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By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By C. C. Miller, A. R. Belyea, C. H. Herty, E. B. Burkart

The removal of sulfur from steel has been studied by many investigators, but the quantitative relationships between the factors involved have not been determined. This is undoubtedly due to the number of variables encountered in practice, an attempt to study any one reaction or relation being affected by other reactions the relative importance of which cannot be estimated. The factors that affect the extent of removal of sulfur in the basic open-hearth process are generally considered to be: 1. Basicity of the slag: (a) Iron oxides in the slag; (b) carbon in the metal or carbide in the slag; (c) temperature. These factors affect the reactions: FeS + CaO = CaS + FeO FeS + CaO + C = CaS + CO + Fe. 2. Amount of sulfur in the gas. 3. Amount of manganese in the metal. The factors which affect the rate of removal of sulfur include, in addition to these: 4. Fluidity of the slag: (a) Normal changes in fluidity with temperature; (b) changes in fluidity because of the addition of special reagents such as fluorspar. 5. Agitation of the bath. Within the past two years, two papers have been presented dealing with the influence of sulfur in the gas on slag and metal. Nead' has shown that if a gas high in sulfur be used for heating, the metal and slag will absorb sulfur. Whitely2 concluded from his experiments that if a

Jan 1, 1925

By A. Raja, C. C. Harris

Apparatus for maintaining constant — but adjustable — pulp level and rate of froth removal are described. The results of preliminary experiments into the effect of scraping speed on the rate of solid and liquid recovery with a semi-batch system are presented. Glass spheres restricted to a narrow size range is the solid under investigation. Graphical methods for estimating the mass of recoverable material and the zero error are given. The semi-batch procedure1 is extensively used in laboratory flotation testing, though the method is subject to variability of moderate severity. Raffinot2 concluded from a statistical study of the difference between replicate tests, that the ptincipal source of errot was the test itself and not sampling or chemical analysis. These differences can be ascribed principally to changes in pulp volume and reagent concentration, and uncontrolled rate and depth of scraping. Semi-batch testing has been criticized1 on these grounds as a means of investigating flotation kinetics. This paper discusses and describes modifications to laboratory flotation equipment which reduce the number of manual operations and lead to improved control. Kinetic studies were the primary reason for developing the apparatus described. It should, however be a useful aid in normal flotation testing. Some preliminary results of experiments are presented.

Jan 1, 1967

By Samuel Hoyt

SOME of the more important properties of finished materials are strength, ductility, toughness, resistance to alternating and repeated stresses, etc: Of these, the property that appears to have received the least consideration, at least in this country, is toughness, which is clue, possibly, to our regarding toughness as a qualitative property or, at any rate, as one that, parallels ductility. This arises out of our greater experience with the simple carbon steels in the rolled or forged (non-heat-treated) condition which, qualitatively, are tough if ductile and are not tough if brittle. In this way we have erroneously become, accustomed to judging the toughness of a material from its behavior in the tensile or similar test. The point of view presented in the present paper is that toughness, like hardness or tensile strength, should be regarded as an independent property and of sufficient importance to require, in so far as that may be possible, quantitative determinations. If such be true, it becomes at once necessary to devise experimental means for measuring, or valuating toughness, and the notched-bar impact test (the Charpy test) is advanced as the most logical test that has so far been developed for this purpose. It is further advanced, with particular emphasis, that we have two kinds of toughness to deal with and, accordingly, they will be dealt with independently. CLASSIFICATION OF MATERIALS ACCORDING TO TOUGHNESS Toughness has been defined somewhat as follows: Tough materials are those that offer considerable resistance to permanent deformation but which, once such resistance has been overcome, may' be deformed plastically, but only by the expenditure of considerable energy. In other words; tough materials may be deformed plastically but they absorb a considerable amount of work in the process. This kind of toughness may be called "static" toughness when the rate of loading is reasonably slow or "dynamic" toughness when the rate of loading is

