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By V. M. Lovell

The recovery of apatite from the phoscorite ores occurring in the Transvaal, Republic of South Africa, involves a flotation process that is particularly difficult to characterize from a fundamental point of view. However, the reagents used, (tall oil fatty acid, nonylphenyltetraglycol ether, sodium silicate, and sodium hydroxide) can successfully bring about a separation of apatite from dolomitic calcite, which is the most troublesome gangue component. Recently, it has been demonstrated with some flotation feeds that the addition of certain polysaccharides can improve the flotation significantly. It has been shown that the metallurgy obtained is closely linked to the nature of the froth, and this, in turn, is influenced, often dramatically, by the presence or absence of certain of the reagents. The character of the froth depends less on the inherent frothing ability of these reagents than on the presence or absence of fine mineral particles in the froth, and on their surface characteristics and state of aggregation. The polyglycol ether and the polysaccharides have been shown to affect these properties, and it is suggested that a major function of these reagents is to modulate the properties of the fine particles in the pulp, thereby changing the character of the froth and giving rise to improved results.

Jan 1, 1976

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.'-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott's excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro's number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By V. Carlson, J. A. Rowe, E. O. Bennett

This report concerns the microbial flora found throughout the surface facilities of six water-injection systems in Texas and Oklahoma. Each system is described in detail and water quality data are presented when available. Pseudomonads and sulfate-reducers (Desulfovibrio) were the predominate organisms found in the systems. The genera Sphaerotilus, Bacillus, Achromobacter, Minococcus, Clostridium, Flavobacteriurn, and Sarcina were also isolated in significant numbers. Molds, iron bacteria, sulfur bacteria and soil bacteria were found less frequently in the systems. It is concluded that a complex microbiological flora exists in oilfield water-injection systems. A tendency for waters to deteriorate in passage through solid bed filters is also noted. INTRODUCTION The injection of water into a subsurface formation is often accompanied by numerous problems, the origin and nature of which are only partially understood. During the past few years, investigators have indicated that bacteria are involved in some of these problems even though very little specific information is available concerning this matter. It is surprising that investigators working on microbiological problems in water injection have never made a complete study of the flora of these systems. The logical course to pursue is that of identifying the microbial flora and then examining each organism individually and in combination with others to determine if they produce a particular problem. The objective of the present investigation is to identify the microbial flora in water-injection systems. In addition. the quality of the water in most of the systems was determined and some observations made on the extent to which passage through surface-handling facilities affects water quality. The information derived from this study can serve as a foundation for additional basic investigations. EXPERIMENTAL PROCEDURE The microbial flora of six water-injection systems were studied at 50 sampling points. These systems are experiencing problems which may be attributable to micro-organisms, and two were being treated with antimicrobial agents at the time of this study. The samples were obtained by inoculating 1.0 ml of the water onto the different media at the sampling point. The media used for primary isolation included nutrient agar, Strokes agar, M-10-E medium and semi-solid thioglycollate medium. The cultures were returned to the laboratory, incubated at 30°C until growth occured; then, pure cultures were obtained from individual colonies. The pure cultures were identified according to standardbacteriologica1 procedures. Those organisms not fitting identification criteria exactly, even though exhibiting close similarities to known species, are listed as unidentified organisms. Membrane filters were used to make water-quality tests at intervals before and after collection of the microbiological samples. The filter discs were 47 mm in diameter with a 0.45-micron particle-size retention, and the tests were done under closed conditions at 20) psi. Membrane flow rates are plotted as increasing filtrate volumes, and the total solids contents arcs given when available. An effort was made to sample at each place in a system where a change in environment occurred. In this manner, the effect of passage through filters, tanks, hay sections, etc., on the microbial flora and water quality could be observed. RESULTS SYSTEM A This waterflood system (Fig. 1) is about four years old and daily pumps approx&ately 110,000 bbl of oil-free sour water from a 3,700-ft deep reef. The

By M. L. Fuller

OWING to the nature of the die-casting process, freshly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effect of reaching a state of equilibrium at the aging temperature, beyond which no further change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (1) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time.

