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By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.' Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By W. L. Crentz, E. E. Donath, D. Doherty

IN 1948, the United States used nearly six million barrels of petroleum products every day. Although substitution of synthetic fuels for the natural petroleum product is not here yet, large quantities of special-purpose coal will be required in ever-increasing volume as the domestic production of oil from other sources fails to meet demand and the production of synthetic fuels begins. Petroleum economists do not agree as to when the shortages of domestic oil will appear; but the increasing per capita consumption of oil, coupled with a constantly growing population drawing on a potential domestic oil supply estimated to be 85 billion barrels, sooner or later will result in demand exceeding domestic supply. When this situation comes about, the excess demand will be either eliminated by curtailment of consumption or the demand met by increasing importation of foreign oil or by the production of synthetic fuels. The first recourse would definitely retard the heretofore unbroken rise in American living standards, while dependence upon a foreign oil supply during a war or other emergency would be dangerous. On the other hand, the enormous coal reserves in the United States, plus sizable deposits of oil shale, indicate adequate means of augmenting a diminishing domestic oil supply. Some idea of the impact of an expanding synthetic liquid fuels program on the coal-mining industry may be gathered when it is considered that to supply just half of our present-day petroleum needs synthetically from coal would increase the coal output by about 500 million tons annually, using an 11,900 Btu bituminous coal as the plant feed. If either a subbituminous coal or lignite were used, the quantity required would be materially increased. Synthetic Fuel Processes: The principal synthetic fuel processes using coal as a raw material are the Bergius, or coal-hydrogenation process, and the Fischer-Tropsch, or gas-synthesis process. These two processes not only produce different end products, but the preparation of the coal used in each presents its own individual problem to the coal-preparation engineer. The hydrogenation process brings together a mixture of dry, finely powdered coal, catalyst, and heavy oil to form a paste. Addition of hydrogen under rather high pressure and temperature conditions brings about transformation of the coal to a liquid product, from which a high-grade gasoline and other motor fuels may be obtained. The Fischer-Tropsch process requires the production of synthesis gas, a mixture of carbon monoxide and hydrogen. At the Bureau of Mines Louisiana, Mo., demonstration plant, this gas is being made by reacting dried pulverized coal with carefully controlled volumes of oxygen and superheated steam. After purification and in the presence of the proper catalyst and suitable conditions of pressure and temperature, the hydrogen and carbon monoxide components of the synthesis gas react to form motor fuel. The two processes are not competitive but rather com-

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

IN 1948, the United States used nearly six million barrels of petroleum products every day. Although substitution of synthetic fuels for the natural petroleum product is not here yet, large quantities of special-purpose coal will be required in ever-increasing volume as the domestic production of oil from other sources fails to meet demand and the production of synthetic fuels begins. Petroleum economists do not agree as to when the shortages of domestic oil will appear; but the increasing per capita consumption of oil, coupled with a constantly growing population drawing on a potential domestic oil supply estimated to be 85 billion barrels, sooner or later will result in demand exceeding domestic supply. When this situation comes about, the excess demand will be either eliminated by curtailment of consumption or the demand met by increasing importation of foreign oil or by the production of synthetic fuels. The first recourse would definitely retard the heretofore unbroken rise in American living standards, while dependence upon a foreign oil supply during a war or other emergency would be dangerous. On the other hand, the enormous coal reserves in the United States, plus sizable deposits of oil shale, indicate adequate means of augmenting a diminishing domestic oil supply. Some idea of the impact of an expanding synthetic liquid fuels program on the coal-mining industry may be gathered when it is considered that to supply just half of our present-day petroleum needs synthetically from coal would increase the coal output by about 500 million tons annually, using an 11,900 Btu bituminous coal as the plant feed. If either a subbituminous coal or lignite were used, the quantity required would be materially increased. Synthetic Fuel Processes: The principal synthetic fuel processes using coal as a raw material are the Bergius, or coal-hydrogenation process, and the Fischer-Tropsch, or gas-synthesis process. These two processes not only produce different end products, but the preparation of the coal used in each presents its own individual problem to the coal-preparation engineer. The hydrogenation process brings together a mixture of dry, finely powdered coal, catalyst, and heavy oil to form a paste. Addition of hydrogen under rather high pressure and temperature conditions brings about transformation of the coal to a liquid product, from which a high-grade gasoline and other motor fuels may be obtained. The Fischer-Tropsch process requires the production of synthesis gas, a mixture of carbon monoxide and hydrogen. At the Bureau of Mines Louisiana, Mo., demonstration plant, this gas is being made by reacting dried pulverized coal with carefully controlled volumes of oxygen and superheated steam. After purification and in the presence of the proper catalyst and suitable conditions of pressure and temperature, the hydrogen and carbon monoxide components of the synthesis gas react to form motor fuel. The two processes are not competitive but rather com-

