact and at an angle of approximately 45' to the vertical. No essential difference was observed in the type of wave obtained with embedded gauges and with gauges on the surface, as may have been anticipated from theory. INTRODUCTION Through the ages great strides have been taken towards improvement of the various techniques applied in the breakage of rock. Indeed, numerous applications of the rock-failure process are an integral part of present-day industry, including oil well drilling. Yet, astonishingly, little is known regarding the behavior of rock under dynamic loading or the mechanism of rock failure. The value of impact loading studies from the point of view of drilling is evident, however, and requires little elaboration because impact of a chisel edge on rock forms the basic action constituting most common methods of drilling. RELATED STUDIES Impact studies of communition and fragmentation conducted by Fahrenwald, et a1,8 Poncelet,l7 Axelson, et a1,2 Piret,16 Hartman and pfleider,ll Charles and deBruyn,5 and others have been of considerable help in understanding rock-breakage phenomena. Further insight into the basic action of drilling and penetration has been obtained by the work of Irving,13 Cherkasov and Shlyapin,6 BOrcherdt,3 Shepherd,19 Shreiner and Pavlova,20 Drilling Research Inc.7 Hartman,10 Appl and Gatley1 and several other investigators. However, knowledge concerning the stresses and strains induced in the rock and bit during impact remains scant. Recent photoelastic studies by Tandanand and Hartman (1961. 1962)22, 23 have shed light on stress distributions and Fracturing produced in plastics by chisel-shaped bits. In the field of transient strain Pulses and their role in rock drilling, the only extensive work has been performed by Drilling Research Inc. (DRI). They attached strain gauges to the shank of a bit and conducted drop-tester studies, using a die-shaped bit to obtain force-time diagrams. Their work led to the conclusion that, for a given rock type, the first peak of force occurs at a fixed level regardless of the total energy in the system, provided it exceeds a certain minimum threshold level. Further, on this basis an explanation was offered for the sequence of events in crater formation as the result of a single blow on rock. PURPOSE OF PRESENT STUDY The investigations reported in this paper were conducted in a manner similar to the DRI approach, but with the objective of determining the strain distribution in the rock around the area of bit impact and, to a limited extent, the strain in the chisel-shaped bit itself. It was expected that a knowledge of the disposition of these strains, along with the rate of attenuation of strain energy in the rock

