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By T. Johnston, B. Cox

The results of oxidation and corrosion experiments on niobium in oxygen and steam at temperatures of 350° to 650°C, and in dilute sulphate solutions at 300°C are presented. The oxidation of niobium in oxygen can be explained in terms of a pre-transition period, which obeys an approximately parabolic rate law, and a post-transition period in which a more rapid linear rate is partially stifled by restriction of the gas flow due to the gvowth of the porous outer film. Due to changes in the porosity of the outer layers the restriction presented by the porous outel. film attains a limiting value. Subsequent oxidation obeys a linear rate law and shows an almost linear dependence of the rate on gas pressure. liltimately a second failure of the protective film may take place leading to a further acceleration in the oxidation rate. In water vapor the oxidation of niobium follows a parabolic rate law and does not show a transition to linear kinetics. The higher oxide, Nba05, was usually absent from the NbO/NbO2 film which was formed. The addition of a small partial pressure of oxygen to the water vapo3, resulted in accelerated oxidation according to the normal kinetics for oxidation in oxygen. The oxygen reacted preferentially with the niobium, and the protective oxide film was reformed when all the oxygen had been consumed. This behavior supports the theory that nucleation of Nb205 on the surface of the protective NbO/NbO2 film is the cause of the accelerated oxidation. After oxidation in steam at high-pressure Nb2Os was found in the protective film. The mode of formation of Nb2O5 under these conditions did not produce a change in kinetics, but was thought to explain the comparatively large dependence on pressure of the oxidation rate. The kinetics of oxidation in oxygenated aqueous solutions at 300°C were similar to those for oxidation in oxygen. A penetrating attack on niobium sheet may be related to the second breakaway observed by some investigators of oxidation in oxygen.

Jan 1, 1963

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By Robert H. Merrill

In 1960, the Kennecott Copper Corp. and the U.S. Bureau of Mines entered into a joint research program to determine the changes in stress, strain, and displacement created by changes in slope angles. The field site was the Kimbley Pit, located near Ely, Nev. The supporting laboratory investigations were made at the Bureau's Denver Mining Research Center. Following a study to determine the rock stresses in the mining district, the strike and dip of geologic defects (fractures) in the rock, and the laboratory-determined strength of the rock, a new slope angle and pit configuration was selected, and instruments were installed to measure changes in stress, strain, displacement, microseismic noise rate, and sonic velocities at several points in the west wall of the pit. Between February and November 1966, the west slope was changed from an average angle of 45' to a slope angle that started at 45° on the south wall, and gradually increased to 575' at the center of the west wall, and to 61° on the north wall. The pit was deepened from about 500 ft to about 550 ft. About 2.55 million tons of waste and ore were removed by stripping and mining. Measurements made between November 1965 and September 1967 showed that the pit wall was stable before excavation began, that changes in the measured quantities occurred in the pit wall during the excavation, and that the wall returned to a condition of equilibrium after the mining was completed. The need for a method and the technology to pre-design a pit slope does not require elaboration. About 5 billion tons of material are excavated yearly by surface mining methods in the United States, and the economics, safety, and availability of lower grade metals, nonmetals and fuels could all be substantially improved if operators could preselect optimum slope angles. Mining companies and the Bureau of Mines have recognized the need for developing engineering methods to determine stable slope angles. In the industry, Kennecott Copper Corp. had been making an

