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By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By J. Chipman, N. J. Grant, J. C. Fulton

This paper contains data on the distribution of silicon between liquid iron-silicon-carbon alloys saturated with respect to graphite and CaO-SiO2-Al2O3 slags under 1 atm of CO at 1600°C. The ranges of slag compositions studied were extended from the dicalcium silicate saturated liquidus composition up to silica concentrations at which Sic appeared as a stable phase. IN blast furnace operation it is not to be expected that slag and metal reach equilibrium with one another. Nevertheless, the silicon content of the metal varies with slag composition and with temperature in a manner which would be predicted from equilibrium considerations. Similarly, the distribution of sulphur between slag and metal does not attain an equilibrium state, yet the influence of slag composition is strongly analogous to its effect on the distribution equilibrium. The desulphurizing power of metallurgical slags has been shown to be highly dependent upon the FeO content of the slag. Moreover, the rate of removal of sulphur from slags is influenced by the oxygen potential of the slag-metal system. Thus it was shown by Grant, Kalling, and Chipman1 that the presence of MnO in slags which are low in FeO causes a marked slowing down of the transfer of sulphur from metal to slag. This led to the hypothesis that the slow removal of sulphur by blast furnace slags of more acid composition might be due in part to the effect of SiO2 on the oxygen potential of the system. This was verified in the work of Grant, Troili, and Chipman,' who found that the desulphurizing power of the more acid blast furnace slags could be markedly improved by an increase in the silicon content of the underlying metal. Their explanation of this improvement was that the higher silicon content of the metal decreased the rate of transfer of more silicon and, along with it, of oxygen from the slag to the metal. The slowness of the transfer of sulphur from metal to slag was the result of the slow reduction of SiO2 from slag to metal. Attempts to study the rate of sulphur removal had in the past resulted in very slow rates corresponding to the rates of silica reduction. It has become evident on the basis of these studies that further experimental studies on the rate of removal of sulphur must take these factors into consideration if there is to be a clear understanding of the rate of sulphur transfer under conditions simulating those existing in the blast furnace. It will be necessary, at least in a part of such study, to employ combinations of slag and metal in which the disturbing effect of silica reduction has been eliminated; in other words, to employ slag-metal combinations which are already in equilibrium with respect to the transfer of silicon. In preparation for such studies of desulphuriza-tion, a preliminary program of research on the distribution of silicon between slag and metal has been undertaken. This will ultimately include a comprehensive survey of the effects of temperature and slag composition on the equilibrium distribution of silicon between slag and metal. The present paper is a report on experimental methods employed and on

Jan 1, 1954

By G. S. Hume

During the war years the drilling activity in Canada has been steadily increasing and still further increase is expected in 1945. The production of oil, which in the past has come largely from the Turner Valley field in Alberta, shows a decline since 1942, the peak year. New discoveries made in 1944, however, give promise of replacing the decrease from Turner Valley where the crude-oil production in 1944 was nearly 1,800,000 bbl. less than in 1942, but with an increase of 145,000 bbl. in natural gasoline, a product of great value to the war effort. A very considerable part of the decline in Alberta has been offset by new production of more than a million barrels in 1944 from the Norman Wells field, in the Mackenzie River area of the Northwest Territories. It should not be forgotten, however, that this is largely due to the Canol development, a war project, the future of which is dependent on many factors not connected with an ordinary commercial operation. The year 1944 has been the best in new discoveries in Alberta for all time. The discovery of a new deep field at Jumping-pound, 20 miles west of Calgary, with the hopc of a type of product similar to that of Turner Valley is the culmination of many years of effort to interpret the subsurface structures in relation to the complicated surface foothills faulting and folding. In this case the subsurface structure on the Paleozoic limestone was inferred from geological investigations but precisely defined by seismograph. In addition to Jumpingpound the discovery of oil of 34.5 gravity at a depth of less than 5000 ft, in the Devonian of the Plains at Princess, 125 miles east of Calgary, is of great significance since this is the first substantial production from the Devonian in Alberta, although previously some oil had been obtained at two places from the Devonian in the foothills. The effect of this discovery is already apparent in the number of wells now drilling to the Devonian in the southern Plains. In southern Alberta a new producing area has been found in a Lower Cretaceous sand at Barnwell, a few miles west of Taber. Also, at Conrad, 20 miles southeast of Taber, an important new discovery has been made at a depth of about 3000 ft. in a sand in Jurassic shales, in a strali-graphic trap on the northeast flank of the Sweetgrass arch. In northeast Central Alberta an important extension has been found in the Lloydminster area, where only a few wells have so far been drilled. A new well 3 1/2 miles south of the previous producers found a coarser sand at the productive horizon and as a result will have an increased daily yield. At Blackfoot, 9 miles west of Lloydrninster, a new producing area in the Lower Cretaceous may have been discovered at a depth of 2004 ft. At the end of 1944 the well was being tested. Forty-four unsuccessful wildcat wells were drilled in Alberta in 1944. The decline of Turner Valley, the major producing field, was anticipated at the beginning of the war and in an effort to offset this and encourage new development the Dominion Government put into force tax concessions and other measures that,