Jan 2, 1919

By C. G. Cheriton

The Bathurst mining district is located near the town of Bathurst on the north shore of the province of New Brunswick in eastern Canada. This region is the northeasterly extension of the Appalachian mountain system. The area is heavily forested and covered with a fairly uniform layer of glacial gravels and boulder clay. The relief is low, increasing to a few hundred feet in the north west and several hundred feet in the extreme southwest. Thus, rock outcrops are scarce and occur mostly along streams and ridges. These factors made conventional prospecting difficult and resulted in the district becoming an excellent place for the application of regional geological studies, air photo techniques, airborne and gound geophysical methods and soil sampling. Late in 1952, The Brunswick Mining and Smelting Company discovered a very large base metal sulphide body presently known as their No. 6 orebody. Early in 1953, another and even larger sulphide body was discovered and is known as the No. 12 ore body. Mining exploration was very active thoughout 1953 and in 1954, The American Metal Company discovered the orebodies which have been developed into The Heath Steele 'Mines. The location of these deposits is shown on figure one. In the latter part of 1954, The Anaconda Company became interested in the district and decided to make a geological study of this new and promising base rrietal area. The following paper presents the story of the application of modern geological and geophysical techniques, leading to the discovery of a large sul-nhidp liodv. The Bathurst district is generally underlain by the Tetagouche group of Middle Ordovician rocks.

Jan 1, 1961

Q: It is May 1961 at Bill Wrather's Washington house. Bill, think back to your first job after college. Wrather: Perhaps I ought to go back a little bit further than my first job. I entered the University of Chicago with the idea of studying law. My intention was to take a 4-yr liberal arts course and superimpose a law degree on that. But during my undergraduate work I fell under the influence of R. D. Salsbury. He decided I had some talent as a geologist and influenced me to take a geological course. Nevertheless, I did not give up the idea of law. While in school I took a spell of typhoid fever and almost died. The doctor recommended outdoor exercise, so a geological job seemed logical. W. H. Emmons was a graduate student in the University and he interceded with Dr. Hayes of the USGS. I went on the payroll as assistant packer at $60 a month. I had one of the most glorious summers I ever spent in my life. That fall and the following year I took law courses and became thoroughly convinced that I was cut out for a geologist rather than a lawyer. I finished up my law work in 1908 while waiting for a job with Bill Emmons, who was doing a careful study of Goldfield and Tonopah.

Jan 4, 1964

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum's work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By A. G. Rozner

TRANSVERSE rupture tests have been commonly used in mechanical investigations of brittle materials. The specimens are simple, easy to prepare, and loading presents no difficulty. Owing to the complexity of stress distribution in bending1 one can determine stresses rigorously only for the elastic range. The bend-test results, however, are at times converted into tensile-strength data, determined as maximum fiber stress. The assumption is made that for small plastic deformations the linear stress-strain relation applies. This problem was experimentally investigated by Bach3 who tested cast iron in bending and in tension and found that the maximum fiber strength obtained in bending exceeded the experimental tensile strength by a factor depending on the geometry of the tested piece. The factor varied from 1.57 for a rectangular cross section to 2.12 for a circular cross section of the tested beam. Since this work was carried out 60 years ago, the cast iron used could be expected to have been highly brittle, thus the extent of plastic deformation prior to fracture very small. We have therefore carried out a number of tests on magnesium-modified cast iron with an average elongation of -5 pct. It was hoped that the data obtained from the tests would serve as a guideline for comparing data obtained in tension and bending for brittle materials. Mechanical properties were measured at room temperature on an Instron tensile machine at a crosshead speed of 0.05 in. per min. The three-point bend test employed cylindrical bars 0.20 in. in diameter with a 1.0-in. span. For the tensile test, cylindrical tensile specimens with a gage length of 0.85 in. and a diameter of 0.160 in. were used. Results are summarized in Table I. From Table I one can see that fracture strength

Jan 1, 1965

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Jan 1, 1938

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

Large deposits of manganiferous iron ores, representing several million tons of metallic manganese, occur in the United States. The Minnesota deposits of such ore are of outstanding importance because of their size, state of development, ease of mining and proximity to the Great Lakes, which permits water transportation to steel centers. In view of the fact that our steel industry requires large quantities of manganese, for which no satisfactory substitute has been found, and because our reserves of ferro-grade ore are comparatively small, the development of methods that will make our large deposits of manganiferous iron ores available as a source of ferromanganese is an important problem. Realizing the importance of this problem, some years ago the North Central Station of the U. S. Bureau of Mines and the Minnesota School of Mines Experiment Station undertook jointly the development of methods for recovering the .manganese content of manganiferous iron ores in a form suitable for the production of ferromanganese, the 80 per cent. alloy indispensable in producing steel. Two types of manganiferous iron ores have been described in previous reports.' The brown ores are higher in iron and lower in manganese than the black ores; the black ores are more siliceous but contain less phosphorus. The utilization of the iron content of the brown ores in the production of steel appears to furnish the best basis for their treatment. The method of attack has been to work out modifications in iron and steel practice so as to recover manganese in the form of slag comparable to ferro-grade ores. The greater part of the experimental work has been conducted with a 6-ton blast furnace and a 1/2-ton basic open hearth. This paper is devoted mainly to open-hearth tests in which high-phosphorus spiegel