Jan 1, 1969

By R. H. McLean

Velocity, kinetic energy and shear in crossflow beneath three-cone jet bits may influence cleaning of the bottom of the borehole and the teeth of the bit. Laboratory investigation shows that each of these parameters is a function of the diameter of the borehole and the product of the volume rate of flow and velocity through the nozzles (QVn). Increasing QV, or decreasing the diameter of the borehole increases each parameter. These functions provide means of predicting the magnitude of each parameter and of scaling the cleaning forces. INTRODUCTION In drilling operations using conventional jet-type rock bits, the impinging jels create an important flow mechanism. Called crossflow, this flow mechanism originates in the impact area of the jets, spreads across the bottom of the hole and supplies the principal source of energy to clean the teeth of the bit and most of the bottom.' Besides providing the means of cleaning cuttings from the bit and the hole bottom, crossflow may also have other, less direct, effects on the rate of penetration. The shear stress generated on the bottom by crossflow will inIluence the thickness and permeability of any filter cake of mud solids or crushed material which forms on the bottom.' These factors may affect the rate of penetration. A previous pulblication introduced some fundamental concepts of crossflow.' Crossllow was shown to occur in a thin layer adjacent to the bottom, and to cover the bottom completely. The maximum velocity in the crossflow above any position on the bottom was found to be directly proporlional to the square root of the product of the volume rate of flow and velocity through the nozzles—the jct QV,,—and inversely proportional to the diameter of the borehole. This information indicated that the effectiveness of crossllow in scavenging the bottom can be improved by maximizing the jet QV. The investigation reported herein amplifies the definition of crossflow. Complete velocity profile data above a representative position on the bottom are analyzed. These data better illustrate control of the capacity of crossflow to scavenge the bottom, and also relate shear stress on the bottom to known, controllable parameters. The conclusion reached in the previous publication that maximization of the jet QV. produces the maximunl cleaning beneath current jet bits is unchanged by these new data; rather, it is strcngthened. Data presented here show that the kinetic energy flux above a representative position on the bottom is maximized by maximizing the jet QV. The shear stress on the bottom will also be shown to be maximized in the same manner. Since the functions relating the jet QV. to velocity, shear stress and kinetic energy also involve the diameter of the borehole, means of equating, or scaling, these quantities in different sizes of boreholes will be illustrated. EXPERIMENTAL EQUIPMENT AND TECHNIQUE JET BIT MODEL Data were recorded from the same laboratory model as used in the aforementioned investigation of the flow around a jet bit.' The model consisted of a 43/4-in. three-cone, jet-type rock bit in a smooth, flat-bottomed borehole constructed of lucite. The bit had a shape and nozzle placement closely resembling larger three-cone jet bits commonly used in field operations. Fig. 1 illustrates the impact area on the bottom of a jet from this bit. Details of the orientation of the jets may be found in the previous publication. TECHNIOU'E OF MEASUREMENT Measurements of the crossflow were made by inserting a very small Pitot tube through the bottom of the simulatetl boreholc. Extreme thinness of the layer of crossflow necessitated accurate measurements of the height of the Pitot tube above the bottom to achieve close definition of the velocity profile. A cathetometer, which could be read to the nearest 0.005 cm, was used to make this measurement.

