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By James E. Hoffmann, John A. Bonucci, Peter D. Parker

A hydrometallurgical process has been developed for the recovery of high-purity silver from sulfated residues. The process eliminates the high temperature operations ordinarily associated with silver recovery and refining. The crux of the process is a metathetical leach which maintains the sulfate ion concentration at a level which both allows silver nitrate to be freely soluble and simultaneously depresses the solubility of lead nitrate. The subsequent hydrolytic purification of the silver nitrate solution, the recovery of high-purity silver by electrowinning in a diaphragm cell, and the final product purity are discussed.

Jan 1, 1981

By D. W. Peaceman

In previous papers by this author on numerical calculations of multidimensional miscible displacement, some simplifying assumptions were made in writing the dispersion term of the differential equation. It was assumed that the flow vectors were essentially parallel to the x-axis. However, in most multidimensional miscible displacements, the flow vectors are not so simply oriented with respect to the coordinate axes. This paper derives the correct dispersion term /or the more general case; gives a difference approximation /or the dispersion tern; and derives the stability criterion for the corresponding explicit difference eguation.

Jan 1, 1967

By G. Herget, O. Garg

Trends will continue towards more automated, and sometimes larger mining and haulage equipment to reduce pit development and haulage costs. To save labour costs, larger capitalization of open pits is required and pit design and stripping ratios have to be firmed up at a very early stage of mine planning. Bench failures will assume a greater importance with larger equipment and at present we have only a limited capability of predicting stable slopes in complex structural geological settings. Deep open pits will pose particular problems in regard to high toe and floor stresses. This will require the development of more efficient systems for rock mass exploration and an improvement of our predictive capability in regard to pit slope stability and appropriate management of ground- water and materials. To meet the challenge, we have to improve: a) Analytical tools to assess slope stability in structurally complex settings as found in large open pits; b) Core orientation methods during diamond drilling operations; c) Geophysical logging methods to obtain geotechnical and structural geological information for large volumes of rock; and d) Geotechnical data handling systems to define mechanical properties

Jan 1, 1983

By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.&apos; In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By Donald E. Garrett

The processing of brines from Searles Lake, California, yields one of the world&apos;s largest supplies of borax and boron chemicals, second probably only to the massive deposit at Boron, California. Two companies produce from this deposit, the American Potash & Chemical Corp. and the West End Chemical Co., a division of the Stauffer Chemical Co. Two processes are employed in recovering borax from the brines; one is used by both companies and consists of carbonating the brine to form sodium bicarbonate, removing this, and then cooling the liquor to crystallize a crop of borax. Only American Potash uses the second process, evaporating the brine to concentrate it and remove (crystallize) much of its NaCl, Na2CO3, Na2SO4, and NaLi2PO4 content, quick cooling the remaining liquor to remove KCI, and then seeding the filtrate to remove borax. Both methods will be briefly described. Searles Lake is a large evaporite body formed during the most recent two Sierra Nevada ice stages, the Tahoe and the Tioga. Runoff waters from the Sierra Nevada Mountains collected in the large Owens Valley drainage basin and from there overflowed into the Indian Wells basin and then into Searles Lake. In each Lake, evaporation took place. To a large extent the Owens and Indian Wells lakes acted as settling basins, for much of the mud, and insoluble calcium and magnesium precipitates were deposited there. Recent volcanic activity in the mountains to the north and east of Owens Lake had scattered considerable mineral-rich volcanic ash and debris throughout the drainage area, and several hot springs were formed that contained boron and other salts. The present flow rate and concentration of several springs, and the known age of at least the Tioga zone, can fairly well account for all of the boron present in Owens and Searles Lakes.1 The tungsten content can be accounted for in a similar manner.2 Most of the salts thus originally present in the fresh water runoff-from ice, snow, and rain-accompanying these two ice stages were ultimately deposited in Searles Lake. During the Tahoe period, from 25 to 40 ft of massive, mixed salts were deposited, along with six interspersed layers of mud (four inches to two feet thick) representing comparatively brief interglacial periods. Before the final desiccation of the lake, from 10 to 14 ft of new mud was deposited, representing the Tioga stage. The crystals subsequently deposited were from 70 to 90 ft thick, and form the present lake surface. The extent of the salt body is about 34 square miles, of which 12 square miles are exposed salt; the remaining area is covered by recent alluvial deposits (chiefly mud). The present lake is generally dry on the surface but floods to a shallow depth following heavy rains. The crystal body of both zones consists of continuous clusters of salts, and the voids between crystals (about 45 pct of the total volume) are occupied by brine. The level of this brine never recedes more than several inches below the salt surface. The brine pumped to the plants for processing is generally saturated with all of the solid phases present in that area, and thus is a complex mixture containing about 35 pct solids (see Table 3). The brine composition varies somewhat at different areas of the lake and from upper to lower structures, so wells are drilled in the areas and to the depths desired. A casing is cemented in the hole to within a short distance from the bottom, and pumps with about 14-ft suctions are mounted on the casing to pump the brine into the plants. The evaporation process of the American Potash & Chemical Corp. treats upper structure brine, evaporating all of the water from