Jan 1, 1930

By Thomas Leonard Watson

Jan 1, 1906

By Ingvar Janelid

DURING the last ten years, in the effort to save manpower and costs, methods of drilling and blasting in Sweden have changed and developed in a revolutionary manner. These developments have been accompanied by extensive alterations in methods of tunneling and in mining technique. Since the end of the 1940's there has been a 100 pct change-over in Sweden to the use of tungsten carbide tipped drill steel. Both investigations and practical results have shown clearly that a tungsten carbide chisel bit fastened directly on the drill steel is the most economical for Swedish conditions. This applies to drill steel up to the longest size it is practical to handle. In terms of drilling footage, durability of the drill steel and the tungsten carbide bit is generally the same. In this respect, therefore, a detachable bit offers no advantage over integral steel. Transportation of integral steel to the grinding plant, instead of detachable bits only, involves heavier work, but this is counteracted by placing grinding plants closer together or by grinding at the working place itself. The drilling rate with integral steel is higher, the trouble of changing bits is avoided, and the difficulties which always arise with joints are eliminated. At present steel dimensions are usually 7/8 in. with a shank 41/4 in. long, whereas the international standard shank was formerly 31/4 in. The longer shank renders possible a better guide control of the steel and consequently longer life for the rotation chuck and the water-flushing pipe. After extensive experiments and investigations, agreement has been reached in Sweden on certain series of standards, shown in Table I. Other steel dimensions are, of course, available for special purposes. The standard drill-steel set begins with a 34-mm diam and has a length interval of 2 2/3 ft. On the other hand, for ordinary drifting it has been proved more economical to use greater length intervals on the steel, so only one steel change is required for a 61/2-ft round. Moreover, owing to the relatively close hole spacing necessary in a drift round, it has been possible to reduce the diameters of the tungsten carbide bits. This results in faster and cheaper drilling. As shown by the table, the lengths of drill steels for normal drifting are 33/4 ft and 71/2 ft, with 29 and 28-mm diam bits. During the last few years operators have begun to use 3/4-in. drill steel in place of the 7/8-in. drill steel chiefly employed earlier. This is a valuable development in drilling technique, particularly in view of

Jan 1, 1955

Four years of intensive exploration effort by Newmont Mining Corp. came to a climax May 27 in Carlin, Nevada, when local, state and federal officials joined with company officers at a dedication ceremony saluting the start-up of the firm's wholly- owned subsidiary, Carlin Gold Mining Co. Before an invited audience at the plant site, Newmont's President Plato Malozemoff and Nevada's Senator Howard D. Cannon pushed a lever and watched the new melting furnace rotate until a brilliant orange-red stream of molten gold poured forth from its mouth. Two 1200-oz bricks of bullion were poured that day, and they are the first of many that will lift this mine into the number two slot among U.S. gold producers and fourth among all gold mines on the North American continent. Although Newmont Mining first entered the gold mining business in 1929 in Grass Valley, California, the Company had operated no gold producers since the well-known Government directive L208, issued in 1942, closed down U.S. gold mines for the duration of World War 11. Now it is back in the business in a big way-a $10 million mine and plant capable of producing 200,000 oz. per year. All the gold from the Carlin operations is earmarked for the U.S. Mint in San Francisco.