Jan 1, 1945

By D. G. Westlake

NUMEROUS hydride habit planes in zirconium, Zircaloy-2, and Zircaloy-4 have been observed by various researchers and have been compiled by Louthan and Angerman.1 While only partial agreement exists on the identification of these habit planes, there is a growing consensus that a tensile stress applied on a polycrystalline rod during slow cooling will cause the hydride platelets to lie perpendicular to the tensile axis. walters2 agrees with Louthan and Angerman who reason that "The particular plane on which precipitation will occur is the plane that will result in the maximum relief of stress by precipitation of the low-density hydride." The experiment described below was initiated to test this hypothesis on a single crystal of zirconium. A single-crystalline tensile specimen of zone-refined zirconium, designated number 13 in a previous study,3 had a square cross section with one pair of parallel faces only 4 deg from the basal plane of the hcp structure. The tensile axis was about 86 deg from the (0001) pole, 14 deg from the (1010) pole, and 16 deg from the (1150) pole. The specimen was charged to 50 ppm H by allowing reaction with the correct amount of hydrogen at 1073°K, homogenizing at this temperature for 2 hr, and cooling in the furnace. Two- surface analysis revealed that hydride platelets had precipitated parallel to the three {1010} prism planes. The specimen was heated to 673°K, in air, for 16 hr to bring the hydrogen back into solid solution, and furnace-cooled to 573°K.* It was then stressed in ten- sion at 1.2 kg per sq mm. (This produced a resolved shear stress of 0.6 kg per sq mm for glide on the prism plane with the highest Schmid factor. A higher stress would have produced significant strain at this temperature because the critical resolved shear stress for prism-plane glide in this crystal was only 1.0 kg per sq mm at ambient temperature.) The poles of the three prism planes were at angles of 14, 46, and 74 deg to the tensile axis so that an applied stress would exert normal stresses on the three planes in the approximate ratios 10:5:1, respectively. As soon as the stress was applied, the sample was furnace-cooled to room temperature. It was ground on wet Sic paper and chemically polished in 50 parts HNO3, 50 parts water, and 7 parts HF before examination. The result of the experiment was negative; i.e., the three (1010) planes were of equal importance as hydride habit planes.* It must be admitted that the ex- periment is not entirely comparable to those performed by walters,2 Louthan,5 and Louthan and Marshall6 on polycrystalline materials. They have found that some critical stress (below the macroscopic yield stress) is required for stress-orienting the hydrides. The applied stress in the present experiment was, by necessity, smaller by an order of magnitude than the critical stresses they report for the various materials. If the critical stress was related to the microstructure, one might postulate that it should be decreased by increasing the degree of perfection of the metal lattice and by increasing the grain size. But the experiment above suggests that, for the extreme case of a zone-refined single crystal of zirconium, the critical stress lies above that which one can apply without introducing gross plastic strain as another variable.