Jan 1, 1960

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By T. F. Mueller, P. A. Witherspoon

For the case of an infinite radial system operating at constant terminal rate, the reservoir engineer often uses the "point source" solution of the diffiusivity equation to study pressure interference effects. At early times and at short distances from the inner boundary these solutions are invalid. The amount of error is often not precisely defined because of mathematical difficulties. Work presented here shows that, if dimensionless time is defined appropriately, previous solutions of the pressure equation can be displayed .as a family of curves on one chart. These solutions include the point source solution (referred to in the field of hydrology as the Theis solution) and other solutions obtained with digital computer methods. With these curves, an exact evaluation of the pressure drop within a reservoir or an aquifer can be made by the engineer. Examples of field problem solutions are presented. In most reservoirs the error involved when the Theis solution is employed is often negligible; whereas, in the calculation of interference effects in an aquifer, a substantial error can occur through such an approach. INTRODUCTION Flow equations are used in petroleum engineering to study the behavior of individual wells and reservoirs. In the case of wells, the pressure response at the wellbore face is the major point of interest; whereas, in the case of reservoirs, the pressure response at the interface of the aquifer boundary is sought. To aid in such studies, the flow equations have been solved in terms of the behavior at these two inner boundaries. Only limited work has been published in regard to the pressure conditions away from these points, i.e., within the reservoir or aquifer. Theis and Mortada are among the few who have reported on this problem. The Theis approach employs the exponential integral and is valid for pressure conditions that occur some distance away from the flow disturbance. It is derived from the concept of a point source, as opposed to a flow across some finite area. The Mortada results, on the other hand, are valid at all points within the reservoir or aquifer. They are presented in terms of dimension less ratios of the radius where the pressure is desired to the radius where the flow rate is measured. Their main use, in the past, has been in aquifer studies. The published results are presented in the form of graphs that are limited to a maximum radius ratio of 64. These graphical results are cumbersome to interpolate at non-integral radius ratios, so that one may be forced to utilize a rather involved analytical expression presented by Mortada. BASIC EQUATIONS The solutions of Mortada and Theis are both based on the diffusivity equation as applied to the case of an infinite radial system subject to a constant terminal rate. The equation is obtained by combining the material balance equation with Darcy&apos;s flow equation. The assumptions implicit in the use of this equation are as follows: (1) a single fluid is present that occupies the entire pore volume; (2) the reservoir is horizontal, homogeneous, uniform in thickness, and of infinite radial extent; (3) compressibility and viscosity of the fluid remain constant at all pressures; and (4) fluid density obeys the equation Using the diffusivity equation in situations where the above conditions do not hold will result in errors. These errors (not discussed here) but only the errors which arise in the solution of the equation itself. The diffusivity equation for the homogeneous reservoir conditions cited above can be written in cylindrical coordinates, as To obtain a dimensionless equation, so a single solution can be used for applications of different porosity, permeability and fluid properties, the following transformations are usually made: After these transformations are made, Eq. 3 .can be written in dimensionless form, as MORTADA SOLUTION One solution of Eq. 6 has been given by Mortada.