Jan 1, 1966

By A. L. Bailey, B. A. Landry

W. W. ANDERSON and G. E. KELLER*—We want to compliment the authors on this very thorough paper. It gives information which the coal industry has needed for some time. We hope that the additional information which the authors are collecting will he available shortly. The mixing and riffling procedure that was followed for experimental purposes is obviously not practical in routine float-and-sink testing because of the particle size degradation which would result in handling the sample so many times. It is important to obtain our tloat-and-sink fractions with a minimum amount of handling of material. A statement is made in the paper (p. 80) that "the variable most likely to affect the size of sample required to meet a given preassigned accuracy would be the state or degree of mixing of the coal." We agree that this is a large factor, but do not believe it is the most important factor. Our own opinion is that the most important single factor governing the total gross weight of sample that must be collected is the percentage of the weight of material in the smallest fraction that results from the screening and float-and-\ink operations. In other words, size of sample is governed by the total number of fractionations that must he made, and the distribution of material within the fractions. We can imagine a coal with perfect mixing, but with such a small amount of material in some float-and-sink fraction in one of the coarse sizes that a much larger sample would have to be taken than would be the case with very poorly mixed material, but with a large percentage of coarse material more evenly distributed in all float-and-sink fractions. Our own observation of many float-and-sink tests that we have run in our own organization on many types of coal is that the size of sample that must be used on fine size float and sink is governed more by the requirements for weight of material to be used for analysis in the laboratory than by weight of material necessary to obtain accurate float and sink percentage of weight values. In other words, it is our opinion that very small samples can be used for float-and-sink fractionation in the fine sizes, but that accurate analysis of the fractions will depend on a larger weight of sample being pulverized for the laboratory than is necessary to establish the float-and-sink distribution with respect to weight. A. L. BAILEY and B. A. LANDRY (authors' reply)—The authors thank Messrs. Anderson and Keller for their comments based on long experience. It is agreed that the involved mixing and riming technique used may be disadvantageous from the standpoint of degradation. Fortunately, the paper does point out that the extended riming was unrewarding in causing further mixing. Two large unknowns remain, however: (1) how much of the mixing from the presumed highly unmixed state in the bed was achieved toward the random state during blasting, loading, transportation, screening, and further transportation to the point where the gross sample was taken, and (2) how much of the mixing took place during the preparation described preceding riming. As has been pointed out by one of the authors.6 the degree of mixing has a very large effect on the size of sample required and there are still too few experimental data to show at what stage of coal handling most of the mixing occurs. The discussion states that the weight of material in a screened fraction, or in a float-and-sink fraction, is more important than the mixing factor. We do not believe that these factors are comparable in this instance inasmuch as our purpose was to give minimum sampling requirements to achieve a preassigned accuracy in the percentages of float, middlings, or sink, and nothing more. The gross sample had already been screened and no further division by screening was made or contemplated; also, it was not intended that the middlings and sink fractions would necessarily be adequate for percentage ash or other determination. In other words, the sample obtained by the method outlined is not intended for washability studies but only for preparation plant control. Further experimental work has been done, since the paper was prepared, to investigate the effect of increasingly larger top and bottom sizes on the variability of float, etc., of a double-screened coal from Western Pennsylvania. Results will be published and eventually attention is to be given to the preparation of sampling specifications. E. H. M. BADGER*—I should like the authors to explain more fully the fundamental assumptions on which their Eq 4 is based. The equation is of the form s2 = p(l - p) which is the usual expression for the (standard deviation)2 when the chance of finding a particular kind of particle in the sample is proportional to the number fraetion, p. But instead of the number fraction, the authors have used the weight fraction, WF/W. The chance of finding a particular kind of particle in the sample can only be proportional to the weight fraction, if the average ?eig?ts of all kinds of particles, that is, float, midlings, or sink, are the same. Surely a much more justifiable assumption would be that the average volumes of the particles are the same, and, if this is so, Eq 4 would not be true. This may be demonstrated as follows: Let be the weight fraction of float, middlings, or sink, dl the density of this fraction, and d2 the density of the rest of the coal. Then assuming that the average volumes of the pieces in the three classes are the same, the number fraction, p, is given by ? P = d1/l-?/d2 + ?/d1 = ?d2/d1 + ?(d2-d1) The weight fraction, w, in terms of p is given by ? = pd1/(l-p)d2 + pd1 = pd1/d2 + p(d1-d2) _____ [61