Jan 1, 1967

By Stanley L. Lopata, Eric B. Kula

The problem of preferred orientation has been considered in quantitative phase analysis by X-ray diffraction techniques. The average intensity of a diffraction peak can be obtained by integration over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. For rod or wire, where the pole figure shows rotational symmetry, the intensity is measured along a radius of the pole figure. Where no symmetry is present, rotational symmetry is imparted by rapid rotation of the sheet around its surface normal during measurement. These methods are applied to the determination of aus-tenite in an Fe-31 pct Ni rod and Fe-28 pct Ni sheet. X-RAY diffraction techniques are frequently used for quantitatively determining the relative amounts of two or more phases present in a structure.1,2 Briefly, the method requires a measurement of the intensity of a Bragg reflection for each phase. The method is based on the principle that the intensity of a Bragg reflection, IA, is directly proportional to the volume fraction of the given phase present, CA: T KRACA/2µ [1] where K is a constant independent of the diffracting phase, RA can be calculated and depends on the Bragg angle ? and the particular reflection measured, and µ is the linear absorption coefficient of the mixture.' For a mixture of two phases A and B, IA = RAcA [2] IA/IB=RAcA/Rbcb and CA+ CB = 1 [3] This allows the volume fraction of a phase to be calculated directly from the measured integrated intensities of the two phases present. This method is frequently used for quantitatively determining retained austenite in steels, but can be used for the quantitative determination of in titanium alloys, as well as phases in other alloy systems. The intensities are generally measured by diffracting only from planes whose normals are perpendicular to the specimen surface, with the implicit assumption being made that this intensity is typical of reflections from planes whose normals lie at other angles to the surface. If the specimen contains a texture or preferred orientation of the crys- tallographic planes by virtue of previous mechanical working, however, this measured intensity is correct only if the intensity level fortuitously is one times random. Examination of pole figures for actual rolled sheet shows that the intensity level at the center of the figure is seldom at the random level, and can very easily differ by a factor of five or more, leading to a commensurate error in the calculated amount of the phases. Textures have been commonly found in materials which are cold-rolled or recrystallized after cold rolling. This problem is becoming of greater importance since structural materials in use today, such as the high-strength stainless steels, frequently are further strengthened by cold rolling, and hence contain textures. Although high-strength carbon-containing alloy steels generally do not contain textures, some of the newer thermomechani-cal treatments will impart a texture even in these cases. In the case of hexagonal metals, such as titanium, probably every wrought sample will show some anisotropy. Since the standard X-ray techniques are inapplicable in all these cases, there is a clear need for some method of taking this anisotropy into account. The specific problem is to obtain the integrated intensity of a Bragg reflection for each phase, averaged over all orientations of the sample with respect to the X-ray beam. This can be done either by purely mechanical means or by a mathematical averaging. Mechanically, a small spherical speci-

Jan 1, 1965

By Pol Duwez, Paul Pietrokowsky

Titanium and vanadium form a complete series of solid solutions at temperatures above 885°C. Below 885°C, vanadium is slightly soluble in a titanium (about 1.5 pct V at 650°C) and a two-phase a plus ß region extends to 18.5 pct V at 650°C. The alloys up to 15.0 pct V transform into a supersaturated a solid solution upon rapid cooling from the ß phase. Above 15 pct V the ß phase may be retained. The temperature at which the ß to a' martensite-type transformation takes place decreases steadily from 850°C for 0.5 pct V to 325°C for 12.7 pct V. IN the transition series of the periodic table, the six elements that have a body-centered cubic structure at all temperatures, namely chromium, vanadium, molybdenum, columbium, tungsten, and tantalum, fulfill the conditions required for the existence of complete series of solid solutions with the high temperature (ß) form of titanium. Up to the present time, complete solubility at temperatures above the a to ß transformation of titanium has been observed in the systems Ti-MO,1,2 Ti-Cb,2 Ti-W,³ and Ti-Ta.³ The two remaining elements, vanadium and chromium, have atomic diameters which are not as near that of titanium as the atomic diameters of the four other elements. Both are smaller than titanium and the difference, expressed in percentage of the titanium atomic diameter, is 12.3 pct for chromium and 8.2 pct for vanadium. On this basis, the least favorable conditions for solid-solution formation are therefore encountered in the Ti-Cr system. The early work on the Ti-Cr system4 revealed that up to about 1100°C the solubility of chromium in ß titanium is limited, and an intermetallic phase exists near the stoichiometric composition TiCr2. It was found later' that a continuous series of solid solutions extends across the diagram at higher temperatures, and TiCr2 forms by solid state reaction. It became apparent therefore that complete solubility would also be present in the Ti-V system. The present investigation confirms this possibility. The iodide-refined titanium used in this investigation was purchased from the New Jersey Zinc Co., New York. According to the manufacturer, a typical analysis of this product is 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb. The Vickers hardness number (10 kg load) of the crystalline bar varies between 55 and 80. The vanadium metal was purchased from the Westinghouse Electric Corp., Lamp Div., Bloomfield, N. J. The purity of this metal is probably above 99 pct V. The oxygen content must have been quite low, since a bar about 1/4 in. square could be cold rolled into a ribbon 0.020 in. thick. To prepare the various alloys on the titanium-rich side of the diagram, the titanium rod was machined into cups 1 cm in diam and about 1.5 cm high. Pieces of vanadium, of the proper weight, were cut from the square bars and placed within the cups prior to melting. On the vanadium-rich end of the diagram, single pieces of the metals, in the proper weight pro-

