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By Fred E. Carter

AT first sight, the platinum group of metals seem of little import to we, the people," although actually the life of the common man is much influenced by them; this influence is usually indirect, hence his lack of knowledge and interest. He generally associates platinum with high-class jewelry and lets it go at that. Were 11e to go deeper, he would find that platinum metals play their part in his food supply, his clothing. his health, his transportation, his home. And the technical man is in general only slightly better informed, for he usually does not realize how necessary platinum metals are in the manufacture of the many construction materials and chemical products with which he is acquainted. Certainly, our daily lives would be profoundly affected if platinum were suddenly to become unavailable.

Jan 1, 1944

By G. W. Housner

The series of earthquakes in the vicinity of Koyna Dam in south- western India, which included a very damaging magnitude 6.5 shock on Dec. 11, 1967 (Dec. 10 GMT), is of much interest. The events are exceptionally well documented, which is a tribute to Indian geologists, seismologists, and engineers. To help in disseminating the information in the United States, this chapter presents a brief summary of the pertinent data and lists references. Koynanagar (Koynatown), which began as the construction camp for the dam, is located about 140 miles southeast of Bombay and 70 miles south of Poona at 17.4ºN and 73.7ºE, about 40 miles inland from the Arabian Sea. Koyna River flows almost due south from its source a distance of about 38 miles and then makes an abrupt turn to the east and travels some 480 miles to empty into the Bay of Bengal. Koyna Dam is located about 3 miles north of this turn. The approximately north-south trending continental divide is a few miles west of Koyna and the terrain drops steeply about 1700 ft to where the hydroelectric generating station is located. The reservoir behind Koyna Dam forms a long, narrow lake (Shiva- jisagar Lake) with mean water level (MWL) at 2160-ft elevation. The 345-sq-mile watershed receives an annual rainfall of about 200 in., most of which falls between mid-June and mid-October. The peak storage is 99 x l09 cu ft. A controlled flow passes under the continental divide in a tunnel and then down to the electric generating station about 5 miles WNW of the dam. The inflow not used for power generation is released to Koyna River. The Koyna project is a major source of electric power for Bombay and produces 540 MW at peak load.

Jan 1, 1970

By Carl F. Floe, Michael B. Bever

ACCELERATED by the demands of war, research and development work in nonferrous physical metallurgy has continued at a rapid pace during the past year. In particular, advances have been made in processing and fabrication, especially of the light alloys, and in the surface treatment of metals. Theoretical physical metallurgy, although less active, has not been neglected and the year has brought forth some -notable contributions to our understanding of the fundamental structure of metals and their behavior in service. Of course, much work that has been done cannot be publicly discussed because of wartime restrictions.

Jan 1, 1945

By ROBERT E. CROCKETT

MAGNETITE mining and milling in New York, New Jersey and Pennsylvania continued to remain comparatively inactive during 1933, owing to the low rate of output of the steel industry and also to unrestricted importation of foreign ores. However, some improvement over conditions existing in 1932 was noticeable, particularly in New Jersey, where one plant, that of the Washington mine of the Alan Wood Mining Co., at Oxford, went on full production in August. At Lyon Mountain, N. Y., the Chateaugay Ore and Iron Co. resumed mining and milling operations in October, on a reduced scale, principally to provide employment during the winter months. The Chateaugay company produces a special low-phosphorus pig iron. During the year they obtained a contract to supply their product for use in the manufacture of the suspension cables of the New. Golden Gate Bridge.

Jan 1, 1934

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By R. L. Bowron

GROWING use of basic slag in the agricultural industry is of special interest and importance to the iron and steel industry of the Birmingham district, providing an increasing outlet for this by- product. Such use of basic slag was first developed in England about fifty years ago where it soon became wide- spread. About twenty years ago the Tennessee Coal, Iron & R. R. Co. began its production in the United States after exhaustive tests had demonstrated its high value here as in Eng- land. It is particularly valuable on heavy clay and acid soils, improving their physical condition, increasing their alkalinity where that is desirable, and providing soluble phosphate and small amounts of manganese to soils deficient in these respects. Its use in agriculture is growing as its advantages are becoming more widely known.