By W. B. Mather

Of the 61 dikes examined some yielded cassiterite, tantalite, and beryl; eight contained spodumene; and six carried amblygonite. Two mines stockpiled spodumene as a byproduct. Only zoned pegmatite dikes carried lithium minerals. GEOLOGICAL studies have revealed the occurrence of hundreds of pegmatite dikes in northeast Brazil, Fig. I, in the three states of Rio Grande do Norte, Paraiba, and Ceara. Heretofore data have not been available on the possible production of lithium minerals from these areas, and in March, April, and May 1953 the author undertook a reconnaissance survey covering a cross-section of the pegmatite~. Sixty-one pegmatites were examined. The pegmatites of Rio Grande do Norte and Paraiba are located in an arid region (Seratao), and except in the most southerly portion there is a minimum of vegetation and overburden. The region is easily prospected and relatively accessible by jeep or truck. The pegmatites examined in Ceara are in an area of lush vegetation along the flanks of the Jaqueribe River valley. It is therefore more difficult to prospect, and the dirt roads, as a means of access, leave much to be desired. For all practical purposes rail transportation, except in Ceara, is not available. The rocks of the area are composed of Pre-Cambrian schist, gneiss, quartzite, and marbles. They have been intruded by granites, monzonites, and diorites and cut by quartz veins and pegmatites. Pre-Cretaceous erosion reduced the area to a peneplain upon which Cretaceous or younger sandstones were deposited. Recent erosion has left only a few remnants of these younger rocks. In most of the Rio Grande do Norte-Paraiba area the pegmatites were more resistant to erosion than the enclosing schists and therefore stand out in relief. This is not true in the rolling country of Ceara, where the pegmatites lack topographic expression. With regard to structure and lithology, the pegmatite~ of northeast Brazil are divided into two types, uniform and zoned. Of the 61 examined, 19 belong to the uniform and 42 to the zoned type. Uniform pegmatites are normally long, narrow, and tabular, with sharp contacts. They are composed of an intimate mixture of feldspar (microcline or ortho-clase), mica (biotite, phlogopite, or muscovite), and quartz. The grain size5 varies from fine at the contact to coarser in the interior. They are not considered a commercial source of pegmatite minerals, although efforts have been made to produce green beryl of gem variety. This type of dike is often abundant in schists and gneisses close to granite intrusives. The productive dikes — lenticular, pod-shaped, or irregular in outline, with sharp contacts — are of the zoned variety. Zone contacts are gradational, except for those with the quartz core. Zones re identified as follows, see also Fig. 3. Border Zone: This outer zone, in contact with the country rock, is composed chiefly of fine-grained muscovite and biotite, with lesser quantities of finegrained microline and quartz. It is the narrowest zone, usually measurable in inches. Wall Zone: Lying between the border and intermediate zones, the wall zone is composed of medium-grained feldspar (often microcline), muscovite, and quartz. Usually it is the widest zone. Widths of 50 ft were noted. Intermediate Zone: Lying between the wall zone and core, the intermediate zone is composed principally of coarse-grained microcline (occasionally with some orthoclase and albite). It may also carry minor amounts of coarse-grained quartz and fine to medium-grained mica. The width varies from less than 3 ft to more than 30 ft. Core: The center of the dike is composed almost entirely of massive quartz, occasionally with minor amounts of fine-grained muscovite. The width reaches 30 ft. Lithium and other minerals of potential economic value are found in the following zones:

Jan 1, 1955

By S. R. B. Cooke, H. S. Choi, D. H. Harraway, I. Iwasaki

The mineralogy of natural iron ore samples and their slimes have been investigated and the nature of slime interference in iron ore flotation has been studied. The results have been correlated with the flotation behavior of a natural ore sample. Various conclusions have been reached as a result of these studies. In the flotation of iron oxide ores, desliming is generally considered to be an essential step to successful separation, irrespective of whether the iron oxide or siliceous gangue minerals are to be floated, although some workers have found empirically that certain collectors and reagent combinations are less sensitive to the presence of slime than others. The detrimental effect of slime is considered to be twofold. First, the presence of slime presupposes a high reagent consumption because of high specific surface. When clays are present and when cationic collectors are used abstraction by ionic exchange may augment this condition. Attempts to compensate by the addition of large amounts of reagent result in only partial correction. Second, slime coatings on granular particles tend to interfere with the bubble-mineral contact. The nature of slime coatings in flotation is quite complex and has been the subject of considerable study; an attempt was recently made by Fuerstenau et al.' to relate the slime-coating density with flotation recovery and with the properties of the electrical double layer at the mineral surfaces. Although major constituent minerals in the oxidized iron ores of the Mesabi and Cuyuna ranges are hematite and goethite (limonite) as the iron oxides, and quartz and chert as the siliceous gangue, very little is known of the mineralogy and of the chemical and physical characteristics of the slimes, and still less of the interaction between slimes, collector, and the mineral surfaces. For pragmatic reasons iron ore slimes are defined as — 20p material, based upon the calculated settling velocity of a quartz sphere of the stated diameter, and of all other equal-settling mineral particles. Active slime interference with flotation is usually attributed to particles 5p in size or finer, the extent of such interference appearing to depend not only on the mineralogy but also on the size distribution of each mineral in the slime fraction. The objective of this work was to acquire a more specific knowledge of the constitution of iron ore slimes and of their role in flotation. The mineralogi-cal composition of natural slimes was obtained by differential thernal analysis (hereinafter referred to as DTA), electron microscopy, and chemical and X-ray analyses. Some flotation tests were made on natural ore samples. The surface properties of several constituent minerals were investigated by electrophoretic measurements and by determination of the adsorption of some typical flotation collectors. Finally, simplified flotation tests were made on granular goethite and quartz in the presence of various artifically prepared slimes; the results were compared with laboratory flotation tests made on natural ores. MATERIAL AND METHODS Mineralogy of Some Iron Ore Slimes: Samples of two wash-ore tailing::, hereinafter identified as A* and B, *Sample A of the present investigation 18 the same am ore A in ref. 3. of a wash ore C, and of a paint rock D, all from the Mesabi range, were selected for investigation on the basis of prior information concerning their flotation behavior. The two wash-ore tailings, when deslimed, were known to respond well to flotation, whereas the wash ore was high in goethite, tended to be slimy, and responded poorly to flotation. The paint rock also exhibited sliming tendencies, and was suspected to contain relatively large quantities of clay minerals because of its high A1203 content. Gruner states that the paint rock of the Mesabi frequently contains kaolinite. To ascertain the relative sliming tendencies of each sample a standardized desliming method was employed. All samples were ground through 65 mesh using jaw and rolls crushers. A 500-g sample of each

