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By F. W. Bowdish

A theoretical and experimental laboratory study has shown that the rate of breaking of oversized particles in a ball mill is proportional to 1) the concentration of such particles, and 2) the area of the balls, provided that the balls are larger than a certain size relative to the particles. If all undersized material were removed as formed, the rate of breaking would be almost independent of the quantity in the mill. Rate equations are given which are similar to those for zero, first, and second order reactions. Deviations of small balls from the equation for a second order phenomena are quantified by a factor called "nipping efficiency." Some data are correlated by a dimension-less equation, which is used to estimate nipping efficiencies from data not in the correlation. The investigation described here was undertaken after a literature survey revealed that little was known concerning the mechanism of breaking of particles within a ball mill and the effect of this mechanism upon grinding rates. One paper, by Roberts1 , offered a theory concerning the mechanism of breaking, and a rate equation for the breaking of particles larger than some size to particles smaller than that size. That paper provided the starting point for a theoretical and experimental investigation of grinding under carefully controlled conditions. THEORETICAL CONSIDERATIONS In his paper on the probability theory of ball mill grinding, Roberts theorized that "... a given expenditure of power leads either to a certain number of point to point blows per bp-hr or to a certain distance of line contact per hp-hr ..." He assumed that the balls touch each other during each blow or during moving contact. Then he said that a volume of pulp, dependent upon the size being considered, would be covered per minute within which all oversized particles would be crushed to particles smaller than that size. Naturally, the higher the concentration of oversized particles in the pulp, the higher the rate of which they would be broken. From this reasoning Roberts obtained the differential equation -dC/dt = k hp/ton C (1) where k is a constant for any size of particle, density of particle, and moisture content of pulp. C is the percentage of oversize in the material to be ground, t is the time, and hp/ton is the power input per ton of material in the mill. He then integrated the equation to log Co/Ct = k/2.3 hp/ton t , where Co and Ct are the percentage of oversize at time zero and t respectively. By always using the same quantity of material in a mill and assuming that it required constant power to run the mill, he was able to combine the horsepower per ton factor with the other constants to give an equation for a first order rate.

Jan 1, 1961

By Sumner M. Anderson

Any discussion of outside support to Latin American mineral industries must concede at once the pre-eminent role of U. S. industry and business. American capital has developed the great copper resources of Chile and Peru, the lead-zinc of Peru and Mexico, the bauxite of Surinam and Jamaica, the petroleum and iron ore of Venezuela. American consumers have provided the market for their products. U. S. companies operating south of the border have trained Latin American geologists, engineers, chemists, and skilled labor—including metal, mineral, and fuel technicians—to new and greater competence. The industrial demands of World War II drastically altered world economics and concepts of U. S. foreign mineral requirements. In this country discovery of vital mineral resources fell far behind the alarming depletion rates, and there was new appreciation of the actual and potential importance of the world's less extensively explored areas. During the war and afterward, the task of supplying the nation's mineral requirements became greater than private industry could carry alone, and the Government assumed a position of continuing support. In Latin America, as elsewhere, this support applies in three categories: banking, procurement, and technical assistance. The first two are now generally accepted as necessary Government functions; the third has often been misunderstood and misinterpreted, although it has given rise to legitimate controversy. There have been major accomplishments in all three categories, as well as some errors of judgment. Since the beginning of World War 11, U. S. Government financing, procurement, and technical assistance have been applied on a large scale to a wide range of commodities and services throughout the free world. The present discussion—under the separate headings mentioned—will concern only the support related to a single industrial group in a single geographic area. During the War Federal banking was conducted on an emergency scale by temporary agencies created to meet the abnormal circumstances. Unfortunately, there are no readily available data on these activities that would permit evaluating loans and credits extended for mineral projects in Latin America. The only agency operating in this field since World War II is the Export-Import Bank, under its own authority and to some extent from credits authorized by the Office of Defense Mobilization. The Bank can offer more capital—on more favorable terms—than is available from most Latin American banks, and its staff of engineers evidently can appraise loan applications more favorably than commercial banks in this country are willing to do. The risks seem to be justified, as defaults have been well under 1 pct of total loans. From V-J day 1945 to the end of 1957, mineral loans to Latin America have been authorized for projects totaling $541.63 million in eight countries. In order of magnitude of credits, they have been made to Brazil, Peru, Chile, Mexico, Argentina, Venezuela, Guatemala, and Bolivia. In order of magnitude by industries. they are for development and expansion of steel mills, copper, manganese, nitrate plants, iron ore, zinc plants, sulfur plants, cement plants, tungsten, coal, and lead. Loan Distribution: By far the largest loans have been $307.9 million for iron and steel projects in Brazil, Chile, Mexico, Argentina, and Peru: $100.4 for developing the great low-grade copper deposits of southern Peru; and $55.3 million for developing manganese deposits in the Territory of Amapa, Brazil. Others range from $20.8 million for a zinc smelter in central Peru to $19 thousand for iron-mine trucking equipment in Chile. It has been noted that 59 pct of the loans have been to foreign companies, 14 pct to companies of mixed foreign and American capital, and 27 pct to American mining companies. About 40 pct of the total authorizations has been disbursed so far. In addition to these amounts, the Strategic Materials Division of the Economic Cooperation Admin-