Jan 1, 1953

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By R. H. Hiltz, R. W. Douglass

Large-grain specimens of iodide titanium prepared metal-lographically were stain etched using the technique of New York University as modified by Watertown Arsenal Laboratories. Orientations of grains showing an abnormal response to stain etching were determined by back-reflection X-ray techniques. X-ray results showed that a-titanium grains, oriented such that their basal planes were parallel to the polished surface, have a slower reactivity to stain etching than any other orientation. Grains oriented such that their basal planes made small angles with the polished surface exhibited reaction rates between that of the true basal orientation and the normal rate. As the angle with the surface increases the reactivity increases up to a maximum angle of 14 deg. Basal planes making an angle with the surface of greater than 14 deg show normal reactivity to stain etching. These data, plus work on polycrystalline specimens, indicate that the oxidation rate of titanium might be reduced by correct alignment of crystal planes. ThE earliest observed phenomenon in the micrography of titanium was the occurrence of a grains which exhibited no birefringency. Even though a titanium possesses a hexagonal-close-packed structure and should be optically anisotropic, it can appear optically isotropic, when the crystal is so oriented that its intersection with the polished surface is perpendicular to the axis of symmetry. During the develoment of color staining techniques for titanium: it was noted that the a phase did not stain uniformly. Staining of specimens of commercially pure titanium resulted in a micro-structure of blue-colored grains, among which were randomly oriented a few grains exhibiting colors between the initial yellow and the final blue color. Under polarized light, these off-colored grains appeared to be optically isotropic. More intense study with polarized light, however, showed only the yellow grains to be isotropic. The intermediate colored grains exhibited weak birefringency, which at first glance is not detectable due to the strong birefringency of the surrounding structure. Aminoff2 and Straumanis3 have previously shown that in zinc the basal orientation is less reactive than other orientations. Leidheiser4 showed the same thing to be true for the hexagonal-close -packed configuration of cobalt. Thus, it would appear that the basal-plane orientation is responsible for the abnormality in stained titanium. Later work by Leidheiser5 on cobalt has shown that other planes besides the basal plane exhibited reaction rates slower than the normal rate. Reported planes were the (100), the (1011) and several planes making small angles with the basal plane. The last observance appears not to be due to the reactivity of the reported plane but due to the reactivity of the basal plane which is very close to being parallel to the surface. There are, then, two possible explanations for the range of colors observed in stain-etched a titanium. Since extensive research on the effect of orientation on surface reaction has failed to provide any definite trend, these two explanations are not adequate in themselves. Planes showing the retarded reactivity differ not only for different crystal structures but for metals of the same crystal structure and even for different reactions of the same metal. Tragert,6 Leidheiser,7 Tammann,6 and wagner9 have shown copper to exhibit retarded reactivity on the (111) plane. However, Leidheiser10 has shown that under other conditions the retarded reactivity of copper is associated with the (100)