Jan 1, 1966

By George Hulst

PRIOR to 1914, there was little demand for antimony in this country; its use was limited almost entirely to the manufacture of type and bearing metals. Practically no antimony ore was mined here, the market being supplied principally from China, and the alloy was produced by a direct mixing of lead and antimony. The great world war, with its demand for shrapnel in hitherto undreamed of quantities, precipitated a great boom in the price of antimony. Nominally quoted at 6 c. to 7 c. in 1914, the price increased by leaps and bounds to 45 c. in March, 1916. Under the stimulus of high prices many shall mines were opened, for it became profitable to work ores containing as low as 20 percent. antimony. High-grade sulfide ores (stibnite), containing 55 per cent. to 60 per cent. antimony, were received from Bolivia, China, and Alaska. Low-grade sulfide ores, running from 20 per cent. to 45 per cent., were produced in Nevada, California, Idaho, Utah, and Mexico; much of this ore was fairly rich in silver. The principal oxide ores came from Mexico and Oregon. The following analyses are representative of various types of antimony ore: Se Pn Cu Ao Au SIC), Fe S CAO ZN As Oxide Ore 25.09 46.02 0.95 0.40 10.98 0.30 0.22 Sulfide ore 5.5.20. 15.12 1.05 19.87 ? 0.40 0.25 Sulfide Ore 37.16 11.30 0.10 34.0 7.60 0.50 17.05 7.40 0.36 0.10 Sulfide Ore 41.55 15.00 0.20 76.0 0.04 5.60 0.25 18.17 0.85 0.25 0.10 The International Lead Refining Co. fortunately was equipped to handle these ores through residue and blast furnaces. The charge consisted of a variety of sulfide ores containing Sb 20 to 60 per cent. and Si02 6 to 45 per cent., oxide ores containing Sb 20 to 40 per cent. and SiO2 10 to 45 per cent. Secondary materials, such as battery plates, battery mud, lead oxide, paint, etc., together with refinery skims, softener skims, and other refinery byproducts, were treated along with the antimony ore to furnish the lead required. All silver-bearing antimony ores were treated in the residue furnace, the sulfur, iron, and copper forming matte that carried part of the silver, the balance going into lead bullion. The

Jan 9, 1919

By Arthur H. Wilson

INTRODUCTION The stratified deposits of the coal measures are strongly laminated and exhibit a high degree of anisotropy. The stronger rocks in the sequence possess joints and shear planes, the coal itself has a closely spaced cleat pattern, and the softer rocks are capable of flowage. To calculate the general distribution of stress in such a medium by analytical means based on the theories of elasticity is difficult, and has not yet been satisfactorily achieved. Nevertheless, some estimate is required to aid the design of supporting pillars and permit the correct siting of main roadways. This is important when laying out districts for longwall extraction, particularly if the results of previous experience are not available in the area to be exploited. Although elastic stress analyses, including finite element analysis, may not be very appropriate, the basic equilibrium conditions will apply. These, combined with logical deductions based on observed fact, can be used to give appropriate solutions which experience has shown to be capable of giving acceptable results in the design of pillars associated with longwall workings. Constancy of cover load is one of the fundamental equilibrium conditions. When mining below ground, the cover is not removed, therefore the average vertical load after mining must equal the initial cover load. If mining produces a local decrease in load in any particular area, it must be balanced by an equivalent increase in load nearby. Bending moments in the strata above are capable of compensating for the turning moments which this redistribution of load may produce, and the existence of a "rear abutment", much discussed between 1950 and 1960, is not an essential equilibrium requirement. If the distribution of vertical stress is plotted three-dimensionally, then the load on any small element of area 6S will be o.6S, where o is the average stress. This also represents the volume of the "stress envelope" which lies above 6s. By making the individual areas very small and summing together, it is possible to show that the total load on any particular area can be found by calculating the volume of the stress distribution envelope which lies above it. A similar consideration applies to the stress distribution in a two-dimensional situation. If the stress distribution curve is drawn, then the area below any portion will represent the load per unit depth of section. For example, Figure 1 represents the possible stress distribution across a caved waste and associated ribside. If AW is the load deficiency [ ] These loads must balance, therefore area AW = AS, and if one can be deduced, the other will then be known. Attempts have been made to measure stress distributions in the ribside and in the waste. Stress meters in soft rocks such as the coal measures have not proved very effective. Those based on the measurement of strain have experienced difficulty in strata capable of flowage, high modulus stress meters suffer from cross sensitivity, and overcoming to obtain absolute stress is almost impossible. Load measuring instruments left in the waste have also proved largely ineffective, mainly as a result of the difficulties of protecting the leads in a caving environment. Certain logical deductions, however, can be made about the conditions in the waste. CONDITIONS IN THE WASTE Over the area of the waste the surface trough which develops is remarkably consistent, despite the geological variations which occur from coalfield to coalfield. In Britain, an accuracy of 210% is claimed for subsidence prediction based on width of extraction and depth of cover (National Coal Board, 1975). The subsidence in the USA is more variable (Adamek and Jeran, 1981), particularly with respect to the point of inflexion, but the same general pattern occurs. At the shallower depths the somewhat harder roof strata involved in the caving in the USA may suffer less compaction, giving reduced values of subsidence. Subsidence at intermediate horizons below the surface