Jan 1, 1959

By Curtis Wilson

FROM the results of his investigation of the hardenable copper-nickel-silicon and copper-cobalt-silicon alloys, M. G. Corson1 explained the dispersion-hardening effect by assuming the precipitation of the inter-metallic compounds nickel silicide and cobalt silicide, and on this basis he constructed diagrams for the pseudobinary systems copper-nickel silicide and copper-cobalt silicide. A consideration of these diagrams and of the factors that exert such an important influence upon the rate of precipitation, such as degree of supersaturation, nucleus number and rate of diffusion, leads to the expectation that the rate of precipitation of the silicides on reheating the quenched solid solutions at temperatures below the alpha-phase boundary should increase continuously as the reheating temperature is raised. The present investigation shows that while this rate does increase with the reheating temperature in a general way, it does not do so continuously. Supplements to Corson's diagrams are offered, showing the discontinuities, and slight modifications in the solubility curves are suggested.

Jan 1, 1933

The pellet plant, built by Dravo Corp, in Groveland, Mich., for the Hanna Mining Co., is now in full operation. Although using jasper, a type of iron ore with low iron content (approximately 28% Fe), the plant has a rated capacity of 1,250,000 tans of pellets per year. In its four years of existence, the nearby concentrating plant has seen its capacity increase from 700,000 tons to 1,500,000 tons a year as part of a major expansion program at Groveland. Utilizing the Dravo-Lurgi continuous grate process, the pellet plant produces %a-in. pellets of more than 60% iron content. The fully-hooded pelletizing grate, largest in the U.S., is 9 ft. 10% in. wide and 223 ft. 1% in. tong over 34 windboxes, with an effective hearth area of 2195 sq. ft. Drying, firing, and cooling functions are all carried out on this single piece of equipment.