Jan 1, 1962

By Nigel B. Pearson

INTRODUCTION Chingola Division of Nchanga Consolidated Copper Mines Limited is situated in the Copper- belt of Zambia, approximately 30 kilometres south of the border with Zaire. It is the country's leading producer of copper and its principal foreign exchange earner, and has been, in its time, the largest single copper producer in the British Commonwealth and the second largest in the world. There are two 'primary' copper sources at the Division, namely Underground producing approximately 100 000 tonnes of contained copper annually, and the Open Pits, producing approximately 200 000 tonnes annually. Following the commissioning of the Tailings Leach Plant in 1974, treating final tailings, metallurgical recovery increased from approximately 70% to in excess of 80%. Extensive deposits of cobalt are present and following the rise in the market price in 1979 and 1980, plans were made to extract this separately. Cobalt production commenced in 1980 from Underground and will increase substantially when the Open Pit cobalt reserves become available in approximately 2 years time. This paper covers the development of the production method of the principal Underground Orebody, known as the Lower Orebody, and the control systems applied to it. HISTORY The Lower Orebody, formerly known as the Nchanga West Orebody, was discovered by extensive Diamond Drilling operations in the late 1920's. Development of the Shaft complex and the orebody commenced and continued until 1931 when flooding from development on the 480 foot horizon necessitated closure. The mine remained closed until 1937 and production commenced from the Lower Orebody in 1939. Various expansion schemes of the Metallurgical Plants and the Underground workings were completed over the years with the result that Underground production increased steadily to in excess of 150 000 tonnes copper annually in the 1960's. In recent years production has levelled out at slightly less than 100 000 tonnes annually. This decrease is as a result of producing from a lower grade reserve, available within a more limited production front, and the application of production constraints in the light of experience gained. GEOLOGY Within the Nchanga Mining Licence Area of Chingola Division, there are a total of 14 known copper orebodies in the basal part of a thick succession of sediments of Pre-Cambrian age. The sediments rest on a Basement Complex of granites, gneisses and schists. Three superimposed stratiform orebodies, known locally as the Lower, Intermediate and Upper Orebodies, occur over a vertical interval of approximately 150m. Current annual copper production is approximately 300 000 tonnes. The ore originates from four different mining operations, one Underground mine and three Open Pits. Approximately 9 million tonnes of ore grading between 3 and 3.5% copper are milled annually. The two largest sources of ore, the Under- ground mine and the Nchanga Open Pit are on the gently dipping south limb of the Nchanga Syncline (Figure 1). In the Nchanga Open Pit the major source of ore is the Upper Orebody with lesser tonnages from the Intermediate and Lower Orebodies. In the Underground mine the Lower Orebody is the only orebody being mined, underground mining of the Upper Orebody being suspended for economic reasons in 1978. The typical stratigraphic column is illust- rated in the legend on Figure 1. The footwall rocks comprise either Nchanga Red Granite or the Arkose formation, both of which are hard competent rocks, offering generally good mining conditions for footwall development. Copper mineralisation of the Lower Orebody extends from the upper part of the Arkose to the top of the Lower Banded Shales. Overlying the Arkose is the Transition zone (0-18111 in thickness). The Transition zone comprise a lower member, Transitional Arkose, consisting of incoherent kaolinised sandstone, and an upper member, Transitional Lower Banded Shales consisting of normally soft bleached and silicified shale. The soft nature of the Transitional rocks is