Jan 1, 1937

By L. W. Emery

Undergrorlnd combustion operations were initiated in a 60-acre Bartlesville sand "shoe-string" reservoir in Allen Connty, Kans., in 1956. Tests in separate patterns were conducted using various co~nbinations of air and recycle gas to propagate combustion fronts from the injection toward the producing wells. These patterns were made up of 6 injection and 20 prodrrcing wells Gas and liquid prorluctiorz from each pattern was measured on an individual-well basis, and comparisons were made between the three patterns to ascertain the relative effects of injected gas composition on production behavior. Breakthrough of the combustion front at a well was characterized by an increase in water production from the well followed by an increase in bottomhole temperatrrre to approximately 250" F. After burning fronts had broken through at five producing wells, operations were terminated in 1960. From the total project approximately 79,000 bbl of oil were produced during thermal operations at a cumulative produced GOR of 23 Mcf/bbl. No appreciable change in the character of the produced crude was observed. Combustion in the reservoir was maintained with injected gas compositions ranging fronz 6 per cent oxygen in recycle gas to 100 per cent air. lnjectiotz of large quantities of recycle gas resulted in higher producing GOR's from offset wells than were measured from a pattern into ~vhich straight air ~vas injected. The air required to move the combustion front through I acre-ft of reservoir was computed to be 20 MMscf. This valrre was found to be relatively independent of the quantities of recycle gas injected. The recovery efficiency from the swept area was esti~izated to be about 59 per cent. Areas swept were similar in shape to tlzose obtained with a laboratory potentiometric model. Samples of sund taken from behind the burning front by coring indicated almost total oil removal from the sand. Petrographic analysis of the core samples indicated that the sand had been heated to peuk temperature of rlbout 1,200" F. No rignificant difference in peak temperature was forrnd in two areas where compositions of injected gas were quite different. Compression costs for thermal recovery were estimated to be $1,20/bhl of produced oil. INTRODUCTION The use of the "forward combustion" process as an oil recovery method has received a great deal of attention. This method involves ignition of the formation in an injection well, followed by propagation of a combustion front through the reservoir. Combustion is maintained by the injection of an oxygen-containing gas to react with reservoir hydrocarbons. As the flame front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase and recondensed in the cooler part of the formation. In turn, the condensed fluids push oil into the producing wellbores. Completed field tests of the process were first reported by Kuhn and Koch,' and by Grant and Szasz.' Results from other tests have since been reported by Walter,3 by Moss, White and McNeil,' and by Gates and Ramey." ach of these tests essentially utilized a single injection well surrounded by four or more producing wells. Sinclair Research, Inc., elected to do field experimental work using a number of test patterns in a single field in order that comparisons between various operating schemes could be made. The site selected and purchased in 1955 for this experimental work was a 60-acre Bartlesville sand reservoir located in Allen County, Kans. Combustion operations were initiated in mid-1956. Between that time and termination of the project in mid-1960, combustion fronts were propagated from injection wells to producers in three separate well patterns, using different mixtures of air and recycle gas. The test was terminated before sweep of the three patterns was complete so that information about the effect of combustion on the swept areas could be obtained by coring. Results from the test in the form of injection and producing well performance have been carefully recorded, and these form the general basis for this paper. DESCRIPTION OF RESERVOIR The reservoir in which the combustion tests were conducted is a Bartlesville sand "shoe-string", typical of a number of small reservoirs in Southeastern Kansas. Average reservoir characteristics are shown in Table 1. Fig. 1 is an isopachous map of the producing sand showing the reservoir to be approximately 400-ft wide and 2,500-ft long. Maximum net productive sand thickness is 21 ft. Fig. 2 shows a typical core analysis obtained by coring with water-base mud. The reservoir has no appreciable dip and is closed on the sides by degradation of sand into shale. The main body of sand is heavily laminated with shale stringers, which are not continuous between wells. The main reservoir is overlain by 30 to 40 ft of laminated low-permeability sand and shale streaks. No information is available on the original properties of

By N. LILIENBERGS

DURING the past few years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice was to mike steel ingots of sufficiently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is ?worked up,? the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnance and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory, is, that the silver-clear blow-holes, without the blue oxide, can be welded by sufficient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the "blue" cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it ?dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of