Jan 1, 1950

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By I. R. Kramer

The stress associated with the high-dislocation layer at the surface of deformed aluminum crystals was measured by progressively polishing the specimen and determining the change in the initial flow stress when the specimen was reloaded. This surface stress increased linearly with strain in the Stage II and Stage III region. The depth to which the high-dislocation layer extends was found to be 0.0025 in. The influence of the surface layer on Stage I is discussed and it is shown that Stage I ends when, on the secondary slip system, the difference between the applied stress and the opposing stress due to the surface layer is equal to the critical resolved shear stress. In previous papers'-3 it was shown that the surface exerts a pronounced effect on the plastic-flow characteristics of metals. For fcc metals it was possible to increase the extent and decrease the slope of Stages I and II and decrease the work-hardening coefficient of Stage II by removing the surface of the specimen continuously during the deformation process.2,3 More recently,L it was shown that the activation energy for plastic deformation and the activated volume were also influenced by the surface. These changes were related to the existence of a high concentration of dislocations in the region near the surface of the deformed specimen and it was concluded' that the effective stress, T, acting on a dislocation was T = Ta-Ti-Ts [1] where 7, is the applied shear stress, Tj is the internal stress, and TS is the stress associated with the surface region containing the high concentration of dislocations. From Eq. [I] it is seen that the effective stress, 7, acting on a dislocation is a function of 7,. Therefore 7, becomes important in any description of the work-hardened state. In this paper the value of 7, as a function of strain and its variation with depth are reported for aluminum single crystals. In particular, it will be shown that the end of Stage I occurs when the net stress, 7, on the secondary slip system is equal to the critical resolved shear stress. To measure Ts, single crystals of aluminum were deformed in tension to various strains, whereupon the load was removed and a known amount of metal was removed by electrolytic polishing. The differ- ence between the final flow stress before the specimen was unloaded and the initial flow stress upon reloading is designated as ?Tp and is the decrease in the stress due to the removal of the surface layer in whole or in part. The value for Tp is taken equal to -Ts. EXPERIMENT PROCEDURE The details of the tensile apparatus, method of electrolytic polishing, and crystal preparation were the same as those used previously,1"3 The single crystals were 1/8 by 1/8 in. in cross section with a 3-in. gage length. The initial purity of the aluminum was 99.997 pet. The specimens were held in vacuo at temperatures 50°C below their melting points for 16 hr and furnace-cooled. Just prior to the application of the tensile stress the specimens were electrolytically polished to remove 0.004 in. from the thickness. This latter operation was conducted after the specimen was placed in the tensile apparatus. The tensile tests were conducted at a strain rate, i, of 10"5 sec-' and a temperature of 3°C. The aluminum crystals used for the determination of 7, are designated A1-3-12 and A1-116. The orientation of the various crystals used throughout the investigation is shown in Fig. 1. The ?Tp values for specimens A1-3-12 as a function of Ax were determined mainly at four strain levels, i.e., ? = 0.0217, 0.0381, 0.0593, and 0.075, where Ax is one half of the total reduction of the thickness after polishing and ? is the re-

Jan 1, 1965

By H. L. Hartman

The estimation of the magnitude of pressure changes which occur in mine ventilation circuits is of primary importance to the mining engineer in making changes in an existing mine or in projecting the ventilation requirements of a new mine. It is a formidable task in many cases, because no adequate theory is available and empirical data are unreliable or even lacking. The common practice of increasing one's estimate of the mine static pressure by an arbitrary "safety factor" to compensate for the unknown is a poor substitute for accuracy. Generally little difficulty is encountered in calculating friction losses in mine airways. As long as the friction factor can be reliably estimated, the well-known Atkinson formula gives accurate results. However, it is in the determination of shock losses that the ventilation engineer encounters difficulty and is apt to resort to an arbitrary allowance. Shock losses may constitute as little as five or as much as twenty-five percent or more of the overall pressure drop in the mine, and such allowances are generally completely unsatisfactory. Since other shock losses have been covered by McElroy (1), this paper deals with a long-neglected source of shock and pressure change in ventilation circuits, divergence and convergence of airflows, here referred to by their more common mining terms, splits and junctions. PREVIOUS WORK There is practically no fundamental information available in ventilation literature on the splitting and junction of airflows, either in mining or mechanical engineering periodicals or handbooks. Fluid mechanics textbooks seemingly avoid the subject of divergence and convergence, except for brief empirical treatment. The only investigation reported for mine ventilation systems was by Weeks, et a1 (21), in 1933. Although applicable to the case of line brattices in coal mines, it cannot be applied to the general case of mine splitting and junctions involving change of direction with little or no area change. In dealing briefly with the subject of shock losses at splits and junctions, McElroy (1) suggests only that they be considered comparable to bends, with losses at junctions being increased 50 pct to allow for interference of merging streams. He recognizes the importance of quantity ratio but concludes that exact quantitative data are lacking to compute losses at splits and junctions. A very capable summary and analysis of the state of knowledge in industrial ventilation and fluid mechanics regarding losses due to divergence has recently been reported by Gilman (3). In considering all earlier work dealing with both air and water as fluids, he compares results on a common basis and obtains good empirical agreement. For divergent flow, the controlling variable in each branch is the quantity ratio, although the deflection angle is of secondary importance. Empirical equations are presented for straight and 90-deg branches with varying velocity ratios, assuming branches smaller than the main duct. These formulas are modifications of the Borda equation for abrupt contraction and expansion. The only information available on shock losses in convergent flow are approximate experimental data presented by Alden (4) and the Manual of Recommended Practice for Industrial Ventilation of the American Conference of Governmental Industrial Hygienists. Alden considers the effects of both quantity ratio and deflection angle. The data indicate an effect opposite to that observed in divergence, the shock loss varying directly with quantity ratio. SHOCK LOSS THEORY Because pressure losses due to shock have been found to bear a constant relation to the mean velocity of flow in a given conduit, they are frequently expressed as a dimensionless function of the velocity head, termed the shock loss factor. For airflow in ducts and mine airways, the shock loss may be represented by the formula (1): Hx - XHv, (1)