Jan 1, 1981

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By R. J. Weege, A. W. Schillinger

Conventional underground mapping methods and diamond drilling are being applied in a study to determine the nature of the copper ore occurrences near the footwall of the Osceola lava flow top, commonly referred to as the Osceola Amygdaloid. The work to date suggests that structures formed by relatively impermeable barriers, created by flowage and injection of still-molten lava from the interior of the flow into the solidified, brecciated crust, acted as the ore receptacles. Ascending hydrothermal fluids traveling near the footwall contact were trapped and confined in these barriers which retarded the direct upward movement of the ore fluids and caused deposition of copper. Oreshoots located near the footwall appear to have been formed spatially independently from the hanging-wall oreshoots by fluids traveling simultaneously, but along different channelways. The barrier concept, as advanced by earlier writers to explain the concentration of the ore-bearing fluids into broad shoots constituting entire ore bodies, is found to be equally as applicable for the localization of smaller oreshoots within the Osceola ore body. Recently, the Calumet Division of Calumet and Hecla, Inc. completed the unwatering of the old mine workings on the Osceola amygdaloid. Two shafts were subsequently reactivated and mining commenced on the Osceola lode after an idle period of over 20 years. Early in 1961, the Calumet and Hecla Geological Dept. was assigned the task of locating additional reserves. Accordingly, an intensive mapping and underground diamond drilling program was initiated. Except for a very few years following the first mining on the amygdaloid, the Osceola lode had never been a high grade producer. It was, therefore, recognized from the onset that a concentrated effort would have to be made by the mining, milling, and geological departments to insure success of the project. Company reports contained many references to ore that had been located near the footwall of the Osceola amygdaloid. Information concerning the grade of this ore was meager, but it was known that at least some was very rich. In contrast to ore that occurred near the hanging-wall, however, the footwall copper did not appear to have a systematic distribution and a large amount of poor rock had to be removed in developing this ore. This, of course, resulted in high development costs and discouraged any extensive mining of footwall ore. The possibility of more continuity than had previously been suspected was recognized by other workers, in particular Dr. T. M. Broderick, formerly Chief Geologist of Calumet and Hecla, who suggested attempts be made on a trial basis to follow the footwall contact with the main development drift. As most mining was done on the Osceola lode before a geological department had been established by the company, and almost all of these openings are now caved, very little information concerning the geology of footwall ore was available. It was, therefore, decided that the first step in the exploration program would be to become familiar with footwall ore occurrences by mapping the geology as the openings were driven. It was possible that a mapping program would reveal the features that controlled the localization of the ore. Furthermore, if it could be shown that footwall ore was more continuous, or if its distribution was more systematic than generally believed, it would be possible to produce a high grade ore that could be blended with the lower grade hanging-wall ore. In connection with the geological program, the Michigan College of Mining and Technology Geophysical Dept. under the direction of Professor Lloyal Bacon, is making a geophysical study of the problems of locating footwall ore by electrical methods. GENERAL GEOLOGY OF MICHIGAN NATIVE COPPER DEPOSITS The native copper deposits of Michigan are located in Keweenaw, Houghton, and Ontonagon Counties. The host rocks are Keweenawan in age and are comprised of interbedded sediments and lava flows which form a belt two to four miles wide and over one hundred miles long. These rocks form part of the south limb