Jan 1, 1982

By E. E. Malouf

For centuries small amounts of copper have been recovered from acid mine-drainage waters. In recent years, the expansion of copper-bearing waste dump leaching for copper recovery has established a technological basis that is rapidly converting the art of copper leaching into a science. Copper leaching and recovery from solution has become an important adjunct of nearly all copper mining operations. Leaching of copper, whether from copper- bearing ore or waste, follows well established chemical reactions commonly in an acid circuit, but where leaching of copper is to be made in rock that is a high acid consumer, ammonia and ammonia carbonate, as well as cyanide leach solutions, can be used effectively. Current hydrometallurgical processes are being applied at an ever increasing rate to recover the trace amounts of copper in copper mine waste by in-place leaching. Currently approximately 300,000 tons of copper are produced annually in this manner while as recently as ten years ago, only one-eighth of this amount of precipitate copper was produced. Where copper occurs as an oxide in higher concentrations as to be classified as an ore rather than waste, then the hydrometallurgical processes are applied as percolation or agitation leaching in vats, pachuca tanks or prepared heaps. This approach gives better control over the recovery of the leach solutions, particularly in the processes where ammonia or cyanide leaching agents are to be used.

Jan 8, 1972

By John J. Gilman

F many years it has been suspected that a correlation existed between pits produced by etching and the density of dislocations in crystals. In 1953, the interest in this correlation was greatly stimulated when Vogel et al&apos; demonstrated a 1:l correlation between etch pits and dislocations in low angle grain boundaries of germanium. About two years ago, the author began attempts to produce etch pits at dislocation sites in zinc mono-crystals. These attempts met with success a year or so ago,&apos; and since that time a survey has been made of the etch pit patterns that are associated with various modes of deformation in zinc monocrystals. Unfortunately, the etching technique that will be described is too delicate for use as an accurate quantitative tool. Nevertheless, it has been of considerable assistance in clarifying the structure of plastically deformed crystals. Technique Many attempts were made to produce etch pits in high purity zinc crystals. It was found that several techniques would produce surface grooves at grain boundaries that had misorientation angles greater than about l°, but no technique was successful for boundaries with smaller angles. Among the things that were tried were: electrolytic CrO, (both etching and polishing concentrations), HNO, in various water and alcohol solutions, dilute HC1, many 0-0,-Na,SO, solutions, Cr0,-HC1 solutions, picral, electrolytic Na,S,O,, and electrolytic NaOH and KOH. A few attempts to use cathodic sputtering and thermal etching were also made.

Jan 1, 1957

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10&apos;" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,&apos; equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,&apos; and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson&apos; have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry&apos; estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and out standing attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated: 1924 What is Steel? By Albert Sauveur.

Jan 1, 1936

The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and out- standing attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated: 1924 What is Steel? By Albert Sauveur.

Jan 1, 1934

The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and out- standing attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated: 1924 What is Steel? By Albert Sauveur.

Jan 1, 1932

The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and out standing attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated: 1924 What is Steel? By Albert Sauveur.

Jan 1, 1934

Much has been written in the past about the non- cataracting ball mill as typified by the installations of the Tennessee Copper Co. at Copperhill and the three units of the Cleveland-Cliffs Iron Co. in its Humboldt and Republic mills. Because no direct comparisons are available from the Cleveland-Cliffs plants and because the published data of Tennessee Copper Co.&apos;s London mill covered a period of development over several years, it has been difficult for engineers to grasp the full significance of the non-cataracting economics.

Jan 11, 1957

Howe Memorial Lecture The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and outstanding attainment in the science and -practice of iron and steel metallurgy- or-metallography, chosen -by-the Board-of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated 1924 What is Steel&apos;., By Albert Sauveur.

Jan 1, 1938