Jan 1, 1934

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By Walter Miller

The broad picture of petroleum refining engineering during 1934 continued to show a tendency in the direction of highly specialized processing improvements, particularly in manufacture of lubricating oil. The slowing up of the trend toward higher octane products in non-premium gasoline noticed in 1933 was definitely established as a fact by 1934 development, with just a slight indication of recession. No outstanding engineering achievements can be credited to 1934 in refinery cracking, unless the completion and successful operation of the 30,000-bbl. crude capacity combination cracking and skimming unit at Texas City, Texas, and a 20,000-bbl. similar unit in the East can be listed as such. Development and improvement was largely a continuation of previous lines of endeavor. Such trend as there is shows a continnation in the direction of very large integrated skimming and cracking units. A lessening of the cost of ethyl lead, coupled with the reaching of the octane number "ceiling," kept the subject of "reforming" low-octane gasoline into high-octane products pretty well in the background. Considerable interest, however, was shown during the year in cracking and polymerizing of refinery gases into high-octane motor fuel. The commercial development and application of this activity was greater in 1934 than during any previous year. Fair yields of gasoline of satisfactory stability and high antiknock value were reported, ranging from 2 to 8 gal. per 1000 cu. ft. of fixed refinery gas, yields varying with both the nature of refinery gas treated and processing methods. Assuming economic feasibility, regarding which there is still difference of opinion, gas polymerization offers the industry a possible outlet for its gases more in keeping with its basic chemical composition and value. The increased interest of railroads and heavy-duty truck and tractor manufacturers served to focus more attention on diesel fuels. The publicity given the Union Pacific diesel train, the Burlington "Zephyr" and others operated on special diesel fuels served to revive the intimations and fears of several years ago as to the ultimate replacement of the gasoline motor by diesel engines in even the passenger car field. How-

Jan 1, 1935

By P. P. Reichert, L. S. Gournay, N. T. Burdine

An investigation of equivalent pore entry radii in typical samples of petroleum reservoir rock and the pore volume associated with each value of pore entry radius has been made. Theoretical discussions together with experimental procedures for obtaining pore entry radii and the distribution of pore volume with pore entry radii are presented. Experimental results on a number of core samples, along with typical distribution curves, are shown. Data on the per cent of the pore volume filled by mercury at a pressure of 1500 psi are included. The results of re-runs of samples, made possible by regenerative apparatus, show the repeatability of the data and indicate the amount of physical change in the samples by mercury penetration. Theoretical equations for calculating permeability from pore size distribution data were derived and the results of such calculations are compared with measured gas permeability data. The effect of the shape, surface area, and weight of the sample on the pore size distribution of reservoir rocks was investigated experimentally. Mercury capillary pressure curves are compared with those obtained by the porous diaphragm method using pas to displace water. Standard core analysis techniques, in general, lead to quantities which are statistical averages of the varying properties of the samples under examination. Although such statistical information has real value in predicting the gross performance of porous bodies. it fails to provide fundamental information concerning the properties of the porous medium itself or any processes which may be occurring in it. For example, a gas permeability measurement on a core sample is an indirect way of determining an average pore radius for that particular sample. Since there are many combinations of pore radii that will give the same radius. and, hence, the same permeability, no information is obtained on the pore size distribution. Furthermore, similar values in permeability do not imply similarity in other properties of a porous medium. For instance, it is possible to have two core samples with identical permeability which would have different residual oil contents at the end of an air-oil drive, or even different amounts of interstitial water. It has been recognized for some time by the petroleum industry that a determination of pore size distribution for porous reservoir rocks offered promise of increased understanding of fundamental flow processes in the porous matrix. and therefore of petroleum res- ervoir performance in general. There have recently been published several methods for determination of pore size distribution in porous materials. A report is given here of the modifications in equipment and technique required to adapt one of these methods to measurements on petroleum reservoir core samples. Although only a few correlations or applications of the method are available for presentation at this time, the technique is brought to the attention of the industry so that the opinions and experience of others with this or similar techniques may be exchanged. It seems possible that the method will have wide application in the future. METHOD There are three general methods which may be employed to measure the pore size distribution in naturally occurring rock formations. One method1 is based on experimentally determined adsorption isotherms for calculating the surface area of the porous medium. Knowing the surface area and the pore volume, a rough estimate of the pore radius can be made. Since this method depends on the thickness and uniformity of the adsorbed layer, the validity of the results would be highly questionable. A second method utilizes capillary pressure data obtained by static dis-