Jan 1, 1951

By Robert T. Howard, Morris Cohen

IT has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkin1 has shown that the compositions of two coexisting phases in a a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanalysis.3 Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantitative way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of, this research could not be treated satisfactorily by other quantitative tools, such as specific volume,4 magnetic,5 dilatometric,6 electrical resistance7 or x-ray measurements.8 It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. LITERATURE SURVEY Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1947

By Donald R. Reichmuth

Most brittle solids are relatively weak in tension and this weakness can be very significant in determining their performance in structures and excavations. Consequently, accurate knowledge of the tensile strength of brittle materials has long been recognized as important. In the past, measurements of the tensile strength of materials such as concrete, ceramics, and particularly rock have been hindered by problems encountered in fabricating test specimens and in accurately loading them. These difficulties have resulted in a scarcity of published tensile strength data. This can be readily seen in tabulations such as Wuerker's "Annotated Tables of Strength and Elastic Properties of Rocks."1 There are now three distinct approaches being used to determine the tensile strength of brittle materials. These are shown schematically in Fig. 1. The first method consists of simply pulling the specimen apart by applying an axial load. Although this procedure is the easiest to understand, the technical problems encountered during testing are numerous. Specimens cannot be readily fabricated into dumbbell-shaped specimen* like those customarily used for testing inetals. Cylindrical specimens cannot be loaded in jaw-clamps because adverse stress conditions arise at the clamping points, which causes unreliable results. An innovation developed by Niles Grosvenor at the Colorado School of Mines, in which the load is applied through steel-end caps glued to the ends of the specimens, has considerable merit, hut the samples are costly to prepare.2 All tests using a direct pull are further handicapped by the possibility of small amounts of bending being present, the specimen's surface condition, and

Jan 1, 1968

By William Hurst

Muskat's depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

By R. S. Sherwin

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

Jan 1, 1951

By C. Z. Serpan, L. J. Wittenberg

The density of liquid plutonium was determined, by a pycnometm'c technique, from 664 to 788°C and exhibited a temperature dependence, which could be expressed as:. P= C17.63 - 1.52 x 10-"t] +0.04 g per cc where t = OC. These density values compare favorably with the values previously obtained by a technique utilizing Archimedes' principle. The apparatus and method were evaluated when the densities 0.f molten tin and bismuth were measured and found to be in agreement with accepted literature values. PLUTONIUM or an alloy of plutonium in the liquid state has been proposed as a fuel for a fast-breeder type nuclear power plant.' Since knowledge of the liquid density of plutonium is required for the proper design of such a system, this study was undertaken. In addition, the density and volume expansion coefficient of liquid plutonium are of interest for comparison with these same properties of the six allotropic modifications of the solid metal. Comstock and GibneyZ were first to report a value for the density of liquid plutonium. The value for only one temperature, 665"C, was calculated from data obtained by the radiography of the meniscus, Fig. 3. Recently, the density at a series of temperatures has been reported by Knight,3 who obtained his values by using a differential volumeter, and by 01-sen, Sandenaw, and Herrik, who obtained their values from measurements of the loss in weight of a tungsten bob immersed in the liquid. The density of liquid plutonium reported here was determined by a vacuum pycnometer method. In an evacuated system, the tips of calibrated tantalum pycnometers were lowered beneath the liquid sur-

Jan 1, 1962

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

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 William Schriever

The flow of a gas-free liquid through a spherical-grain sand has been investigated by S1ichter.l By theoretical considerations involving a rather large number of approximations he arrives at the following flow-formula: V = CPd2At NLB{1 - m) where V is the volume of liquid delivered in time t through a cylindrical column of sand of length L and cross-sectional area A by a pressure-drop P when the sand grains of diameter d are packed to a porosity m and the coefficient of viscosity of the liquid is n. C and B are constants which were determined from geometrical relations; B was in reality a function of . Values of B(l — m) for various values of m were given in a table. In the same Annual Report of the U. S. Geological Survey, King reported the results of his experiments on the flow of water through porous media. He found that there was a departure of about 86 per cent. from a linear relationship between rate of flow and pressure, for a specimen of Dunnville sandstone for pressure drops not exceeding 60 cm. of mercury. The specimen was approximately 4 cm. in diameter and 5.1 cm. in length. Over the same range of pressure he found a departure of 45 per cent. for a specimen of Madison sandstone. For unconsolidated sands he found departures as great as 49 per cent. for pressure drops of 70 cm. of mercury; for pressure drops not exceeding a few inches of water he obtained a close approximation to a linear relation. He also investi-