Jan 1, 1960

By H. H. Rachford, D. W. Peaceman

A system of partial differential equations describing miscible displacement of fluids in porous media is derived The system takes into account the influence of gravity, the spatial distribution of permeability, diffusion, and fluid viscosities and densities. A numerical procedure for approximating solutions to the differential systems has been tested for a horizontal two-dimensional geometry. In end-to-end displacements of oil with less-viscous solvents, the numerical solutions exhibited fingering qualitatively similar to that observed in laboratory models. Small random spatial variations in permeability about the mean value are sufficient to initiate fingering. Quantitative comparisons of computed results with laboratory data show good agreement. INTRODUCTION Miscible flooding of oil by solvent is receiving increasing consideration for field use.1-4 Unfortunately, such floods potentially present severe problems in loss of recovery through the by-passing of oil by expensive solvent. Consequently, their economic evaluation requires sound techniques for predicting recovery. The purposes of this work are to present a finite-difference method for calculating the multidimensional displacement of oil by solvent and to investigate the validity of the method by comparing results of calculations with data from displacements in laboratory models.5 The formulation of the method to simulate the model experiments treats a case of limited scope in the description of solvent flooding in the reservoir. The model experiments were carried out with fluids that were assumed to form an incompressible, ideal, two-component system with constant diffusivity. Establishing the validity of the method even in its present form provides a major step toward the goal of quantitatively evaluating individual solvent flooding projects. First, it demonstrates the fea- sibility of calculating the course of displacements which are dominated by an inherent macroscopic instability, i.e., viscous fingering. In addition, the method provides almost the only practical means of examining the effect of the size and extent of reservoir inhomogeneities on the development and propagation of the fingers, taking into account the important influences of diffusion and gravitational segregation. It might be inferred that such studies cannot yield results of practical value because in displacements dominated by macroscopic instability the pattern of finger development and the resulting performance should depend critically on small variations in the geometric distribution of reservoir inhomogeneities. The present method offers the capability inherent in computational techniques of predicting performance reproducibly with any arbitrary distribution of reservoir properties and, as such, provides a means of evaluating the sensitivity of behavior to uncertainties in reservoir definition and, thus, assessing the reliability of prediction of performance. THE PHYSICAL PROBLEM DATA USED FOR QUANTITATIVE TESTS OF CALCULATIONS In this work, a calculation for treating the miscible-displacement process is tested by comparing calculated results with experimental data. The experiments chosen for comparison have been described in detail,5 and the quantitative features are summarized in a later section. Briefly, oil was flooded by solvent of equal density from a thin rectangular channel in Lucite packed with uniform Ottawa sand. Under these conditions, two-dimensional geometry is considered adequate to represent the process. Inasmuch as the present work is concerned with testing of the method by comparison with specific two-dimensional data, the system of equations presented in the succeeding section will be oriented to defining the physical system specifically. THE DIFFERENTIAL EQUATIONS Suppose x, y to be a Cartesian co-ordinate system and define h(x, y) to be the height of a point above a horizontal reference plane. It will be assumed

By A. Heim, M. Gondouin

Invasion experiments were run on Berea sandstone cores to get laboratory measurements of resistivity and saturation profiles characteristic of water and oil sands invaded by mud filtrate. Injection rates were as low as 1.13 cm/D, and the cores were 30 to 36 in. long, cut parallel to the bedding planes. In the water-sand case, the resistivity profiles revealed the existence of an extensive transition zone between flushed and uncontaminated zones. In the linear geometry of the experiment, the width of the transition zone increased as the square root of the injected fluid volume. For the oil-sand case the core was prepared by displacing the formation water with kerosene to minimum water saturation. During the subsequent invasion experiment. oil saturation was measured directly by means of an oil-soluble radioactive tracer, and resistivity profiles along the core were taken at the same time. These data were interpreted in terms of an oil-water front, followed by a formation water bank, a zone of mixed waters, and finally, invaded mud filtrate near the borehole. Micro-fingering and capillarity seemed to affect considerably the resistivity profiles observed in the invaded oil-sand experiment. Beyond the regular conductive annulus or "low zone", it was found that a resistive "anti-annulus" could also be formed. As a result of these experiments, some simplified invasion profiles have been accepted and are being used in Grand Slam* interpretations. INTRODUCTION The importance of the mud filtrate-invaded zone in interpreting electrical logs has long been recognized.',* In trying to account for its effect, only very simple models of the resistivity profiles in the radial direction from the borehole have been used. In fact, most log interpretation charts have been based on resistivity models consisiting of two media of uniform resistivity (R, and R,) abruptly separated at the diameter of invasion. Such a clean separation of the media of different resistivities seems unrealistic, since flushing may not be perfect and may vary with radial distance into the formation.3** The nature of the transition zone, when it is within the radius of investigation of the surveying devices, may affect the log readings. Campbell and Martin' verified that a conductive annulus containing a high percentage of formation water may be formed when mud filtrate invades an oil-bearing sand. Interpretations which are to include the effect of such an annulus require the addition to the model of a conductive zone located at the outer rim of the invaded zone.' Using the Buckley-Leverett relations,6 aturation profiles may be derived, from which resistivity profiles can be calculated. Results of such computations by K. S. Kunz and J. H. Moran were given in a paper by Dumanoir. Tixier and Martin,7 and led to the construction of log interpretation charts which were based on a representation with three media of resistivities R, R0 and R1. Fig. 1 shows a schematic representation of a resistivity profile which includes an annulus. Campbell and Martin realized that, during the invasion of an oil sand, both capillarity and mixing would contribute to rounding of the profile shown in Fig. 1. Capillarity tends to draw some of the formation water from the annulus into the uncontaminated (Rt) zone, whereas mixing of the mud filtrate with formation water of the

