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By A. F. Lucas

The discovery of oil in 1901 on the Spindletop dome, Texas, inaugurated a new industry on the Gulf Coast, an industry which has gran with the discovery of successive fields, until today it engages the services of thousands of workers and employs enormous capital. New fields are being discovered from time to time and doubtless some still remain to be found, though of late years discoveries have become more infrequent. Nowadays several hundred dry holes are drilled each year in a fruitless and blind effort to discover new fields, for as yet geologic science has developed no effectual method of locating the coastal oil deposits in advance of drilling. Moreover despite the occasional discovery of new fields, the total production of the Gulf Coast is today no greater than it was in 1906, for the added production of the new fields has been offset by the rapid decline and more or less complete exhaustion of some of the older ones. Careful geologic work within the fields has in some cases increased the production temporarily, but has developed no really new supplies. The Gulf Coast oil industry seems to have passed its period of greatest expansion and to be declining at a fairly steady rate, and this condition is naturally viewed with alarm by the more farsighted operators. In my opinion, the time has come for the adoption of radical and aggressive methods of prospecting; and a fraction of the money wasted yearly in drilling shallow wells in hopeless locations might well be devoted to this purpose. Many facts lead me to believe that all the salt-dome oil has had a common origin; that it has migrated up from considerable depth along lines of structural weakness; and that a deep well, properly located, stands an excellent chance of discovering the parent reservoir and thus of developing new and probably great supplies. This paper is presented as a discussion—necessarily hypothetical and based largely on personal opinion—of the possibility of encountering deep-seated oil deposits beneath the salt domes. Salt-dome Structure All of the oil produced in the coastal region of Texas and Louisiana is probably associated with salt domes, though in Goose Creek, Edgerly, and one or two other fields no salt has yet been actually penetrated. As

Jan 1, 1920

By E. S. Greiner

STUDY of the plasticity of germanium or other semiconductor crystals affords unusual opportunities to extend our knowledge of deformation mechanisms. Crystals are available having extraordinary perfection and very high purity. They deform by slip on the systems {111} <110>,1-3 as do crystals of the simple face-centered-cubic structure. Dislocations generated in them during slip are easily revealed in the form of etch pits on either (111) or (100) surfaces.4,5 This fact alone makes possible more detailed studies of mechanisms than is usually the case with metals but, even further, the effect of deformation on their electrical conductivity is very large compared with metals. This comes about not only because the mobility of the charge carriers is reduced, as in deformed metals, but also because the number of these carriers is greatly altered. This latter effect seems closely related to the formation of both line and point imperfections during deformation and thus provides a needed tool for the study of the kinds and distributions of these imperfections. Other investigators have deformed germanium at elevated temperatures by bending,1, 6-8 compres-sion,6, 0,10 tension,2,3,6,11,12 torsion,23 and indentation." Wang and Alexander" have also reported successful indentation at room temperature. Dislocation etch pits consequent to deformation have been observed and studied.7,8,10,18,14,20 The experiments to be de- scribed here include principally the compression and the subsequent annealing of germanium with concomitant studies of etch pits, microstructures, and electrical properties. Both single crystals and heavily twinned specimens were used. Some indentation studies are included. Experimental Methods Plastic compression was effected in the apparatus shown schematically in Fig. 1. It consists of two tantalum platens contained in a helium atmosphere and so arranged that pressure can be applied by a hydraulic press. The specimen between the platens is heated by the surrounding furnace. The specimen is usually a small crystal cube about 0.30 in. on an edge. A control specimen is always inserted so, that it is subject to the same thermal cycle as the one being deformed. This serves to detect any impurity contamination that might accompany the thermal treatment. For high temperature work, where such impurity contamination often occurs, the specimens were first plated with gold whenever subsequent electrical properties were to be determined. This method" is effective in preventing significant contamination of germanium up to temperatures at least as high as 750°C, as evidenced by the constancy of the electrical conductivities of control specimens subjected to the same heat treatments. The total range of temperature used for deformation was from 375°C, the lowest at which significant flow was observed, up to 900°C. Microscopic examination was made after mechanical and chemical polishing and etching. Dislocation pits were revealed with CP-4 etchant by the tech-

Jan 1, 1958

By E. Posnjak

IT is rather the general belief that acidified, solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as. cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by passing air for 3 hr.. through solutions of Mohr&apos;s salt acidified with sulfuric acid." While this statement will bee proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2 His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 12, 1926

By John C. Cook

Long-wave short-pulse radar has been shown capable of exploring to distances of several hundred feet through massive, dry rock salt. Exploration distances of 30 to 60 ft through bituminous coal and massive limestone, respectively, have also been demonstrated with low-power experimental radar equipment in underground mines. Working ranges up to 250 ft in limestone and coal are considered feasible. Radar reflections should be produced by all large electrically contrasting objects such as fault gouge masses, wet shattered ground, metallic mineralization, adjacent mine workings (dry or flooded), and abandoned drill holes. It is believed that radar can locate such obstacles in advance of underground mining through all massive rocks of low free-water content, including many igneous and metamorphic rocks. Three years of studies and experiments in radar exploration through rocks are reported.