Jan 1, 1950

By M. P. E. Desvaux, P. Charsley

OLIP-line observations on copper alloys, using the electron microscope, have been made by a number of workers,13 but this work has been confined to a brass. In a CuAl alloys Koppenaal4 and Koppenaal and Fine5 have made observations with the optical microscope and by the use of interferometry. They found that the observed slip step heights inside the Liiders bands accounted for only 42 pet of the total macroscopic strain. The suggestion was put forward that optically unresolvable slip in other parts of the specimen accounted for a major part of the macroscopic strain. This is surprising since it is known from other workers that slip in a brass is inhomogeneous; i.e., large amounts of slip occur on individual {lll) closelys paced than being shared by a large number of closely spaced planes. Furthermore, a brass and a CuAl alloys with high concentration of aluminum exhibit similar deformation characteristics and slip-line patterns. Prior to investigations into the behavior of copper and a CuAl alloys under reversed stresses in tension and compression, some preliminary experiments have yielded results which the authors think resolve this discrepancy, and throw some further light on the behavior of a CuAl in tension. An experiment was carried out on a 10 at. pet CuAl single crystal, of gage length 7.5 cm, diameter 3.1 mm, and orientation shown in Fig. 3 (inset), for the purpose of resolving the above discrepancy. The specimen gage length was electropolished for 10 min in a 50:50 orthophosphoric acid (SG=1.75)-distilled water system, with 2 v across the cell and a current density of 0.5 amp per sq cm. The cathode was made of copper. After a tensile strain of 0.067 ± 0.001, intense slip was observed over a length 2 cm of the gage length whilst the rest of the specimen was relatively undeformed. In the lightly deformed region, slip bands of mean width 20 /x were spaced about 1 mm apart on average. The transition from the heavily slipped region (usually called a Liiders band) to the lightly deformed region was gradual, the slip-band density increasing as the "Liiders band" was approached. In the latter, the slip bands became so close together that, to the naked eye, the specimen appeared to be continously slipped, and the typical microtopography of this region is shown in Fig. 1. Twelve electron micrographs were taken at random from replicas of the Liiders-band region, and the widths of the slip lines were measured. The slip lines account for an over-all tensile deformation of 7.0 ± 0.7 pet, after allowing for the lengths of the un-slipped regions, which is in good agreement with the macroscopic strain. The distribution of slip-line widths was also measured and is shown in Fig. 3. Since Koppenaal could not resolve slip lines with height less than 540A (limit of resolution represented by dashed line), then it was deduced that he could have measured only about 50 pet of the deformation within the 'Liiders Band'. It is concluded, contrary to the suggestion of Koppenaal,5 that virtually all the macroscopic strain is accommodated within the "Luders band" and that there is no need to invoke fine slip distributed uniformly over the gage length.