Jan 1, 1965

By Edwin S. Smith

Current research in the phenomenon of liquefaction has indicated some of the in situ material properties which should be considered in the planning of waste deposits. Practical experience in tailings disposal, however, must be combined with the results of theoretical and laboratory studies to develop the most economical and safe techniques against liquefaction failure. One of the many responsibilities of mining engineers and mill superintendents is providing for the safe and economic disposal of wastes (or tailings) that remain after a mineral has been extracted from an ore. The cost of disposal of these tailings exerts a considerable influence on the minimum grade of ore extracted from the mine. It varies to a great extent with each project and is dependent on many diverse factors, such as the local topographical, meteorological and seismological conditions together with the applicable water pollution laws of the area. The process used to extract a mineral from an ore determines the physical characteristics of the tailings and, thus, is one of the more important factors to be considered in the planning of disposal facilities. Today's trends in ore-processing operations complicate the problems of waste disposal: recently developed extraction methods result in the production of finer tailings, the use of lower grade ores produces greater volumes of wastes, and the enhanced land values in the vicinity of industrial plants preclude the former practice of spreading wastes laterally and force the expansion of waste deposits upwards to greater heights. The frequent occurrence of stability problems in waste deposits indicates that many mining organizations may not be employing current soil mechanics concepts and practices. One of the most spectacular, and often most disastrous, types of tailings dike failure is that resulting from liquefaction of the fine particles combined with a breach of the main retaining dike. TAILINGS DISPOSAL Since the many variations in site conditions, ore bodies and extraction processes dictate the general disposal procedures and mill superintendents incorporate special facilities to provide the most economical disposal method consistent with accepted safety standards, it is only natural that there are almost as many different disposal techniques as there are disposal areas. Methods used in the construction of retaining dikes include: (1) transporting granular material from an adjacent borrow pit and (2) mechanically segregating the total effluent and allowing the coarse fraction to form a retaining dike by hydraulic deposition. The location of a plant and the surrounding topography exert the greatest influence on the layout of tailings disposal facilities. Most of the above-ground waste deposits can be classified as side-hill, (Fig. 1,) cross-valley, (Fig. 2,) or stockpile deposits. Side-hill disposal areas are probably the most common type of layout because of the natural advantage of gravity flow, without the disadvantage of river diversion usually needed for tailings ponds formed behind cross-valley dikes. Stockpiles, which are placed on relatively level ground, require four retaining dikes and the effluent generally has to be pumped up into the disposal area. Changing production techniques or developments adjacent to disposal areas have produced variations or partial combinations of these three categories. In a series of articles, Lenhart describes many of the problems encountered in the disposal of tailings and certain innovations used to overcome them. He discusses weaknesses in design and layout and shows that disposal techniques are often learned the