Jan 1, 1962

By C. N. Reid

Slip-line studies on deformed chromium single cvystals showed the usual bcc behavior. At room temperatuve, cross slip was prevalent—slip was not confined to a given plane, but the slip direction was (111). At -10O0K, slip occuvred on (110) planes, twins on(112) planes, and cleavage on (1001 planes. A single-crystal tensile specimen with an axis close to [011] showed a pronounced yield drop and high strain rate sensitivity which zclere used to derive relevant parame tevs in a dislocation dynamics treatment. Transmission electron microscope studies confirmed the existence of (110) slip planes and showed ecidence of loops punched out by precipitates and of grown-in dislocations promoting tangling. OF recent years experimental studies have been made of the deformation characteristics of single-crystal molybdenum and tungsten, but very little has been published on the behavior of single-crystal chromium. During a study of the mechanical properties of chromium, single-crystal studies were made which have already been partially described.&apos; However, additional information was generated which was not directly relevant to the main theme of Ref. 1, and, therefore, was not reported. In view of the need for complete documentation of deformation modes, the experimental observations made on the deformation of single-crystal chromium are summarized here, together with an electron-microscope study of the associated dislocation structures. It was found that, in terms of the deformation modes, chromium is a conventional bcc metal, showing a very pronounced yield-point phenomenon. Further, it was found that the flow strength of these crystals is very sensitive to the strain rate. Finally, the crystals were observed to contain many unidentified precipitates, which often were associated with prismatic dislocation loops. EXPERIMENTAL METHODS Single crystals were grown from rods of wrought chromium by the method of zone annealing. Rods of "1/4in.-diam were supported vertically in an argon atmosphere while an induction coil was moved up the rod at 1 in. per hr. The power was adjusted to just below that required for melting, and the process produced single crystals in about 30 pct of the rods used. The orientations of the crystals, in general, lay near [011] and are summarized in Fig. 1. Before this treatment, the wrought material contained 35 pprn C, 68 ppm O, and 12 ppm N.* An analyzed single crystal *Usual metallic impurities found in iodide chromium are: Al, 5 ppm; Ca, A ppm; Cu, 2 ppm; Fe, 75 ppm; Yg, 0.5 ppm; Yn, < 3 ppm; Mo, < 3 ppm; Ni, 4 ppm; Si, < 20 ppm; Ti, < 1 ppm; V, 4 ppm; Zr, < 3 ppm. contained 10 pprn C, 79 ppm O, and 50 pprn N. Tension and compression specimens were shaped from the crystals by mechanical grinding, followed by the electrolytic removal of about 0.010 in. from the surface in a perchloric/acetic acid bath. All specimens had a gage length of 0.75 in., and tension specimens had a diameter of 0.100 in., while that of the compression samples was 0.200 in. Mechanical tests were carried out at a rate of 1.3 pct per min, and temperatures below 0°C were attained by means of a nitrogen cryostat similar to that of Wessel.2 EXPERIMENTAL RESULTS Modes of Deformation. In addition to the tensile properties of these crystals, which are described in Ref. 1, deformation markings on the surface were studied. Crystals A and F, Fig. 1, were deformed in tension at 300°K to 10 and 16 pct strain, respectively. The surfaces contained visible slip lines, about 1 C( apart, composed of both straight and wavy segments. They did not define a single plane, and so determination of the slip plane was not possible. However, the slip direction was deduced by comparing the axial orientations of the crystals before and after deformation. Fig. 2 is representative, and shows that the axis ro-