Jan 1, 1961

By J. H. Polhems, R. B. Brackin, D. B. Grove

THE heavy media separation process plays an outstanding role in the concentration of 4000 tons of zinc ore per day at the Mascot mill of the American Zinc Co. of Tennessee. Of the total tonnage, 72 pct is treated in the heavy media separation plant to reject 56 pct of the ore as a coarse tailing, which has a ready market. Concentrates from this separation are beneficiated further by jigging and flotation. Approximately 25 pct of the total zinc concentrate production is made in the jig mill. Jig tailings are ground and pumped to the flotation circuit where the balance of the production is made. Fig. 1 shows a generalized flowsheet of the mill. The Mascot ore is a lead-free, honey-colored sphalerite in dolomitic limestone, with lesser amounts of chert and some pyrite. A mineralogical analysis is given in Table I. After 10 years of successful operation with galena medium and treatment of nearly 10,000,000 tons of ore, a decision to convert to ferrosilicon was made early in 1948 because of the increasing price of galena and consequent high operating costs. The conversion was made on Nov. 6, 1948, and the results obtained since that time have shown remarkable improvement over those made with galena. The Table I. Mineralogical Analysis of Mill Feed, Pct Calcium carbonate 49.5 Magnesium carbonate 35.2 Iron oxide and aluminum oxide 1.5 Zinc sulphide 4.5 Insoluble 9.3 100.0 Table II. Comparative Data, Galena and Ferrosilicon Ferro- Diner-Gelenaa siliconb ence Operating costs per ton milled, ct. 21.21 9.12 12.09 Medium consumption per ton milled, lb 0.80c 0.15 0.65 Reagent consumption per ton milled, lb 0.45 0.02 0.43 Tailing assay, pct Zn 0.310 0.297 0.013 Concentrate. oct Zn 12.08 10.33 1.75 Heavy medla ieparatlon recovery. pct 89.38 90.22 0.84 Mill feed rate, tons per hr 153 166 13 Heavy mesa separation feed rate. tons per hr 100 10 0 Tons milled per heavy media separation man shift 350 620 270 Mill feed to coarse tailings, pct 51.0 56.7 5.7 Lost mill time, pct 5.6 5.0 0.6 Power consumption, kw-hr per ton 2.06 1.92 0.14 a 1947. " First 6 months of 1950. c Net consumption after deducting credit for reclaimed waste galena. Consumption of new galena was 1.320 lb per ton milled. For entire life of galena operation, a credit of 40 pct of the value of the new galena added was realized from the sale of waste galena. comparisons given in this report cover the first 6 months of 1950 as representing the ferrosilicon operation, and the year 1947 as representing the galena operation. This was the last full year in which galena was used exclusively and is representative of the best work done during the 10 years of operation with this medium. After only 2 years' operating experience, with ferrosilicon and treatment of 1,807,585 tons many advantages have been revealed and are summarized in Table 11. Development Prior to the introduction of the heavy media process, all the mill feed was crushed through 5/8 in. and treated by jigging. A finished tailing assaying 0.66 pct Zn was made on rougher bull jigs, and cleaner jig tailings were ground for treatment by flotation. The first test work on the sink-and-float method of mineral beneficiation was carried out at Mascot in 1935, using a 3-ft cone and galena medium for batch tests. The following year a 6-ft cone was installed for pilot-plant work. This unit became a part of the mill circuit on March 1, 1936, and handled a gradually increasing tonnage in the next 2 years as the process developed to the point where it could treat all the + 3/8-in. material in the mill feed. Coarse jigging was then discontinued on March 1, 1939, and all coarse tailings have been made by the heavy media separation plant since that time. Feed Preparation: The original feed preparation plant consisted of a drag washer followed by two 4x10-ft Allis-Chalmers washing screens. A surge bin and two additional 5x12-ft AC washing screens were added in 1943. Use of primary and secondary washing screens was found essential to provide the cleanest possible feed for the cone and thereby avoid excessive contamination of the galena medium. Improved washing was obtained by replacing the drag washer with a 7x20-ft Allis-Chalmers scrubber, shown in Fig. 2, which has been in service since May 1944. Throughout the life of the galena operation, delivery of extremely muddy ore to the mill overloaded the medium cleaning system, and it frequently was necessary to cut off the feed and clean the medium for several hours until its normal viscosity had been re-established. The cleaning circuit