Jan 1, 1970

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By F. G. Jaicks

RECOGNITION of the benefits to be gained from the continuous casting of molten steel into finished or semifinished products has been given by scientific minds since the very beginnings of steel plant technology. In fact, Sir Henry Bessemer is credited with the first of a long list of patents' issued by the U. S. Patent Office for a process which would accomplish this desirable end. None of these early ideas attained practical success and, as a result, the conventional method of teeming into ingot molds became an integral part of modern steelmaking operations. This procedure, although refined to keep pace with the changes which have come about in steelmaking and finishing facilities, is recognized to have inherent shortcomings which adversely affect manufacturing costs and steel quality. Interest in the continuous casting of steel persists because the process is directed toward avoiding some obvious weaknesses of conventional ingot casting. It has been recognized that should it be possible to substitute any of the continuous casting techniques under current development for ingot casting, it would no longer be necessary to make large capital investments in primary rolling equipment, the sole purpose of which is to reduce ingot castings to a form rollable on finishing mills. The results reported in the continuous casting of non-ferrous metals and specialty steels indicate that in addition to avoiding the primary rolling mills there is some basis for expecting significant improvements in yield, surface, and internal quality. Recognizing the shortcomings of the conventional procedures, the Inland Steel Co., in cooperation with Atlas Steels Ltd. and the Freyn Dept. of the Kop- pers Co. Inc., embarked upon a program to evaluate certain aspects of continuous casting in order to determine whether the process could be applied practically to an existing integrated steel plant producing 'large tonnages of carbon steels. TO assist in this evaluation a study was carried out in which several types of low carbon steel were continuously cast in an existing machine. It is the purpose of this paper to review some of the results obtained in the casting studies and to interpret the information that was obtained so as to indicate factors that must be considered in assessing operating limitations and plant capacities. Despite the early interest in the continuous casting of steel, the actual application to the steel industry is relatively recent. At present, there are about 25 operating plants casting steel, most of which have been built in the past decade. None of these plants could be classified as large in terms of the tonnages that are being processed by the major integrated steel plants. In contrast to the situation in the steel industry, there has been widespread adoption of the continuous process in the casting of nonferrous alloys, particularly aluminum and copper. As a result, much of the basic information that was required to apply the process to steel was developed in the nonferrous industries. In this respect, a most important contribution was the development of the Junghans2 system, which was initially designed for the casting of nonferrous metals and later applied to the casting of steel. Alternative methods for casting have also been proposed by Babcock and Wilcox Tube Co.,'" the British Iron and Steel Research Association,5 and the Gebruder Bohler A. G.13 Each of these methods is now being used successfully for the casting of special steels in small experimental plants or in modest sized commercial steelworks. The Original Junghans process was first developcd in Germany. Further application of the process has been made by Rossi in other countries.'*' The experi-

Jan 1, 1958

By James J. Bean

F. M. Lewis—I believe that density recorders are a prerequisite to all well operated ore concentrators. Well designed density instruments are very accurate and give an excellent record of the steadiness of the operation. Controlling the density of a pulp with an instrument, as described by Mr. Bean, is new and the experiences in developing this controller at the American Cyanimid Co.'s Mineral Dressing Laboratory are very interesting and should be extremely helpful to others who are planning on designing or installing controlling density instruments. Instruments for recording the density of the classifier overflow or flotation feed are rather common in ore concentrators, but there are a number of profitable uses for these instruments that are not too well known. Density recorders with bubble tubes submerged to different depth in a classifier pool give an excellent record of the classifier operation. The loading and unloading of the machine, that is so easily masked in the density of the overflow, can be easily recorded if the instrument is installed at some depth in the classifier pool. On some occasions, two instruments with bubble tubes at different depths give a more candid picture of the irregularities in the classifier operation. When cleaner machines are operated in closed circuit with roughers, a record of the density of the cleaner tails will indicate the circulating load in the circuit and is very helpful in coordinating different operators, because quite often the circulating load will be increasing for some time before the analyses of the products will change. Density recorders are used to record the variations in the dilution of the underflow from thickening tanks and in at least one plant the instrument controls the underflow.

Jan 1, 1951

By James J. Bean

F. M. Lewis—I believe that density recorders are a prerequisite to all well operated ore concentrators. Well designed density instruments are very accurate and give an excellent record of the steadiness of the operation. Controlling the density of a pulp with an instrument, as described by Mr. Bean, is new and the experiences in developing this controller at the American Cyanimid Co.'s Mineral Dressing Laboratory are very interesting and should be extremely helpful to others who are planning on designing or installing controlling density instruments. Instruments for recording the density of the classifier overflow or flotation feed are rather common in ore concentrators, but there are a number of profitable uses for these instruments that are not too well known. Density recorders with bubble tubes submerged to different depth in a classifier pool give an excellent record of the classifier operation. The loading and unloading of the machine, that is so easily masked in the density of the overflow, can be easily recorded if the instrument is installed at some depth in the classifier pool. On some occasions, two instruments with bubble tubes at different depths give a more candid picture of the irregularities in the classifier operation. When cleaner machines are operated in closed circuit with roughers, a record of the density of the cleaner tails will indicate the circulating load in the circuit and is very helpful in coordinating different operators, because quite often the circulating load will be increasing for some time before the analyses of the products will change. Density recorders are used to record the variations in the dilution of the underflow from thickening tanks and in at least one plant the instrument controls the underflow.