Jan 1, 1974

By F. Morgan, M. Muskat, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.&apos; Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

By M. Muskat, F. Morgan, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.&apos; Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

Discussion of the paper of Earl S. Bardwell, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 79, July, 1913, pp. .1429 to 1441. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :-It is pleasing to the originators of the planimetric determination of oxygen in refined copper to see that the method has been taken up by a large smelting plant to be used in every-day work after it has been simplified to suit the new conditions. Several years ago Huntington and Desch 1 had improved our mode of working. They projected the developed negative on to a screen, traced the outlines of the picture with a pencil, drew a border, and measured one constituent with. the planimeter. In order to give the work greater precision, they divided the area into squares of 1 cm. side, shaded the

Jan 11, 1913

By B. Sadtler

The oldest producing district of Park county, and in fact one of the oldest producing gold-districts of the State, is situated on the head-waters of the Platte and tributary streams. Geo-

Jan 1, 1897

By W. L. Phillips

Single crystals of aluminum, brass, and copper oriented for (100) and (110) slip were extended at 25°, 400°, and 600°C in simple shear. Aluminum specimens oriented for nonoctahedral slip began to shear at a higher critical resolved shear stress than specimens oriented for octahedral slip. Parabolic stress-strain curves were obtained from zero strain. The initial rate of parabolic hardening was lower for specimens sheared on the (100) plane in a close-packed direction <110>, than for specimens sheared in a nonclose-packed direction <100>. metallographic evidence, however, showed that all slip traces could be explained in terms of (111) <100> slip. All attempts to cause nonoctahedral slip in copper and 70-30 a-brass single crystals were unsuccessful. Instead of shearing, the crystals bent, allowing {111} type planes to come into action. NONOCTAHEDRAL slip in aluminum has been reported under three different conditions: first, as the main mode of slip in tension experiments at elevated temperatures;&apos;-&apos; second, as the main mode of slip in direct shear experiments at room temperat~re; and third, as a minor mode of deformation, i.e., as cross-slip, in tension, shear, and bicrystal experiments at room and elevated temperatures."-l2 However, as far as the author knows, nonoctahedral slip has not been reported in either copper or 70-30 a-brass. The present study was undertaken to determine whether nonoctahedral slip could be obtained in aluminum, brass, or copper at room or elevated temperatures when the shear stress was approximately constant over the cross-section, a maximum at the center, or a maximum at the surface. EXPERIMENTAL PROCEDURE A detailed description of the crystal preparation and shearing apparatus has been given previo~sly. Cylindrical crystals 1/2 in. in diam and 8 in. long were grown from the melt in a temperature-gradient furnace. The aluminum contained 0.001 pct Zn, 0.001 pct S, and 0.001 pct Fe; the 70-30 brass contained 0.015 pct Pb, 0.001 pct Fe, 0.01 pct Ni, 0.02 pct Sn, and 0.005 pct Se; the copper was certified OFHC of 99.98 pct purity. All samples were electropolished prior to testing. The shear apparatus was a modified Bausch type. The strain sensitivity was 4 x lob4 Load was applied by clamping the rods attached to the shear plates in an Instron tensile machine. The rate of loading was 0.02 in. per min. In all cases a 1/8-in. gage length was used. For the tests performed at 400° and 600°C the shear plates, collars, and rods were made of stainless steel. These elevated-temperature tests were performed in an argon atmosphere. A) Aluminum at Room Temperature. Values of a and ß for the various slip planes and slip directions investigated are shown in Table I where a is the complement of the angle between the specimen axis and the slip direction, and ß is the angle between the specimen axis and the normal to the shear plane. The shear stress is a function of a (assuming ß - 0);10 when a is less than 27 deg, the shear stress on the slip plane for which the specimen is oriented has a maximum at the center of the crystal; at a = 27 deg the shear stress is constant across the slip plane; for a greater than 27 deg the shear stress is a minimum at the center. Fig. 1 shows the stress-strain curves for specimens cut from crystals 1, 2, and 5, which were sheared on the (010) plane in the [loll direction at room temperature. These three crystals have shear-stress distributions corresponding to the three dif-

Jan 1, 1962

Jan 1, 1964

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

ARTHUR KNAPP, Ardmore, Pa. (communication to the Secretary*). -The author has failed to consider the point which in my mind is the most convincing in advocating some sort of a bureau for the collection of well logs. I venture to say that 90 per cent. of the logs as taken today are absolutely worthless to any one but the one who has taken the log. This is largely due to the careless use of nomenclature. The author says on page 289, "He must ascertain which of the many factors might account for the dry hole in question and often only careful examination of well logs will convey this information." I believe that even a most careful examination of the average log reveals nothing. I have at hand a book on petroleum, by a well-known author. This book has a number of logs from fields all over the world, from which I shall illustrate. In a well log from Kansas I find "Soft gray shale" and in one from Humble I find "Hard blue shale." As a matter of fact the shale from Humble is softer than the shale from the Kansas well. The difference is that the drillers in Kansas, being used to limestone and