Jan 1, 1967

By George A. Roberts, Arthur H. Grobe

Tensile, hardness and density properties are presented for a new 18-8 stainless steel powder for the —50, —100, and —140 mesh cuts and also for a prepared blend containing 62 pct —325 mesh powder. The data were obtained for sintering temperatures of 2100° to 2350°F and for compacting pressures of 30 to 50 tons per sq in. A NEED has existed for a stainless steel powder of uniform composition from particle to particle, which could be readily molded and sintered, and which would yield moderate to high strength and ductility when processed into parts by standard powder metallurgy techniques. The literature reveals that previously available powders have been lacking in one or several of these desirable characteristics. Originally attempts to produce stainless steel powder by blending and diffusing elemental metal powders were unsuccessfu1.l A truly alloyed stainless steel powder reported by Dale in 1947 yielded reasonable mechanical properties but required an exceptionally high sintering temperature of 2400°F in pure dry hydrogen.' A later development reported in 1950 by Stern provided a stainless type powder of excellent molding properties' but this powder likewise required sintering at temperatures over 2350 °F and did not yield properties as high as those previously reported. The powder was not truly alloyed prior to sintering. A prealloyed stainless steel powder has been developed that is readily moldable at 30 to 50 tons per sq in., can be sintered at low temperatures (2100" to 2300°F), and which yields compacts with both high strength and ductility. The powder is prepared by the liquid disintegration method," direct from molten metal. Early attempts to make 18 pct Cr, 8 pct Ni stainless steel powder by this method did not produce a usable powder for pressing and sintering because of a preponderance of spherical particles with relatively high, surface oxide content. It was learned that silicon additions to iron alloys, powdered by this process, gave bright powder of low-oxide content and such additions were made to 18-8 stainless with similar results. An attendant change in particle shape occurred reducing the number of spheroids materially. The optimum composition which has been studied and is reported here contains approximately 2.5 pct Si. Silicon additions to stainless steel of the 18-8 type improve the resistance to high-temperature oxidation and promote the formation of ferrite. Corrosion resistance is, however, controlled by chromium content and even though ferrite may exist the corrosion resistance is not generally impaired.4 Experimental Procedure A detailed study of the 18-8, 2.5 pct Si powder has been made in accordance with the following outline: 1. Four blends a. — 50 mesh b. —100 mesh

Jan 1, 1952

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski's formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner's, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.' This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By W. E. Showalter

This paper discusses some of the results of combstion-drive tests which were made in a test cell using a sand bed 10 in. in diameter x 10-ft long. The test method is illustrated and described. The relationship between the API gravity of the in situ oil and the amount of air required for combustion drive is discussed in detail. Other things constant, the air requirement for combustion drive increases as the APl gravity of the in situ oil decreases. If the test results apply to actual reservoirs, the lowest-priced oils may cost the most to recover by this method. Information is shown which indicates that the effect of pressure on the amount of hydrocarbon burned is not large. A method of predicting air requirements from the API gravity of the in situ oil is presented. INTRODUCTION Combustion drive is the term used to identify the process of interstitial or in situ burning as an oil recovery method. Part of the in situ oil is burned to generate the energy needed to produce the remainder of the oil. Combustion drive as an oil recovery mechanism remains an economic uncertainty in spite of all the work that has been done by the industry in both laboratory and field?-6 This paper will show some of the results of tests which were made in a test cell for the purpose of studying the nature of the combustion-drive process. It will present data which indicate that the API gravity of the in situ oil is a significant indicator of the amount of air required to drive a burning front through oil sand. Air requirement varies inversely as the API gravity of the in situ oil. EXPERIMENTAL The tests were performed in a cell which utilized a cylindrical sand section 10 in. in diameter x 10-ft long. The thin-walled metal pipe which held the sand was wound with twenty external electrical resistance heaters which, by means of an automatic controller, maintained adjacent sections of the wall of the pipe at temperatures equal to the temperatures of the contained sand. Each heater covered 6 linear in. of the pipe. By this means lateral heat loss from the sand section was minimized, thereby causing the sand section to simulate more closely a horizontal increment of a combustion-drive reservoir. Fig. 1 shows a schematic diagram of the test assembly. Thermocouples to measure the temperature in the sand were located every 6 in. along the length of the sand section. The pipe containing the sand was enclosed in a cell designed for an operating pressure of 500 psig. The inlet air pressure was controlled at the inlet, and the gas flow rate was controlled and measured at the outlet of the cell. The oil sand used for the tests was prepared by mixing first water and then oil with the noncon-solidated sand using a closed mixer similar to a cement mixer. Table 1 shows a screen analysis of the sand. Ninety percent of the sand was 100 mesh or finer. This sand was a mixture of 80 per cent No. 120 Nevada White Sand and 20 per cent Tennessee Hi-Fusion Moulding Sand No. 3. The Nevada sand was a clean silica sand. The Tennessee sand con-