Jan 1, 1951

By Albert Sauveur

IN an important paper on The Critical Ranges of Pure Iron1 presented at the May, 1913, meeting of the Iron and Steel Institute, Professor Carpenter reports and illustrates the results obtained by him in determining the critical points of some very pure electrolytic iron sheet about 0.01 in. thick. The iron strip was rolled into the form of a cylinder 1; in. long and fn in. wide, weighing 42 g., the thermo-couple being inserted in a small hole in the center. The points Ac3 and Ar3 were readily detected, as well as the point Art, but the point Act was absent from every heating curve. The author concluded from this occurrence that the conception of A2 as an independent allotropic change must be abandoned. At the October, 1913, meeting of the American Institute of Mining Engineers, Dr. G. K. Burgess and J. J. Crowe read a paper on The Critical Ranges A2 and A3 of Pure Iron2 in which they described some extremely important experiments conducted by them at the Bureau of Standards, Washington, D. C. They tested Professor Carpenter's electrolytic iron and detected a sharp and well-defined absorption of heat corresponding to the point Act. Professor Carpenter's failure to detect this point is explained by them on the ground that unless the iron be in a single piece entirely surrounding and in contact with the thermo-couple junction, the thermo-couple will integrate the irregular progress of the heat through the sample and the curves will lose their sharpness. In discussing Messrs. Burgess and Crowe's paper, Professor Carpenter accepted this explanation as probably accounting for the absence of Act in his heating curves.

Jan 2, 1914

By J. W. Furness

THE utilization and collection of waste materials have gone on for centuries, and have become a habit of the human race. The degree to which the salvaging of waste plays a part in a nation's industry depends largely on the availability of raw materials within the political confines of the country itself, or its ability to purchase such material from outside. When purchase is necessary careful economical use of the raw materials results. These economies, as a rule, are represented by lengthening the life of the given article as well as much re-use. For many years the steel industry of Italy and Japan has depended largely on importations of scrap, yet both are important. As long as the expenses incident to the conditioning and marketing of materials manufactured from salvaged waste are less than the cost of virgin material, the salvaged material will be re-fabricated and in many cases will compete with primary materials. One of the most obvious methods for furthering the efficient utilization of our limited mineral resources is the salvaging of mineral wastes. This method, moreover, in¬creases the available supply of a given material. If the price depends on a balance of supply and demand and the recovery from wastes enlarges. the supply, there can be no question but that it influences the sales price of primary.

Jan 1, 1931

By Cyril Stanley Smith

ARCHEOLOGISTS, by use of the terms Bronze Age and Iron Age, indicate that metals have in the past determined the character of civilization. The relatively simple discovery by a primitive metallurgist that the addition of tin to copper both facilitated the production of castings and increased the durability of the product enabled hunter, warrior, and housewife alike to do things never dreamed of before. Similarly, the smelting of iron and the discovery of hardening methods greatly changed the arts of peace and war. Discoveries of low-melting-point alloys for joining and for making household utensils, and perhaps the adornment of a feminine form by sparkling precious-metal jewelry, have at times changed the destiny of a country. Bronze cannon, the cast and wrought iron Watt engine, copper transmission lines, and aluminum alloy aircraft, are cases of particular metals making possible the realization of an improved engineering design. Perhaps of the greatest influence of all upon civilization was the development of type metal. The rapid increase in the rate of dissemination of knowledge dates from the day that the technique of the pewterer was utilized in making rapidly reproducible and accurately sized letters for printing. It was not movable type, but metal type that was important, for metal castings could be made of identically the same shape and size at an enormous rate, and possessed excellent inking and wearing characteristics.

Jan 1, 1946

By George S. Rice

THE year 1929 has shown a surprising growth in the attention given by mining men to the subject of ground movement and subsidence from mining, as evidenced by the large number of articles that have appeared in technical journals, also papers and discussions in mining societies in the leading mining countries of the world. These have not been confined to consideration of the narrower limits of the subject but in application have extended to many of the fundamental questions involved in mining. The papers and discussions have been concerned with .ground movements resulting from mining of a great variety of minerals, metallic and lion-metallic. Examples of the former are: the mining of gold ore at Johannesburg, South Africa, and in the Kolar field, India; mining copper ores in Arizona and Utah; and lead and zinc in the Joplin region. Examples of ground movement resulting from mining non-metallic minerals are found in: the mining of. coal in many countries; potash mining in Germany; the mining of- common salt in several parts of the' United States; and the mining of sulfur in Texas and Louisiana; and examples of subsidence in the non-metallics are found exceptionally in the extraction of petroleum by wells, as in the Goose Creek field, on the Gulf Coast,' and recently in the Sour Lake field' of Texas

Jan 1, 1930