Jan 1, 1968

By T. B. Massalski, C. S. Barett

THAT metals and alloys of the body-centered-cubic structure tend to become unstable at low temperatures is so nearly universal that any exceptions are worthy of special attention. Studies of the exceptions may disclose unrecognized examples of metastability or may shed light on the nature of some of the factors that stabilize the body-centered-cubic phase. Among the structurally analogous body-centered-cubic 3/2 electron compounds, the ß-phase in the Cu-Zn system deserves further attention for, although this phase is known to undergo partial mar-tensitic transformation on cooling below room temperature to the temperature of liquid nitrogen when the composition is less than about 42 wt pct Zn, it does not transform on cooling .when there is more than this amount of zinc present.1-4 The present authors recently found that an alloy containing 48.35 wt pct Zn could be transformed, however, if deformed severely at room temperature or lower temperatures.V his discovery led to the suggestion that the jerky flow of ß-brass single crystals6 and some of the unusual temperature variations of the yield strength and hardness are due to strain-induced transformation during the tensile tests. The present investigation is an extension of that work to cover the entire available range of compositions of Cu-Zn ß-phase alloys and certain interesting compositions of the ß-phase in the Cu-Zn-Ga system. Particular attention is given to the structure of the transformation product resulting from cold work, which is found to vary with alloy composition, and to the temperature range in which transformation can be induced in the various alloys. The composition limits of the body-centered-cubic phase in the Cu-Zn system, based on a recent review by Raynor7 and the precision determinations of Beck and Smith: are shown in Fig. la; in the ß region the alloys are disordered and in the ß region they are ordered. The rate of ordering is so rapid that a high degree of order is found in any of these alloys immediately after quenching. Experimental The nine binary and four ternary alloys of this investigation were prepared from cathode copper (99.99 pct purity), electrolytic zinc (99.99+ pct), and gallium (99.98+ pct). All alloys were cast in transparent Vycor tubing, homogenized at temperatures between 800° and 890°C, and quenched in water. Ternary alloys were cast in small amounts (-5 g) to predetermined compositions to fall along a line of constant electron concentration in the ternary system. Changes of weight during the casting operation of the ternary alloys were not greater than 1 part in 2500 from the intended nominal weights and therefore their compositions were accepted without chemical analyses. All binary alloys were cast in larger amounts (100 to 150 g), homogenized, and hot rolled after preheating to 800°C. The central portion of the rolled strip of each alloy was annealed for eight days and quenched in brine. All binary alloys were analyzed chemically. The compositions, heat treatments, and metallographic appearances of all alloys are tabulated in Table I. Various samples were subjected to heat treatment or cold work at several temperatures and were then examined metallographically or by means of X-rays. Specimens about 6x6x3 mm in size were examined metallographic ally to confirm the presence of the ß-phase after quenching. Cold work was introduced by fastening each sample between two pieces of steel, cooling the assembly to the desired temperature, and transfering it rapidly to a vise where moderate or severe compression was immediately applied. Cold working at liquid helium temperature was done by a chisel-shaped tool mounted on an X-ray spectrometer, described elsewhere.% A!! metal-

Jan 1, 1958

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland&apos; found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.&apos; determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-&apos; torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.&apos; These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren&apos; and Miller&apos; were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski&apos; have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By Orville R. Lyons

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

Jan 1, 1952

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By Harvey T. Kennedy, Erasmo T. Guerrero

In this investigation, the effects of the surface tension of brine and the interfacial tension between oil and brine on the recovery of oil by water flooding of Woodbine sand were studied. Variation of the surface forces was obtained by the addition of small amounts of commercially available chemicals, which did not appreciably change the surface tension of the oil. Fourteen surface-active agents, which were found to be effective in lowering the surface and interfacial tensions, were further investigated to determine the extent of their adsorption by the Woodbine Sand cores. It was found that adsorption was sufficient in all cases to prevent any substantial concentration of chemical at the flood front. The flow system was, therefore, brought to equilibrium with definite concentrations in the flood water by circulation before each test. The data thus have no relation to the results obtainable by using the chemicals in full-scale water floods, but should be helpful in predicting the performance of surface-active chemicals which are not lost by adsorption, if such can be found. Flow tests were made on various concentrations 01 six chemicals selected from the 14 investigated for surface activity and adsorption, with and without the presence of gas in the core. It was found that lowering the interfacial tension had a tendency toward reducing the recovery of oil and that the reduction of the surface tension of the brine had little or no effect. A substantial beneficial effect, however, resulted from the presence of gas in the cores. INTRODUCTION The movement and distribution of crude oil in a porous medium are governed by such factors as surfacc and interfacial tensions, viscosity of the oil, pore size configuration, and wetting characteristics of the medium. The knowledge of the part played by each of these factors is limited. If the oil is assumed to be distributed in droplets whose movement is restricted only by the pore openings, the following equation may be applied: ?P= 2r(1/r1-1/r2) .......(1) In this equation ?P is the pressure drop necessary to force an oil droplet through the construction, r is the oil-brine interfacial tension, r1 is the radius of curvature at the forward and smaller end of the deformed droplet, and r2 is the larger radius. This equation neglects the effects of viscosity, as a static or near static condition is assumed. It would apply equally well for a bubble of gas in liquid if r were taken as the surface tension of the liquid. This relation shows that droplets can be more easily displaced if the interfacial tension is decreased. The displacement of oil from the surface of a sand particle may also be considered from the basis of selective wetting assuming that the oil droplets are smaller than the pore constructions and that the sand surfaces may be considered as planes. A relation of the forces involved can be derived from Dupre&apos;s equation to give: Wos = row (1 +Cos?)........(2) where Wos = Work of adhesion between the sand and the oil row = Oil-water interfacial tension 0 = Contact angle ros = Oil-solid interfacial tension This equation would indicate that the displacement of oil from a sand surface is more readily obtained when the water-oil interfacial tension is reduced provided the contact angle remains constant. Evidently. however, the values of Cos 0 may vary along with the water-oil interfacial tension due to changes in the other surfaces of the system. The above theoretical considerations suggest that perhaps even the static behavior of a dispersed oil phase in a porous medium is considerably more complex than may be inferred by the simple systems