By Clarence Woods

ONCE a millionaire's plaything, the Santo Domingo mine, in Peru, is now, because of its metallurgical problem, an engineer's nightmare. It is deep in the montaña jungles of the Amazon basin, 140 mi. northeast of Tirapata, which is a rail- way station between Puno and Cuzco, and about 250 mi. east of Mollendo on the Pacific. The discovery was 111ade by Marian(-) Quispe, an Indian, who, while searching for quinine bark, was attracted by a slab of gold quartz 1x1 the rock wall of a narrow canyon. He broke off a piece, weighing 47 Spanish ounces and, that time, worth approximately $900. This he took to Francisco Velasco and Manuel Estrada, merchants of Coaza, who persuaded Quispe to lead them to the place, five days' journey on foot through a tangled wilderness. Velasco ' and Estrada denounced the claim

Jan 1, 1938

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By S. R. B. Cooke, R. O. Huch, C. S. Chang

IN the flotation of iron ores laurylamine derivatives have been used for considerable time.12 To effect satisfactory separation of the gangue, predominantly silica, from the iron oxide minerals, the addition of specific depressants for the iron oxides has been found necessary. Starches and starch products have been used for this purpose. 3 There is, however, very little published information on the effects of these materials and other variables on this process. In some cases it has been found that prior acid scrubbing and desliming are essential, 4 and depending upon the efficiency of the subsequent washing step, there will be accompanying changes in pH. It was the object of this investigation to test and observe the effects of the above factor as well as to examine and compare the action of various starches and starch products.

Jan 12, 1953

By R. S. Sherwin

The extractive metallurgy of primary aluminum from its ores is discussed with special attention to the production of alumina from high grade ores by the Bayer process, including differences between American and European practice and a brief description of some processes for lower grade ores and the electrolytic reduction of the oxide to aluminum. METALLIC aluminum is not found in nature, but the oxides, hydroxides, and especially the silicates are plentiful. The estimated percentage of in in the crust of the earth is about 8 pct while that of iron is about 5 pct. By far the larger portion of this is combined with silica in the form of various clay minerals and igneous silicate rocks. From the point of view of extractive metallurgy of aluminum, these are low grade ores while the better qualities of bauxite are the high grade ores. There have been various definitions of bauxite but perhaps the best definition at the present time is that bauxite is a rock or earth commonly used as an ore of aluminum or its salts in which the aluminum is present predominantly as a hydrate or a mixture of hydrates and hydrous oxides. It contains varying amounts of oxides of silicon, iron, and titanium and traces of compounds of some of the less common elements. The silica is mainly combined with alumina as clay or clay minerals which are hydrous aluminum silicates, although a part of it may be present as quartz sand. On the American continents, the alumina is mainly present as gibbsite, Al2O3 . 3H2O, and the same may be said of the best known deposits of the Dutch East Indies and some of the deposits in India. In France and other countries in Europe as well as in Africa, the alumina is present mainly as boeh-mite, A12O3 . H2O, but in some of these deposits it is mixed with minor amounts of gibbsite. Some other deposits, such as those in the islands of Haiti and Jamaica, evidently contain two or more hydrates or hydrous oxides of alumina in varying proportions. Perhaps the main portion of the alumina may be present as gibbsite and boehmite with the proportion between the two varying rather widely. In the silicate minerals, including clay, the alumina is chemically combined with silica and has not been separated satisfactorily by mechanical or physical ore-dressing methods. Low grade bauxites are mixtures of hydrates, usually gibbsite or boehmite, with clay, iron oxides, etc. In some low grade bauxites, it is possible to separate a portion of the gibbsite or boehmite, which may be present as relatively hard and coarse particles, from soft or finely divided clay minerals by log washing or similar methods. This has been applied to the product of some mines or parts of them, but on other ores it is not applicable. In some cases the gibbsite or boehmite is almost as fine and soft and of nearly the same specific gravity as the clay minerals so that washing and gravity separations are not successful. The iron oxide, the clay minerals, and a part of the titanium minerals are often so finely dispersed in the ore that any of the physical mineral separation methods, including separations by gravity, particle size, flotation, and electrostatic or magnetic separation, have not been commercially SUCCESSFUL except on relatively small lots of ore. For these reasons, the only available methods of separation on the general run of ores have been methods which would be classed as chemical rather than physical or mechanical separations. Aluminum oxide can be reduced by carbon at temperatures above 1800°C to form metallic aluminum and aluminum carbide or nitride. The temperature for rapid reduction of aluminum oxide to metallic aluminum is about the boiling point of aluminum and above the temperatures necessary to reduce iron, silicon, and titanium so that the direct reduction of an aluminum ore with carbon will produce an alloy of aluminum, iron, titanium, silicon, etc., which may be mixed with carbides and nitrides. Also a large amount of the reduced aluminum may be lost as a vapor except in the presence of some alloying agent such as copper or other metals. While it is possible to refine such alloys or mixtures so as to produce commercially pure aluminum, the methods which have been found are too expensive for the present market. One direct reduction method which found limited commercial use in Germany during World War II was the direct reduction of a mixture of clay containing very little