Jan 1, 1952

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.&apos; Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.&apos; The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By E. C. Barfield, D. G. McCarty

Two-dimensional analyses offer considerable promise in providing the basic information required to effect more precise control of petroleum reservoir performance. This paper describes a method for conducting some engineering analyses of this type using a high-qreed digital computer. The general approach is to (I) develop a representative numerical model of the reservoir and (2) employ a suitable numerical technique to solve the basic equation of flow and to develop the required engineering information for the particular case represented by the model. This technique has been used to calculate pattern performance in connection with several field projects involving water injection into oil reservoirs. This type of analysis involves sequentially (I) calculating the pres-&apos; sure distribution in the reservoir and (2) tracking the progress of the interface between the displaced and displacing fluids in a step-wise manner to provide a depletion history of the operation. The particular analysis presented in this discussion is subject to the restriction that the mobility of the displaced and displacing fluids be equal and assumes that the fluids are incompressible and that gravity and capillary pressure do not affect the shape of the flood pattern. Complete two-dimensional .flexibility is maintained with regard to definition of reservoir rock and fluid characteristics, placement of physical restrains and boundary conditions, investigation of flow characteristics in the reservoir, and movement of the displaced and displacing fluid interface. The results of these studies indicate that the highspeed digital computer is well suited for conducting reservoir performance studies in two-space dimensions and that dependable numerical techniques are available for making such analyses. INTRODUCTION One of the problems facing petroleum engineers is that of providing more precise engineering control over reservoir operations at all stages during the depletion cycle. The most direct approach to this problem is to simulate the reservoir with some type of physical or mathematical model and use the information developed from the behavior of the prototype to predict the performance of the actual reservoir. This principle is, of course, not new, and a variety of simulation techniques have been developed to provide information on the behavior of oil and gas reservoirs. One straightforward refinement of present reservoir analysis techniques is the progress from one-dimensional reservoir models to those where the reservoir can be represented in two- and three-space dimensions. Multidimensional reservoir analyses are desired in order to show not only what is happening in the reservoir but in addition to show where in the reservoir the various phenomena of interest are occurring. Thus far, two-dimensional analyses have been confined predominantly to potentiometric and electrolytic model studies. However, when large numbers of wells are involved and where large-scale models are required, such problems become very tedious and instrumentation problems become acute." It is possible through use of numerical methods and general purpose digital computers to avoid many of the instrumentation difficulties and to relax some of the restrictions of previous techniques. The purpose of this paper is to discuss some recent experiences with the use of high-speed digital computers for predicting pattern performance in fluid injection operations and to describe the numerical procedures which have been used for making such analyses. THE NUMERICAL MODEL The problem of representing the reservoir with an appropriate numerical model is composed of at least two important considerations. The first requires that an adequate description of the reservoir mechanism be formulated in the form of the basic differential equation describing the process. The second consideration is definition of the physical characteristics of the reservoir. The latter requires that representative basic data be obtained, examined, and interpreted to provide sufficient detailed definition of the pertinent physical properties throughout the system. The Differential Equation One of the basic assumptions made for the purpose of performing the two-dimensional studies being dis-

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.&apos; At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.&apos;-&apos; The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By T. I. Moore, L. A. Painter