Jan 4, 1964

By H. K. VAN POOLLEEN, W. Hurst, H. C. Bixel

In an earlier publication* I showed the development of the instantaneous point source solution for a well producing at a constant rate at the center of a system of two radial, adjoining sands of different permeabilities. I also showed how a wellbore radius could be incorporated if this were the development required. For the purpose of that paper and the point I wished to make, this solution served. It yielded a simplifying solution of sands in series identified by Eqs. VI-26 and VI-27. (These equations are reproduced in part by Bixel and van Poollen as their Eq. 3, Page 302.) I am well aware that the simplified solutions are approximations. The facts that these Ei-functions satisfy the diffusivity equation and meet the boundary conditions both at the well and at the interface between sands, and that the earliest time considerations yield zero pressure drop, are evidence that the solutions are good approximations. This was the purpose for these formulas, which I interpret that where the permeabilities are of finite order of magnitudes in the respective media, the relations give satisfactory answers. However, from the authors' point of view there are reservations, which leads me to consider their entire generalization as illustrated in their Figs. 1 through 14. What I understand from their storage capacity, relationship Fs, which is the ratio of the product of porosity and compressibility of Sand II to Sand I, that is employed here by the authors as a correlative means of identifying one figure from another, there is nothing in the exact mathematics that supports such a term as a means of correlation. This is taken out of context, unsustained that this applies. Here the mathematics are known, where the true correlation is the diffusivity term of one sand to another. This entails permeability that refers back again to the term M in their paper for the transmis-sibility of fluid from one sand to the other that should have also been a part of this storage capacity. In Figs. 8 through 14, which purported to show the simplified equation following this correlation, there are apparent discontinuities for M equal to or less than 0.1000 that differ from the trends for greater values of M. In this connection there is no reference radius given for this cumulative pressure drop in the paper that would permit me to make these calculations. However, what is clear for M equal to 0.1000 or less we are treated to almost a closed barrier at the interface; a condition entered by the writers without qualification. This across-the-board treatment of these simplified formulas, whatever the motive of the authors, enters into a range of permeabilities that even I as the contributor would have reservations that such could apply. Under comparable conditions I would be looking at a closed reservoir or some facsimile for such. The extent to which the approximation or the exact equations pertain is not evident in the generality offered by Bixel and van Poollen in their paper. Only when they or other writers show the comparison of the pressure distributions within the formations can one be able to judge the rational limits to subscribe to the simplified formulas.

Jan 1, 1969

By L. H. Simons, H. H. Spain

I NT RODUCTION Theory indicates that linear water-floods should exhibit scaling and stabilization properties in both oil-wet and water-wet porous media'. Experimental verification of these proper-ties in oil-wet media was obtained some time ago', and more recently, Perkins', employing a high permeability unconsoli dated sand and a low oil-to-water viscosity ratio, has obtained flooding data in a water-wet medium which follow the pattern of scaling and stabilization. Also, Root and Calhoun3 have found similar trends in the displacement of gas by liquids from unconsolidated sands. In general, however, the experimen-tal evidence appears still somewhat conflicting since scaling and stabilization of water floods in water-wet media has not been observed in most of the studies to date'.".'. The purpose of this paper is to provide a more comprehensive picture of waterflood behavior in water-wet media and to corroborate the validity of the scaling and stabiliza-tion concepts. The need for differentiating between the intrinsic nature of water-oil displacements inside a porous medium and perturbating secondary end effects is discussed, pertinent experimental procedures are outlined and the results of flooding tests conducted at low and at high oil-to-water viscosity ratios on con- solidated, water-wet Alundum cores are analyzed. END EFFECTS IN WATER-WET MEDIA Outlet End Effects The peculiar feature of the outlet end effect in water-wet cores is that it not only results in an excessive wetting phase saturation at the outflow face,'.' but that it also retards the moment of water breakthrough: i.e., causes an undue delay in the appearance of water in the produced effluent. Conditions existing in a water-wet core when water first arrives at the outflow face are schematically shown in Fig. 1. At this flooding stage the saturation distribution, Fig. la, has not yet been distorted by the outlet end effect. A water-invaded pore at the outlet core face, opening into the oil-filled void space between the end of the core and the end plate of the flooding cell, is illustrated in Fig. lb. The curvature of the water-oil interface is concave toward the outlet, and the pressure on the water side of the interface is lower than on the oil side by an amount equal to a certain capillary pressure (Fig. lc). Before the water (of this particular pore) can be produced from the core, it is apparent that the pressure in the water phase must exceed that in the oil outside the core. Accordingly. when water first reaches the outlet face, it will not leave the core but will accumulate inside, and only oil will be produced. Eventually, as the water injection is continued. sufficient pressure is built up in the water to reverse the curvature of the interfaces in the outlet pores, and only then will water be produced from the core. This stage, illustrated in Fig. 2. corresponds to the conventional "water breakthrough" observed in flooding experiments. For purposes of discussion, it is convenient to distinguish between the flooding stage at which water first arrives at the outlet face of a core (Fig. 1) and the stage at which water is first produced from the core ( Fig. 2). The former will be referred to as "water arrival" and the latter water breakthrough. In oil-wet media

By D. P. Harris

This paper examines recent developments and work in progress on the application of quantitative methods and computers to the appraisal of the mineral resource potential of discrete areas by employing reconnaissance geological information and general economic relationships. The perspective of this paper might be that of a firm planning a regional exploration program or of a legislative body seeking to choose between several alternative actions on the basis of their impact upon the regional resources. In addition to this general survey and commentary, an example is presented of the use of geostatistical analysis and computer simulation to evaluate the economic mineral resources of the Seward Peninsula of Alaska.