Jan 1, 1930

By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.' The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967

The Fifth Annual National Exposition of Chemical Industries will be held in Chicago at the Coliseum and First Regiment Armory during the week of Sept. 22. It was decided to hold the exposition in Chicago, this year, for two reasons: The U. S. Army commandeered the Grand Central Palace Exposition Building in New York, immediately on the close of the last exposition and converted it into a receiving hospital, the use for which is now, happily, nearly ceased; and it was thought that the Exposition would succeed in bringing about a greater development of chemical industries in the Chicago district and the adjoining states. The Advisory Committee of the Exposition consists of: Charles H. Herty, Chairman, Editor Journal of Industrial and Engineering Chemistry; Raymond F. Bacon, Director, Mellon Institute; L. H. Baekeland, Member Naval Consulting Board; W. D. Bancroft, President, American Electrochemical Society; Henry B. Faber, Industrial Filtration Corpn.; Ellwood Hendrick, President, The Chemists' Club; Bernard C. Hesse, Chemist, General Chemical Co.; A. D. Little, President, Arthur D. Little Inc.; Wm. H. Nichols, President, American Chemical Society; R. P. Perry, Vice-president, The Barrett Co.; H. C. Parmelee, Editor Chemical &; Metallurgical Engineering, G. W. Thompson, President, American Institute of Chemical Engineers; T. B. Wagner, Vice-president, U. S. Food Products Corpn.; M. C. Whitaker, President, U. S. Industrial Chemical Co.; and Charles F. Roth and Fred W. Payne. There is also added a special Chicago committee consisting of L. V. Redman, W. D. Richardson, A. V. H. Mory, Carl S. Minor, F. W. Willard, and Wm. Hoskins; the managers, as in the past, are Charles F. Roth and Fred W. Payne.

Jan 6, 1919

By J. N. Anderson

Developments in reverberatory furnace practice at Noranda over the period 1928 to 1953 are described. Features of interest are increasing furnace tonnage from 700 to 2000 tons per furnace day, the use of the suspended basic roof, and improvements in furnace fuel ratio. Points of comparison and contrast between Canadian and American furnace practice are given. OPERATIONS at the Noranda smelter have been described in a series of papers published between 1930 and 1945.1-4 In the present paper the development of reverberatory furnace practice over the 25 year period from the beginning of operations up to the present time will be reviewed and current furnace practice will be described in some detail. Particular attention will be given to those features which are characteristic of Canadian practice: first, the use of the suspended basic roof; second, the deliberate driving of furnaces to give tonnages in the range of 1400 to 2000 tons of solid charge per furnace day; and third, the continuous operation of furnaces at high tonnage for many years without any extended shutdown for repairs or rebuilding. Finally, points of comparison and contrast between reverberatory furnace practice in Canada and the United States will be discussed. The Noranda smelter, which started in December 1927, was built for the reduction of ore from the Horne mine where early development had shown a comparatively small tonnage of rich cop-per-gold ore of a grade and character which would require direct smelting. The smelter was designed for a capacity of 1000 tons of ore a day and originally consisted of eight roasters, two reverberatory furnaces, and two converters, together with necessary auxiliaries. The discovery of a large new body of ore in 1928 made it necessary to increase both the size and the scope of the reduction plant. A mill which was ultimately brought to a capacity of 3000 tons a day was built for concentrating low grade ore and in addition the capacity of the smelting plant had to be greatly expanded, so that for the next fifteen years every effort in the smelter was directed toward achieving maximum tonnage. Because the layout and design of the smelter made it impracticable to add a third furnace, it was necessary to increase the tonnage on the two original furnaces by improvements in furnace design and operation, roasting and converting equipment being added as required to meet the demands of increased furnace capacity. The smelter tonnage, which reached a peak in 1941, was curtailed in 1944 when it became necessary to operate on a one-furnace basis because of a reduction in the output of the Horne mine due to a shortage of labor. Two-furnace operation at a moderate tonnage was resumed in 1949. In the early years the smelter tonnage was made up almost entirely of Noranda ores and concentrates. However, since 1937 an increasing tonnage of ores and concentrates from other mines has been treated in the smelter. In recent years, with decreased production from the Horne mine, copper concentrates from several mines in the district, treated on a custom basis, have formed an important part of the smelter tonnage. A review of developments in reverberatory furnace practice at Noranda falls naturally into the following four periods: 1—1928 to 1935, the early years; 2—1935 to 1944, the period of greatest change and development; 3—1944 to 1949, one-furnace op-