May 1, 1906

By A. Hamilton Garner

The occurrence of oil seepages in Venezuela has been known since the early days of Spanish occupation. It was not until 1912, however, that any serious exploration work was undertaken. In that year, the Caribbean Petroleum Co., then a subsidiary of the General Asphalt Co., employed a large staff of geologists to make a systematic survey of large areas in eastern and western Venezuela, selecting the most desirable localities out of the immense area covered by the Valladares concession. This preliminary work was completed in the fall of 1913, and in February, 1914, the company completed its first commercial well at Mene Grande. Development work has progressed slowly, for various reasons, but petroleum in quantity has been encountered in nine widely separated localities. The Mene Grande field has been put on a producing basis and approximately 4,000,000 bbl. of oil is being shipped annually. Increasing quantities of oil are now being drawn from El Mene and La Rosa. In the light of these developments, the world's need for oil reserves, and the proximity of Venezuela to the United States, American capital is being attracted more and more to Venezuela. Although considerable careful geological work has been done in Venezuela by the various oil companies now operating, most of the data is buried in the company files, and the published literature has been extremely meager. The most valuable contribution to date has been a map and report by Jahn, which, as it was printed in Spanish, is not generally available to the American oil public. Venezuela, located in the northwestern part of South America on the Caribbean Sea, lies between l° and 12° north latitude. Its principal

Jan 1, 1925

By J. E. Willson, N. K. Bohidar

An evaluation of internal stress distribution based on photoelastic studies and destructive testing of simulation models shows that pillar failure is a function of the internal stress distribution, and that stability can be changed by altering the internal stress pattern. Induced stresses in three-dimensional epoxy disks subjected to uniaxial forces were evaluated by photoelastic studies. Stress profiles across different sections perpendicular to the loading direction revealed two maxima for each profile. Based on the stress distribution for the entire column, an attempt was made to explain pillar spalling and the hour glass pattern of failure in a mine pillar. For maximum stability and optimum design of mine pillars, it is necessary to consider the external forces, the nature and distribution of induced stresses and the characteristics of the pillar material as determined in the laboratory. This paper summarizes the research done by N. K. Bohidarl and Ben L. seegrniller2 as partial fulfilment of the requirement for Master of Science degree in Mining Engineering, University of Utah. It is an evaluation of a study to determine the stress distribution in short columns in order that regions of high stress concentration in mine pillars may be found and their effect on pillar failure be ascertained. The ratios of the dimensions of the columns studied are representative of those found in mines located in flat-bedded deposits. The weight of the overburden generally constitutes the major external force. This force is calculated by taking into account specific weight and thickness of the cover. Determination of the distribution of this force on pillars may often require a complex analytical study. There have been many investigations of the strength

Jan 1, 1968

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of 'InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of' metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.'-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.' This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.' A concurrent publication'0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.'' Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By B. K. Larkin

Solutions to the diffusion equation for a line source located anywhere in a region bounded by a circular discontinuity are presented. Such solutions follow automatically from the Green&apos;s function presented by Jaeger.4 Petroleum industry applications of this problem would include transient compressible fluid flow in porous media bounded by a discontinuity. Since several recent papers have treated the subject in less general form, it would appear that many workers in this area of the petroleum industry are not aware of Jaeger&apos;s work. STATEMENT OF THE PROBLEM In several trearments1,2,3 of the transient flow of compressible fluids in porous media it was convenient to consider a region to be bounded by a circular discontinuity. In such a region (Fig. I), the properties in Region 1, r < a, are constant but different from the properties in Region 2, r > a. Hurst, l using the Laplace transform, obtained solutions for a line source located in the center of such a porous medium. The purpose of this work is to point out that a much earlier paper by Jaeger4 presents the solution for a line source located anywhere inside the discontinuity. The assumption is made that a line source may be used to approximate a well. In the following material it is convenient to use the terms source and well as being equivalent; however, the reader should remember the distinction in applications. SOLUTIONS Jaeger presented the Green&apos;s function for a line source, or well, in the composite region shown in Fig. 1. In the most general form, the solution for a system of j wells in Region 1, each producing at a time varying rate, qi (t), is