Jan 1, 1969

By H. E. Criner, M. G. Driessen

THE cyclone thickener has two important applications in wet washing plants: (1) water clarification, and (2) fine coal recovery. The thickener consists of a conical chamber into which the fluid is injected through a tangential nozzle at the periphery of the large end. The solids of the slurry are concentrated and removed from the apex of the cone while the "thinner" portion is discharged from a central tube in a flat head at the large end, fig. 1. The advantages of the cyclone thickener are that large volumes of slurry may be treated with small space requirements and that the underflow concentration may be controlled easily and readily to meet varying feed conditions. Control of Washery Water Solids Concentration: The first requirement, in the process of controlling solids concentration, is that the solids be removed from the body of circulating water at the rate at which they are introduced. If this condition is satisfied the concentration will remain at a fixed value and will not increase to uncontrollable levels. The second requirement is that the solids concentration

Jan 1, 1951

By A. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

Jan 1, 1967

By M. G. Driessen, H. E. Criner

THE cyclone thickener has two important applications in wet washing plants: (1) water clarification, and (2) fine coal recovery. The thickener consists of a conical chamber into which the fluid is injected through a tangential nozzle at the periphery of the large end. The solids of the slurry are concentrated and removed from the apex of the cone while the "thinner" portion is discharged from a central tube in a flat head at the large end, fig. 1. The advantages of the cyclone thickener are that large volumes of slurry may be treated with small space requirements and that the underflow concentration may be controlled easily and readily to meet varying feed conditions. Control of Washery Water Solids Concentration: The first requirement, in the process of controlling solids concentration, is that the solids be removed from the body of circulating water at the rate at which they are introduced. If this condition is satisfied the concentration will remain at a fixed value and will not increase to uncontrollable levels. The second requirement is that the solids concentration

Jan 1, 1951

Large deposits of manganiferous iron ores, representing several million tons of metallic manganese, occur in the United States. The Minnesota deposits of such ore are of outstanding importance because of their size, state of development, ease of mining and proximity to the Great Lakes, which permits water transportation to steel centers. In view of the fact that our steel industry requires large quantities of manganese, for which no satisfactory substitute has been found, and because our reserves of ferro-grade ore are comparatively small, the development of methods that will make our large deposits of manganiferous iron ores available as a source of ferromanganese is an important problem. Realizing the importance of this problem, some years ago the North Central Station of the U. S. Bureau of Mines and the Minnesota School of Mines Experiment Station undertook jointly the development of methods for recovering the .manganese content of manganiferous iron ores in a form suitable for the production of ferromanganese, the 80 per cent. alloy indispensable in producing steel. Two types of manganiferous iron ores have been described in previous reports.' The brown ores are higher in iron and lower in manganese than the black ores; the black ores are more siliceous but contain less phosphorus. The utilization of the iron content of the brown ores in the production of steel appears to furnish the best basis for their treatment. The method of attack has been to work out modifications in iron and steel practice so as to recover manganese in the form of slag comparable to ferro-grade ores. The greater part of the experimental work has been conducted with a 6-ton blast furnace and a 1/2-ton basic open hearth. This paper is devoted mainly to open-hearth tests in which high-phosphorus spiegel