Jan 1, 1955

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,&apos; work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.&apos;-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5&apos;6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram for the gadolinium-cobalt system has been determined. Seven intermetallic compounds have been found at compositions corresponding to the follwing gadolinium-cobalt ratios: 3:1, 1:1, 2:3, 1:2, 1:3, 1:4, 1:5. The GdCor compound has a congruent melting point above 1600°C. whereas the remaining compounds melt incongruently. Eutectics exist at 16 wt pct Co and 84 wt pct Co, with melting points of 620° and 1260°C, respectively. PREVIOUS papers&apos;" have recorded constitutional data for systems of gadolinium with iron and nickel. This paper presents data obtained on alloys of gadolinium with the remaining 3d transition element-cobalt. voge13 found that cerium forms, with cobalt, the intermetallic compounds; Ce3Co, CeCo, CeCo2, CeCo3, CeCo4, and CeCo5 Other workers4-&apos; found the 1:2 compound in this series to exist in a C-15 (face-centered cubic) structure and the 1:5 compound to exist in a hexagonal crystal system. Comparison of earlier data with that now reported will be made subsequently. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been previously reported.&apos; The cobalt content of alloy specimens was determined volumetrically. RESULTS Microstructure—The alloy containing 10.5 wt pct Co corresponds closely to the composition of the first intermetallic compound Gd3CO. In Fig. 1 the microstructure is essentially single phase composed of Gd3Co which formed peritectically. The globular areas are remnants of the peritectic reaction which did not quite go to completion. A eutectic occurs between Gd3Co and the next higher compound GdCO, which is followed by a series of peritectic compounds. Fig. 2, an arc-cast alloy containing 20.2 wt pct Co, shows large primary crystals of GdCo etching either white or black (depending on crystallographic orientation), embedded in the eutectic. Similarly, in Fig. 3 at 31.2 wt pct Co, a compound, probably GdCo3, has separated from the melt. Subsequent peritectic reactions were almost completely by-passed as the alloy cooled, the residual liquid freezing as a fine eutectic. In the 47.5 wt pct Co alloy, Fig. 4, the high melting point compound, GdCO4, has solidified as massive, white-etching grains, which reacted with the liquid to form GdCo3 as the second phase. The microstructure of an arc-melted alloy containing 60.5 pct Co is complex, Fig. 5, and presents some difficulty in interpretation. The grey etching matrix is probably primary GdCO4. The dappled phase represents grains of GdCO5 which have separated from the melt on cooling. The discrete spots in this phase are eutectic liquid. Small light etching crystallites are probably GdCO5 formed by the incomplete high-temperature peritectic reaction. GdCO4 is retained in arc-melted specimens containing 70.5 wt pct Co, Fig. 6. White areas of this compound are held in a matrix of GdCO5 the appearance of which is mottled slightly by inclusions of the second eutectic in this system. The development of the spheroidized eutectic at high cobalt contents is depicted in Fig. 7 (80.3 wt pct Co) in which the white massive crystals are GdCO5 compound. Further development of this eutectic is seen in Fig. 8, the primary white phase here being pure cobalt. Thermal Studies—Differential thermal analyses and melting point determinations have yielded the data shown in Fig. 10. The high gadolinium eutectic, indicated by microscopy, was confirmed at about 16 wt pct Co, melting at 620°C . A eutectic also occurs at about 84 wt pct Co melting at about 1260°C. The thermal arrests at 8803 960°, 1060; and 1210°C,