By Hsun Hu

Based on Kurdjumoiv-Sachs orientation relationship for the fee bee transformation in metals, the jirzal crystal orientation resulting from successive transformations of bee-fee-bee has been analyzed mathematically. There are 528 different variants; many of ther are crystallograpyically equirvalent. Specific examples show that, for equal probability of all the variants, the principal crystallographic axes [100 ], [110], and [111] of the initial bcc crystal can be transformed into vairous axes in the fina1 crystal However, fur each of these principal crystallographic axes, a continuous range of orientation within certain regions of the unit triangle is completely avoided by the finctl Crystals. For uses of higher indices, the final orientations are more uniformly distributed throughout the unit triangle. Results from the PI-esent analysis are in good agreement with preferred Oientations Observed in a zone-meltecl iron bar. THE allotropic forms of iron are characterized by the unusual fact that at both high and low temperatures a bcc structure is stable, whereas at intermediate temperatures (1400" to 910°C) the metal is fcc. Hence, during cooling from its melting temperature, iron undergoes successive phase transformations ofd—? —a with corresponding changes in the crystal structure of bcc — fcc -bcc. while numerous studies have been made in the past of the 1 — a transformation in iron and in various iron-base alloys, no information is available in the literature as to the mechanism of 6 — l transformation and the lattice orientation relationship between these two phases. Experimental difficulties have apparently prevented researchers from undertaking these studies. The laltice orientation relationship between the parent and the new phases of iron resulting from

Jan 1, 1965

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,&apos; is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By P. A. van der Meulen

Some time ago, the writer received from W. O. Borcherdt, Superintendent of the works of the Bertha Mineral Co. at Austinville, Va., several specimens of a dense yellowish slag-like material, containing cavities showing clear needle-like crystals, and representing a product formed by the fumes of zinc oxide and basic lead sulphate from the oxide furnace, attacking the firebrick lining of the flues. The matrix, which is of a greenish-yellow &apos;color, is made up chiefly of an amorphous glass, carrying numerous crystals, the latter being well-defined, clear, and transparent, but colored a very light yellow by small amounts of ferric oxide. A number of the crystals were carefully separated from the matrix and tested with the blowpipe. They have a fusibility of about 2, yield a globule of lead and a coating of lead oxide before the blowpipe on charcoal, and contain some zinc. Their hardness is 5 to 6. Under the microscope the crystals appear to be made up of a prism, with narrow faces, and a fairly large pinacoid, but unfortunately show no terminal faces (Fig. 1). Between crossed nicols they gave parallel extinction in the three planes containing the crystallographic axes, and are therefore orthorhombic. The index of refraction is high. A number of the best crystals were measured on the reflection goniometer, the angles given below representing the average of measurements made on different individuals. mm = 46º 52&apos; mb = 66º 34&apos; a :b :c = 0.4334:l:? Inasmuch as the results indicate that the crystals do not correspond with any silicate of lead and zinc, either natural or artificial, heretofore

Jan 1, 1918

By R. J. Jackson, D. E. Williams, W. L. Larsen

The phase diagram of the Ta-Zr system is presented with a discussion of the methods used in its determination. The solidus contains a minimum at 1820°C near 25 wt pet Ta. A complete solid solution exists at elevated temperatures between tantalum and ß zirconium. This solid solution decomposes monotectoidally at 800°C and 12 wt pet Ta. The maximum solubility of tantalum in a zirconium is slightly less than 2 wt pet, and decreases with decreasing temperature. The solubility of zirconium in tantalum is 5 wt pet at the monotectoid temperature and about 2 wt pet at room temperature. THIS investigation was part of a program of research on refractory metal alloy systems having potential application in nuclear reactor technology. Preliminary prop-ess has been reported in the Ames Laboratory annual research reports.l Most of the previously reported work on the Ta-Zr alloy system consisted of partial phase diagram investigations and the determination of the mechanical properties of the zirconium-rich alloys. Anderson eta1.2 studied alloys containing up to 30 wt pet Ta as part of an investigation of several zirconium alloy systems. These investigators also determined some of the mechanical properties of the alloys at room temperature and 650°C. In a discussion of Anderson&apos;s work, Pfei13 suggested that the bright phase in the microstructures of the intermediate alloys is a tantalum-rich solid solution or an intermediate phase in a matrix of ß zirconium solid solution. Litton,4 Keeler,5 and Chubb6 determined the mechanical properties of zirconium-rich alloys at ambient and elevated temperatures. Van Thyne and McPherson7 reported the tensile properties

Jan 1, 1962