Jan 1, 1930

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By J. B. Clark

In multiphase ternary diffusion studies, plots of the variation bf the composition on the isotherm constitutes one of the most effective methods of presenting experimental results, especially if such plots are made in a manner which relates the composition path on the isotherm with the diffusion layer structure in the couple. Unfortunately, if different conventions for plotting are used serious misinterpretations occur readily, causing apparent disagreement between investigators who actually share the same viewpoint. A common convention for mapping these diffusion paths is needed at this time because with the increasing use of the electron-probe X-ray microanalyzer, a much greater number of ternary diffusion studies can be expected in the near future. In an effort to prevent unnecessary confusion in the future litera- ture, a convention for these plots is proposed, as outlined below. A hypothetical example of the use of these conventions is given in Fig. 1 where the path of composition through the diffusion structure of the 100 pct A/50 pct B, 50 pct C couple is plotted on the appropriate isotherm of the ABC system. The lower case letters relate the region in the diffusion layer structure to the appropriate composition on the ternary isotherm. 1) The diffusion path is plotted on the isothermal section corresponding to the diffusion temperature of the couple. 2) The terminal compositions of the plotted diffusion path are the initial compositions of the couple halves—provided infinite boundary conditions are maintained. If, in either couple half, infinite conditions are not maintained, then the path terminates at the composition of the exterior surface of the couple. If, at this surface, the composition varies with time or if the plotted path is time dependent, then the diffusion time should be noted beside the plotted path. 3) A solid line crossing a single phase field (e.g., line a-b in Fig. 1) denotes an existing layer of that phase in the diffused couple. 4) A dashed line crossing a two-phase field parallel to the tie lines (e.g., line g-h) represents an interface between the two phases with interfacial compositions designated by the ends of the tie-line. The line represents no spatial extent. 5) A solid line crossing a two-phase field so as to cut tie lines (e.g., line b-c or line j-k) represents a locally equilibrated columnar two-phase layer. The solid line should cut those tie lines which correspond to the lateral interfacial equilibria along the columnar

Jan 1, 1963

By K. C. Ko, D. A. Pifer

The theory of probability with respect to the failure of structures is discussed. It is shown that the probability of safety, probability of failure, and factor of safety are directly related to each other and that as standard deviation approaches zero, the probability curves approach a unit step function which can be interpreted as the conventional factor of safety. The factor of safety is numerically the ratio of the load to the strength of the material at a particular point or plane in an engineering structure. Mathematically, it can be illustrated as a unit step function undefined at the point where the factor of safety is one (Fig. 1). The uncertainty of variation of soil and rock strengths require factors of safety much higher than those used in other engineering structures. The factors of safety used are generally determined from past experiences with similar structures. However, the factors thus determined do not have any theoretical meaning or do not indicate any relationship to actual safety.' It seems, therefore, logical to develop a system with a sound theoretical basis to obtain a more suitable factor of safety for structures. An application of elementary theory of probability indicates that it is possible to relate this number to theoretical and practical engineering facts.

Jan 1, 1971

By Gerald Greene

Tan various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulfur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1) states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As.