Jan 1, 1951

By A. W. Schlechten, R. P. Abendroth

Equilibrium H2S/4 ratios were determined as functions of temperatunz and composition in a hydrogen recirculation apparatus. A high-temperature solid solution exists in the range two-phase regionfrom TiS 1.96, to TiS1.30, Various thermodynamic quantities were calculated from the data. COMPOUNDS in the titanium -sulfur system have not receiyed much attention in the past, probably because they do not occur naturally in the earth's crust. However, titanium-sulfur compounds have been used in various metallurgical processes. The U.S. Bureau of klines' studied the formation of ti- tanium-sulfide mattes from charges composed of rutile, pyrite, and carbon, with the resulting sulfide matte being chlorinated to form titanium tetrachlo-ride. Fishel, Roe, and Ellis' investigated the de-sulfurizing action of titanium in steels, and Schwarz and Koster studied the preparation of metallic titanium from the sulfide using aluminum and magnesium reduction. The thermodynamic properties of some of the compounds present in the titanium-sulfur system may prove to be of some use in the consideration of future processes using these sulfides, and would

Jan 1, 1960

By R. B. Ladoo, C. A. Stokes, R. N. Secord, A. L. Hall

INDUSTRIAL mineral history shows that the entrance of new, nonmetallic minerals into commercial production can be expected to occur from time to time. Latest entrant into the field is wollastonite. Except for one short-lived period in Kern County, Calif., starting in 1933, wollastonite has never before been produced on a commercial scale. But the signs are up for its entrance as an economic factor in the mineral market. Small scale experimental production from a deposit near Willsboro, N. Y., started about 1943. A pilot plant was built in 1949-50 and irregular, small scale, production has continued. In early 1951 Godfrey L. Cabot, Inc. of Boston, world's largest producer of carbon black, took an operational lease on the property to study the deposits and make market surveys. This became Cabot's first venture in the mineral field, when they took over operations and began design of a new mill, expected in production in 1953. Properties The properties and major uses of wollastonite are comparable to New York fibrous talc. It has about the same specific gravity and index of refraction as talc, but is somewhat whiter and softer. The two most important fields of use, paint and ceramics, are the same as for talc. Ground wollastonite has a fiber length as much as 13 to 15 times the diameter. This particular property makes it applicable in the paint field and others. In addition, the length-diameter ratio may be controlled to rather narrow limits by choice of grinding method. Another important commercial property is brightness or whiteness. Wollastonite reads from 92 to 96 pct of MgO on the G.E. brightness meter for a 99 pct -325 mesh grind. Purity and uniformity of product are important. Chemically, the wollastonite now being mined analyzes SiO2 51.76, CaO 47.56, FeO 0.46, MnO 0.04, and H2O 0.09 pct. Theoretically pure wollastonite analyzes SiO2 51.75 and CaO 48.25 pct. This analysis indicates over 98 pct calcium silicate, with only small amounts of contaminating ingredients. That these ingredients are not detrimental to color or brightness is shown by the high brightness value of the fine ground material. [ ] By-product calcium silicate from electric furnace production of phosphoric acid has little physical re-semblance. to this wollastonite, being an off color white, and lacking in fibrous crystalline character. Minerology Wollastonite is a calcium metasilicate, CaSiO3, a white, medium hard, fibrous mineral. In this deposit wollastonite occurs as well crystallized aggregates of bladed crystals intergrown with garnet, and with a few percent of green diopside. The beneficiated product is about 75 pct wollastonite, 15 pct garnet, and 10 pct waste, largely middling. Wollastonite-garnet ore occurs in at least two beds. The main bed, varying in true thickness from 30 to 70 ft, dips into the hill at an average 30° and is enclosed in gneisses. Diamond drilling has proven the orebody to an average depth of 200 ft along 2000 ft of outcrop with adequate tonnage for many years of quarry operation. The wollastonite-garnet ratio varies locally, but average composition is uniform over long distances. A friable ore, it is easy to drill, shoot, and crush. Beneficiation Unlike talc this ore has to be beneficiated. Successful treatment depends upon the fact that it contains virtually nothing but wollastonite, garnet and a minor percentage of diopside. A very pure wollastonite product can be made by high intensity magnetic and/or gravity separation methods.