Jan 1, 1955

By D. T. Goettge, E. L. Robinson

The phase changes occurring in low carbon steel during hot strip mill rolling are shown to be metallurgically significant when related to commonly used temperature control points, particularly finishing and coiling temperatures. In combination, these temperatures are shown to have an important influence on the level and uniformity of hardness, grain size, and carbide characteristics of the finished hot and cold rolled sheets. PRODUCTION of wide flat-rolled products ordinarily requires a number of operations in sequence to prepare the material for shipment to the customer. Most products are tailor-made for specific end uses, with each operation contributing certain properties to the finished material. Since the characteristics imparted to the semifinished product by a given step in processing carry through to the finished product in varying degrees, it is important that the intermediate stages of production of flat-rolled strip be carried out with the same care which characterizes the last or finishing operations. The step of hot strip mill rolling is common to the production of all of the various types of flat-rolled product; therefore, the hot strip rolling is an especially important point at which to recognize and control those variables which have an effect on the surface characteristics and metallurgical properties of the finished product and which influence the ease of conducting subsequent operations. Orders entered at a producing mill usually show an end use or describe an article or part into which the ordered product is to be fabricated. Applying his experience as to the properties necessary in a finished sheet to suit the end use and to perform successfully in the fabrication involved, the metallurgist selects a steel of suitable composition and deoxidation practice, and slabs of appropriate dimensions are produced for rolling on the hot strip mill. At this stage of processing, the metallurgist faces the problem of controlling hot strip mill practice in the light of his diagnosis of the properties necessary to meet the end use, paying due attention to the accompanying problem of producing a strip which can meet processing requirements on subsequent units in the mill. It is the purpose of this paper to describe some of the factors which he must consider in solving these problems and to indicate some of the principles which guide him. Equipment, Physical Requirements of the Strip, and Temperature Measurement The metallurgist must, of course, be familiar with the physical layout of the mill, the temperature-measuring equipment available, and the physical requirements of the hot strip product before he can apply his metallurgical knowledge to the problem; hence, the first section will consist of a brief discussion of these matters. The usual hot strip mill consists of reheating furnaces, five or six roughing stands including a scale-breaker, holding table, and second scalebreaker, six-stand finishing mill, runout table with spray cooling facilities, and coilers. A schematic diagram of a typical layout is shown in Fig. 1. Slab temperatures are primarily a function of heating time and furnace temperatures, while mill speeds, spray practice, drafting practice, available water pressure, temperature of the cooling water, cross sectional dimensions of the strip, coil size, and equipment limitations, either singly or in combination, determine what rolling temperatures are practical on a given hot strip mill unit. Thus, it is possible that a set of temperatures which can be utilized successfully on one mill cannot be used on another. However, adjustments in temperatures and rolling practice can usually be made to develop the desired metallurgical properties. In addition to the metallurgical properties developed through proper temperature control, the hot strip mill must also provide strip with certain physical attributes which may be summarized as follows: Strip Cross Section—The strip contour should conform to a section which will give the best results in the cold reduction operation. This is generally recognized as a strip with 0.001 to 0.003 in. crown or shoulder-to-shoulder convexity depending on width, and freedom from concave, flat, or wedge-shaped cross sections which cause metal buildup in cold reduction. Excessive drop off in thickness at the edges can also be very detrimental in cold reducing to light gages. Gage, Width, and Camber—All of these must be controlled. For example, rundown or increasing thickness from the front to the back of the coil results in nonuniformity in the thickness of hot-rolled sheet product and in added difficulty with gage and welds in cold reduction. Similarly, excessive width variation is the cause of guide trouble and excessive edge scrap at later stages of processing, while excessive camber is the source of a variety of processing troubles. Type of Oxide—Product intended for pickling should have a predominance of the type of oxide most easily removable in sulfuric acid. It is generally recognized that this type is obtained by use of maximum table cooling water and cold coiling

Jan 1, 1957

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962