THE electrolytic zinc plant of the American Zinc Co. of Illinois was described by Davidson&apos; in 1944. Since then, improvements as well as expansion of the plant facilities have been made. In order to increase the production of high grade zinc which was needed for war purposes, an expansion program designed to double the slab zinc capacity was started in 1942 and completed in March 1943. This expansion was propagated by a contract between the American Zinc Co. of Ill. and the Defense Plant Corp. The contract included the facilities of the Fairmont City, Ill., property of the American Zinc Co., where a suspension-type roaster with contact acid plant, cadmium distillation furnace, Waelz oxide and densifying plant, and horizontal retort furnaces were installed. The expanded Monsanto, Ill., plant and the additional facilities of&apos; the Fairmont plant were designed to integrate the metallurgical treatment of zinc concentrates for the production of special high grade zinc at Monsanto with the production of acid, cadmium, high grade zinc from furnace skimmings and the Waelz treatment of leach residue at Fairmont. In general, the original flowsheet was not changed, except for the addition of the filtering, drying and reclaiming of leach residue, and the treatment of purification cake for the recovery of copper, cadmium sponge, and zinc. Fig. 1 is a flow diagram of present operations. The original plant facilities, desi-gned for 50 tons daily production of slab zinc, had some units which were more than adequate. Therefore, in expanding the facilities to 100 tons per day, it was not necessary to double all operating components. Table I gives the comparison of the changes made in the unit operating components for the original facilities, 1941, the 1943 expansion, and the 1951 facilities. During the past 11 years a number of improvenients have been made resulting in: 1—an increase in slab production, 2—higher recoveries on the calcine treated, 3—better quality of slab zinc produced, 4—higher current efficiencies, and 5—less man hours Table I. Changes in Operating Facilities Operating Unit 1941 1943 1951 Calcine unloading (pneumatic), 10 tons per hr 12 calcine unloading track hpr. and elev., 60 tons per hr 1 Calcine storage, tons 1,000 2,000 2,000 Leach tanks, 35 vol. tons. No. 3 5 6 slurry mixing 6x6 ft stainless tank, No. 1 Ball mill. 4.5 rt x 16 in. conical. No. 1 CLassifier duplex, No. 1 1 Thickeners. 50 it diam. No. 2 9 2 Filter thickeners, sq ft &apos;-- Moore filters, sq ft 5.760 11,520 Drum filters, 10 ft diam x 16 ft, No. 3 3 Rotary arlers, No. 1 2 1st stage Cu-As purificatlon tank. 90 vol. tons, No. 3 Solution heaters, No. 3 Filter press, 30x30 bronze, No. 4 Zinc dust purification tanks, 45 vol tons. No. 3 5 4 Filter press, 36x36 bronze, No. 3 5 3 Cadmium recovery plant: Process tank. No. 5 2 Cake roaster, 20 ft diam x 4 hearth. No. 1 Filter press, 24x24, No. 4 1 Sponge wash box, 4x6 ft, No. 1 Evaporative cooling unit (vacuum), No. 1 Purified storage tank, vol. tons 400 400 400 Cell acid storage, vol. tons 400 400 400 Electrolytic cells, No. 180 372 372 Cell room ventilation, cu ft per min 35,000 125,000 125,000 Cell cooling water. gal per min 1,500 2,300 2,300 Deep well 16 in. x 95 ft, 1500 gal per min, No. 2 3 3 Melting and casting furnace, 130 ton. No. I Furnace fume scrubber unit, No. 1 Dross drums, No. 2 Dross roaster, 8 ft diam x 8 hearth, No. 1 Electrolysis power conversion, kw 6,250 23,750 23,750 Power transformers, 13,800/440, kva 1,000 1,500 2,000 Steam boilers fire tube, 15 psi, lb per hr 12,000 18,000 18,000 Steam boilers water tube. 125 psi, Ib per hr 30,000 Air compressor, 2 stage. 300 cu ft per min. 100 psi, No. 1 2 Air compressor, 1 stage, 300 cu ft per min, 20 psi, No. 1 Vacuum pumps, 18x7, 720 cu ft per day, No. - - . Vacuum pumps, 24x11, 1.633 cu ft per day, No. 3 3 Building area, sq ft 60,854 113,568 115,000 per ton of metal produced. In the summer of 1944, the "reverse" leaching process was placed in operation and since it has been described,&apos; no further description will be given. Other facilities and changes which have contributed to the process improvements were the scrubbing of fume from the melting and