Jan 1, 1935

By J. M. Uys, T. B. King

WalSH, Chipman, King, and rant' have measured the water content (as hydrogen) of actual steel-making slags. An average water content of 290 ppm was found for basic open-hearth tapping slags and 114 ppm for acid open-hearth slags. Upon equilibration of these slags at 1550°C with a 25 pct H20-75 pct Nz atmosphere, the water content increased to about 410 and 300 ppm for the basic and acid slags, respectively. Walsh et al. concluded that an acid slag was thus relatively far removed from equilibrium, and that basic slags showed a closer approach to equilibrium, with the water vapor in the furnace atmosphere. Herasymenko2 contended that these conclusions were unjustified, as the oxygen pressure used in the equilibration experiments, ;bout 5 x X atm, was quite different from that found in the furnace. Consequently, during the experiments the slag composition would have changed due to oxidation of ferrous iron. As an extension of Walsh's work and to attempt to clarify this matter, the solubility of water in a basic open-hearth slag was measured as a function of oxygen pressure. Similar measurements were also made on synthetic silicates in the "Fe0"-Fe203-SiO, system. The experimental technique has been described previously by Walsh et a1.l and Uys and King.3 Samples of the basic open-hearth finishing slag, contained in 10-cc platinum crucibles, were equilibrated at 1550°C with atmospheres of different oxygen pressure but constant water-vapor pressure, Ph~o = 0.192 atm. Calculations, as well as measurements, indicate that this figure approximates the water pressure of the combustion gases in a steam-atomized, oil-fired open hearth. Oxygen pressures in the open hearth can vary from 10"2 atm in the combustion gases to between l0-' and 10" atm in the steel bath. The former figure depends on the combustion practice and the latter on the carbon content and temperature of the bath. The oxygen pressure of the slag should lie somewhere between these extremes and is expected to be closer to that of the steel bath than that of the combustion gases. Oxygen pressures were therefore varied between 10" and 6 x l0 atm. At the lowest pressure the slag "puffed up" when quenched (indicating possible loss of water) so experiments were not conducted at lower oxygen pressures. The results are shown in Fig. 1, which includes the water content of the slag "as sampled". The results show that the water content of the slag increased appreciably on equilibration with water vapor at 0.192 atm pressure and that the water solubility apparently decreases with increased oxygen pressure. The solubilities found are comparable to those of the Li20-Ca0-Si02 system.3 Work with synthetic slags in the "Fe0"-Fe203-SiOz system was performed at 1500" C, with Ph20 = 0.192 atrn and for oxygen pressures varying between 10"2 and 10-lo atm. Samples for chemical analysis were prepared as described by Larson.4 The results are shown in Fig. 2. Some low-silica melts tested at low oxygen pressures "puffed up" when quenched and analyzed less than 100 ppm water; these results are not included in Fig. 2. The melts containing 40 mol pct silica also showed a tendency to "puff up" during the quench, when they were tested at the lowest oxygen pressure. These results indicate that, at constant silica content, the solubility of water decreases somewhat with increased oxygen pressure. The effect is, however, small considering the wide range of oxygen pressures studied. Also, at constant oxygen pressure (above about lom5 atm) the solubility increases

Jan 1, 1963

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By W. C. Winegard, A. Galibois, C. J. Beingessner

The effects of solutes on the distribution of two-dimensional configurations of grains in zone-refined tin have been studied. When solutes with partition coefficients (ko) greater than unity are added, three-sided pains become more prevalent and the growth law changes. It is shown by electron-Probe micro-analysis that a solute buildup occurs ahead of a moving grain boundary when ko > 1. It has been found recently1, 2 that solutes with partition coefficients greater than unity have a larger retarding effect on grain growth than solutes with k, less than unity. ko is defined as the ratio of the concentration of solute in the solid to the concentration of solute in the liquid with which the solid is in equilibrium. Niessen and winegard2 have suggested that this effect is probably due to the complex shape changes which occur during the process of grain growth and that no theory based on single boundary motion3-5 can explain the results. They suggested that the dissociation of the unstable fourfold junction was delayed in alloys where ko was greater than 1 because the boundaries at the junction had to move into a region of high solute concentration. If indeed this mechanism were correct, it was felt that not only would the dissociation of fourfold junctions be affected by the solute buildup ahead of the boundaries, but the collapse of three-sided grains would be impaired. These combined effects would naturally lead to a modification in the distribution of the number of sides per grain seen on a two-dimensional section. The present investigation was undertaken to test these hypotheses by examining the grain-growth process in detail. EXPERIMENTS The Distribution of Grain Configurations in Zone-Refined Tin as Seen on a Two-Dimensional Section. Following the method of Bolling and Winegard,6 zone-refined tin was cast into button-shaped specimens and, subsequently, plastically deformed under a drop hammer at room temperature. The resulting flat coin-shaped samples were annealed at 200°C, some for 50 sec and others for 100 sec. The specimens were then examined to determine the distribution of the number of sides per grain, i.e., the num- ber of crystals adjacent to any particular grain in the section. For simplicity, the grains were classified as three-sided, four-sided, and so forth; this concept is schematically illustrated in Fig. 1. As indicated by smith,' it was necessary to examine every grain within an enclosed area to obtain a proper distribution of the relative frequency of each type. The distributions for the two annealing times are illustrated in Fig. 2. The total number of grains examined is also indicated on the figure. It is evi-

Jan 1, 1965

By Richard Miller

RECENT studies of creep have made it apparent that plastic deforma-tion may occur in metals under stresses less than the elastic limit as deter-mined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapsell1 said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a. definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was deter-mined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instru-ments by A. W. Hanson4 on zinc and by Podaschowsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc.

Jan 1, 1936