Jan 1, 1952

By P. G. Winchell, M. Cohen, J. Woodilla

The kinetics of stabilization have been studied with respect to the isothermal component of the martensitic reaction in ivon-nickel alloys. Although the carbun (or nit-vogen) content may be very low in these alloys, it plays an important vole in the stabilization phenomenon. In fact, if these interstitial elements are removed by moist-hydrogen treatment, no evidence of stabilization is found. In the pvesence of 0.007 wt pct C, the activation energy for the stabilization process is comparable to that -for the diffusion of carbon (or nitrogen) in ferrite) rather than in austenitc. This suggests that the interstitial diffiision controlling the stabilization occurs within the martensitic embryos rather than in the matrix of the parent phase. The kinetics furthev indicate that the interstitial atoms tend to diffuse -from the embryos toward the suvroundings, thereby immobilizing the interface. This appears to be the origin of the stabilizing effect -found in these alloys. PHILIBERT' has shown recently that interstitial elements play an important role in the stabilization of martensitic transformations in iron-base alloys. However, determination of the temperature dependence for this stabilization process has produced values (- 11,000 cal per mol) that cannot be readily identified with the activation energy for diffusion of carbon (or nitrogen) in either ferrite or austenite. In the present work, the isothermal mode of the martensitic reaction was employed to derive the activation energy for stabilization, and this was found to agree fairly well with that for diffusion of carbon (or nitrogen) in ferrite. An iron-nickel alloy with 30.8 wt pct Ni and 0.007 wt pct C was used in these experiments, the specimens being in the form of rods 0.074 in. in diam and 2 1/2 in. long. The specimens were sealed in evacuated vycor tubes and austenitized at 1100°C for 1/2 hr prior to quenching in water. A second series of specimens was decarburized (and denitrogenized) prior to the above austenitizing treatment by annealing in moist hydrogen for 182 hr at 1215°C. In order to achieve a "standard" condition in the austenitic state, all the specimens were transformed to martensite by cooling to - 195°C before the final austenitizing. Both the 0.007 pct C and the decarburized series then had an Mi temperature of about - 30°C. The isothermal martensitic transformation was carried out at a reference temperature of -88"C, and was traced by means of electrical resistance measurements. Each resistance value was normalized by dividing by the resistance of the austenitic specimen at O°C, thus giving a resist- ance ratio R. The rate of decrease of the resistance ratio (-dR/dt) provided a measure of the transformation rate. It was found that a plot of R vs log t at the reference temperature resulted in a slightly curved line which could be closely approximated by two straight lines intersecting at a time of 10 min, as shown in Fig. 1. If G = dR/dlogt is the linear slope of either straight segment, the rate of transformation at any given time is: The ratio of G for 1 less than 10 min to that for t greater than 10 min was 1.19 for the 0.007 pct C series and 1.24 for the decarburized series. These ratios made it possible to compute the transformation rate at any time greater than 10 min, knowing the transformation kinetics prior to 10 min. The stabilization treatment was introduced by up-quenching from the reference temperature, usually after 10 min of isothermal transformation: to one of four stabilizing temperatures between 0" and 22"C. After holding for various times, the specimens were down-quenched to the reference temperature for additional isothermal transformation. In this way, it was possible to compare the transformation rate (- dR/dt), immediately after stabilization with the transformation rate (- dR/dt)U in the unstabilized condition. The degree of stabilization was defined as: Ordinarily, Gs and Gu would be measured after the same time of prim isothermal transformation.

Jan 1, 1960