Jan 1, 1962

By G. W. Neighbor, M. S. Abrahams

The actice slip plane in InSb is found to be of the {111} type by using the method of two-tmce anulysis. Measurements of the rotation of the tensile axis with increasing plastic shear strain indicate that the tnacroscopic slip direction is a <110>. Recrystal-lization is first observed at a sheav strain of about 70 pct for a crystal deformed at a temperatzcre of 473° C and at a shear strain rate of 2.90 times 10- %ecc-I; the dislocation density corresponding to this value of the strain is 1 x 108 em-&apos;. At a shear strain of about 170 pct, the recrystallization process is complete. This appears to be the fimt time re-crystallization has heen observed in a semiconductor. V HE operation of the {Hi} glide plane in Ge was first noted by Gallagher.&apos; This finding was confirmed by Treuting who also extended the result to Si. Using X-ray techniques, Treuting3 demonstrated that the macroscopic slip direction in Ge was of the <110> type. The choice of the (111) <110> slip system in Ge is exected since in the diamond-type structure the {Ill7 plane is the plane of highest density and the <110> direction is the direction of closest packing.4 There is little reason to expect that the glide elements of InSb are different from those of Ge, since the zinc-blende structure characteristic of InSb is quite similar to the structure of Ge. With regard to InSb, Allen5 has indicated that the glide plane is the {111} type. There appears to be no quantitative determination of the glide direction, however. The present work was undertaken to establish both the glide plane and glide direction in InSb and also to see if recrystallization occurs at large shear strains. EXPERIMENTAL PROCEDURE Mechanical Deformation. The single crystals of InSb used in this investigation were deformed in uni-axial tension. The tensile axis of the specimens was [145] and the periphery was bounded by (111) and (321) planes as shown in Fig. 1. The metallographi-cally polished specimens were deformed in a dynamic atmosphere of He, using an Instron machine. The tensile tests were performed at temperatures in the range of 300°C to the melting point (525OC) and at shear strain-rates varying between 1.94 X 104 sec-&apos; to 1.94 x 103 sec-&apos;. Additional details concerning the preparation and deformation of the specimens have been presented previously.&apos; Analysis of the Glide Elements. The traces of the active slip plane in both (111) and (321) planes were analyzed according to the usual method of two-trace analysis." The macroscopic slip direction was determined by measuring the rotation of the tensile axis as a function of plastic strain,8 These measurements were made from Laue back-reflection X-ray photographs. The X-ray beam was perpendicular to the (111) plane. A given crystal was used for only one measurement of the rotation of the tensile axis after it had been strained to a predetermined value. Therefore, care was taken at all times to insure that the X-ray beam was parallel to the [Ill ] direction of all the samples. RESULTS AND DISCUSSION Glide Plane. After 3.4 pct plastic shear-strain, at a temperature of 369°C and a shear strain-rate of 1.94 x 104 sec-&apos;, the slip traces on the (111) and (3.21) planes appear as in Figs. 2(a) and 2(b), respectively. The results of an analysis of these glide markings demonstrate that the slip plane is (111). The operation of this plane is expected on the basis of the orientation of the specimen, since glide on this plane and in the [I011 direction will result in

Jan 1, 1962