Jan 5, 1917

By George E. Aiken

Modern high speed bucket wheel excavators (BWEs) can dig materials which power shovels can&apos;t handle without blasting. Yet these machines are not used in any large, open pit ore mines in the United States. American mining has been slow to use the wheel&apos;s special capabilities of high production volume at low cost, due perhaps to a traditional familiarity with shovels and draglines and/or the lack of data of BWE operation, design and cost. Of course, shovels and draglines can not be replaced by BWEs in all cases, but under suitable conditions bucket wheels can out-perform other conventional excavators and simultaneously permit significant operating savings. The latter aspect will become increasingly important to American mining men because as more low to medium grade orebodies are found in regions of thick overburden, better and cheaper ways of uncovering them must be developed. Typical of such areas are the thick alluvial fans of the Southwest and the glacial drift areas in northern regions. Much of this material would handle well with a wheel excavator without blasting, although ripping might be necessary in some cases.

Jan 1, 1966

I. C. WHITE, Morgantown, W. Va. (written discussion *).-The writer&apos;s conclusions with reference to the possibility of finding commercial deposits of petroleum in Brazil were published in 1908 in the Final Report of the Coal Commission of Brazil.1 Since this volume is not generally accessible, and the author has nothing to acid thereto, the following quotation found on pages 243-7 may prove of interest: The Possibility of Petroleum Deposits in Brazil "The writer has often been asked to express an opinion as to the possibility of finding petroleum in commercial quantity in Brazil. "The question is one that does not admit of an adequate answer except for the regions visited by the writer, which as already stated, include only, a portion of that great territory, and only the southern portion of Brazil; namely, the states of Rio Grande do Sul, Santa Catharina, Paraná, and a few rapid excursions across São Paulo, and Minas Geraes, as well as the brief visit to Marahú in Bahia. "That the sedimentary beds of the Brazilian Permian once held some petroleum is attested by the evidence of the Iraty black shale which gives off the characteristic odor of this substance from São Paulo to Rio Grande do Sul.

Jan 1, 1918

By E. Swartzman

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button.

Jan 10, 1951

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. JOHN HAYS HAMMOND NEW YORK, N. Y. (Term expires February, 1908.) VICE-PRESIDENTS OF THE COUNCIL. HENRY M. HOWE NEW YORK, N. Y. J. B. GRANT DENVER, COLO. JAMES D. HAGUE NEW YORK, N. Y. (Term expires February, 1908.) SAMUEL B. CHRISTY BERKELEY, CAL. JOHN A. CHURCH NEW YORK; N. Y. New PERSIFOR FRAZER PHILADELPHIA, PA. (Term expires February, 1909.)

Mar 1, 1907

By A. V. Henry

THE kaolins of the southeastern United States were known to civiliza-tion as early as the latter part of the eighteenth century-and yet the Fig. 1.-KAOLIN PRODUCTION AND IMPORTS. commercial history of Georgia kaolins may be said to begin in the year 1900. The U. S. Bureau of Mines reported for that year a production of 6885 tons of "miscellaneous" clays in Georgia. A comparison of these figures with those of 1934, when the production rose to 284,556 tons (65 per cent of the domestic production), indicates the growing economic and technologic importance of this raw material. Fig. 1 clearly shows that a part of the increase is due to a normal growth in the use of kaolinitic clays and a part is due to replacement of clays formerly imported.

Jan 1, 1937

By W. P. Sykes

RECENT investigations of the molybdenum-carbon alloys have been reported by Becker and Ebert1,? Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses.

Jan 1, 1935

By D. A. Vaughan

COMPOUNDS in the U-N system have received little attention since the work of Rundle, Baen-ziger, Wilson, and McDonald in 1948.&apos; They described the three nitrides UN2, U2,N2, and UN as the only phases in this system. The region between UN and U,N, was reported to consist of the two phases while the region between U,N, and UN, is a homogeneous solid solution in which the U,N3, structure transforms with increasing nitrogen content into the UN, structure. This report presents the results of an X-ray diffraction study of the phases present in the region of the diffusion gradient on uranium reacted with nitrogen at several temperatures between 500" and 915°C. Several samples of uranium used in U-N gas-metal reactions by Mallett and Gerds were available for X-ray diffraction study of phase composition through the diffusion gradient. X-ray diffraction data were obtained using filtered iron radiation at intervals through the diffusion layer of the several samples on filings or turnings at approximately 0.001 in. increments down to the base metal. Representative X-ray diffraction patterns from various layers through the case on uranium after nitriding at 850°C are shown in Fig. 1. These data show that three different phases are present in the

Jan 1, 1957

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~&apos; The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht&apos; studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969