Jan 1, 1953

By R. L. Fleischer, W. F. Hosford

Tensile data for coarse grained aluminum Polycrystals suggest that the "grain size" effect is not due to dislocations piled up at grain boundaries but rather is primarily a relative size effect due to surface crystals being weaker and less confined. STUDIES directed at interpreting hardening of poly-crystalline metals normally identify their strain hardening properties with those in some particular type of single crystal.1"4 The recent recognition in face centered-cubic metals of a nearly linear stage with rapid hardening occuring at comparable rates for both polycrystals and single crystals, suggested that the same process or processes determine both cases and hence that there exists some justification for the use of single crystals to understand polycrystals. Further evidence for the above view may be found by an approach initiated by Chalmers:5 By using bicrystals of controlled orientation it is possible to begin to assemble a polycrystal and also to study grain boundary effects in detail. In this way it has been found that a single grain boundary affects easy glide but not the subsequent stage II hardening.6 This result suggests that a sensitive way to observe grain boundary effects in polycrystals would be to vary grain size and measure easy glide. As will be seen, easy glide is only possible for coarse-grained samples, and hence the results will serve to fill in the gap in measurements between single crystals and bicrystals on one hand and fine-grained polycrystals on the other. One problem inherent in comparing single crystals with polycrystals is the uncertainty as to what slip systems are acting in a polycrystal. To compare the two types of samples, rates of shear hardeninn---L. on the acting -planes are needed. and these may be computed only if it is known what particular systems are active. The acting systems were examined for a coarse-grained polycrystal and it will be shown that the systems supplying the preponderance of slip can be determined with little ambiguity. EXPERIMENTAL PROCEDURE Twelve samples of aluminum were prepared by chill casting into a heated graphite mold, followed by annealing at 635° ± 5°C for 24 hr with an 8-hr fur- nace cool, and finally either etching7 or electropol-ishing.&apos; The samples, with a 7 to 10 cm length between grips and 4.4 by 6.6 mm in cross section, were deformed at a strain rate of about 3 10 -3 . per min in a tensile device which has been described elsewhere.5 The composition was reported by Alcoa as 99.992 pct Al, 0.004 pct Zn, 0.002 pct Cu, 0.001 pct Fe, and 0.001 pct Si; nine samples were deformed while immersed in liquid helium and three in air at room temperature. The stress-strain curve for one of the samples (P-1) deformed at 4.2 "K has been reported previ~usl~.~ This sample was selected for determination of active slip systems. Eighteen of the crystals were examined by optical microscopy to determine the angles of slip line traces and by X-ray back reflection to determine orientation. By this means the slip planes were determined and the resolved shear stress factors for possible slip systems could be computed. Finally each sample was sectioned so that after etching, the number of crystals could be counted for each of ten newly exposed surfaces. The average of these ten values will be termed n, the number of crystals per cross section. Values of 11, varied from 1.9 (nearly bamboo structure) to 12.7. Sketches of typical cross sections appear in Fig. 1. RESULTS AND DISCUSSION: SLIP SYSTEMS 1) Determination of Acting Slip Planes—The stress axis orientation and operative slip planes in eighteen crystals of sample P-1, as determined by slip line traces and crystal orientation, are summarized in Fig. 2. For one of the crystals two planes had a common trace. so that the traces alone did not distinguish which plane or planes were slipping. However it was found that the stress resolving factor for the primary system was 0.386, .while that for the most stressed system in the other plane (indicated bv the dotted arrow) is 0.138. It will be assumed tgerefore that only the primary plane acted. Since the orientations were determined after extending the samples 4 pct, the stress axes may be rotated from their original value by as much as 2 deg in some cases. It is interesting to note that in five crystals only one slip plane acted, in eight two acted, and in five three planes were observed—an average of two slip

Jan 1, 1962

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.&apos; &apos; Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.&apos;" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.&apos; Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964