Jan 7, 1965

By L. F. Pease, J. H. Brophy

A phase diagram for the Ta-Zr system is presented. The system is of the minimum-melting point type with the 0-zirconium phase decomposing monotectoidally at 785°C and 95.5 at. pct Zr. The minimum solidus temperature is 1875°C and the temperature of the top of the monotectoid loop is 1775°C. Techniques employed included X-ray diffraction and fluorescmce, electron microprobe analyses, diffusion couples, metallography, and melting-point measurements. Errors due to interstitial solutes and in melting observations are particularly common in this system, and their occurrence is discussed. SEVERAL versions of the Ta-Zr phase diagram have been reported in the literature.lm7 Williams et al.' report a diagram of the minimum-melting point type with a monotectoid reaction at 800°C and 12 wt pct Ta. The minimum in the solidus occurs at 1820°C and 25 wt pct Ta, while the top of the monotectoid gap is located at 1780°C and 80 wt pct Ta. The experimental techniques employed were metallography, electrical resistance variation with temperature, dilatometry, X-ray diffraction, and direct observation of melting by the technique of Pirani and ~lterthum.' Experience in the Nb-Zr phase diagram has shown that small changes in the interstitial content can cause large shifts in the positions of the phase boundaries. Small amounts of inter -stitials can cause similar changes in the Ta-Zr system and may be responsible for the wide variations in the phase diagrams previously reported.'-' The authors15 have found that alloys containing 0.75 wt pct 0 and 1.0 wt pct Ni with tantalum contents from 19 to 85 at. pct often contain a lamellar or cellular precipitate after annealing above 1400°C. This precipitate is very similar to that reported by pollack,12 Ralls," and Donlevy17 for the Ni-Zr system. In the present investigation, a wider variety of experimental techniques and improved alloy purity were applied to the resolution of errors in diagrams for this system as they now appear in the literature. New results have been obtained in the areas of alloy homogeneity and purity. Errors in the common techniques of direct melting observation in binary alloys have been demonstrated. In the commercially important high-tantalum region, the more accurate metallographic method of solidus determination has been employed. EXPERIMENTAL PROCEDURE Nominal analyses of the materials employed are given in Table I. The zirconium was low hafnium reactor grade iodide crystal bar, and the tantalum was in the form of high-purity sheet. Powders were impossible to use because of gas content. Alloys were melted on a water-cooled copper hearth, with a thoriated tungsten-tipped nonconsumable electrode in 2/3 atm of Zr "gettered" argon. Alloys were

Jan 1, 1963

By F. C. Langenberg, J. Chipman

Jan 1, 1959

By W. J. Verner, J. R. Lucas

Billions of tons of bulk solid materials are processed through our industrial plants each year, and the tonnage is steadily rising. It has been estimated that for every dollar spent in industry as a whole, approxinlately 30 cents is consumed in the handling of bulk solid materials. It is in this category that tremendous savings are possible through the use of improved techniques. Since World War 11, the mining, steel, chemical, and grain industries, among others have made use of increased materials-handling automation in order to gain some of these savings. However, in a chain of automatic operations, every link must be completely reliable, for if there is a single failure, the whole system immediately becomes ineffective. Only too often the weak link in the chain proves to be the flow of bulk solids from bins. To contribute to the fundamental knowledge in this area, a research study has been continuing at The Ohio State University. The principal objective of the investigation has been to study the internal stresses existing in confined bulk solids. LITERATURE SURVEY Literature studies have revealed that many outstanding people have made contributions to the field of bulk solids. For instance, C. F. Jenkin,1 suggested: a. The pressure on a bin wall is not directly proportional to the depth beneath the surface of material in the bin. b. The vertical pressure distribution on the base of a bin is not actually uniform but is a variable. c. Arches form in bins as a result of very small deformations of the material in the bin. This deformation causes a series of gaps to appear, and consequently causes the disappearance of diagonal forces that cannot act across these gaps. The removal of the diagonal forces causes horizontal forces to be introduced which seem to be the chief cause of arching. 11. A. Janssen,4 in 1895 in connection with his experiments on bins, derived a differential equation to describe both the lateral and vertical pressure in bins with vertical sides. This represents a significant contribution to bulk solid theory, and thus its solution is reproduced as follows: L = KV = RW/U' [l-e -U'KY/R] I where L is the lateral pressure of the bulk solid in psf., V is the vertical pressure of the bulk solid in psf., K is the ratio of the lateral pressure to the vertical pressure at any point, R is the hydraulic radius of the bin in feet, W is the density of the bulk solid in lbs. per cubic feet, U' is the coefficient of friction between the stored material and the bin wall, and Y is the head of material above the point in question in feet. In 1903, Jamieson,6 in an elaborate series of experiments on full sized bins measured vertical and lateral pressures by hydraulic diaphragms. He determined many values for mediums of corn, wheat, peas, and flaxseed. In 1951, Caughey, Tooles, and scheer3 measured both lateral and vertical pressure in deep bins by using strain guages on steel bands. Values were calculated for cement, gravel, sand, soy beans, shelled corn

Jan 1, 1961

By M. N. Shetty

LARGE copper whiskers (-100 p) of 11111 orientation were tested in a floor-model Instron testing machine, at liquid nitrogen temperature. (Testing methods will appear elsewhere.) Whiskers deformed by twinning after some initial deformation. A load-elongation curve at the onset of twinning is reproduced in Fig. 1. Twinning was confirmed by taking a back-reflection Laue picture, using a slit colli-mator, which showed distinct splitting of reflections. The tensile stress reached just before twinning is about 1.4 x 107 g per sq cm (-7.0 x106 g per sq cm—resolved shear stress) which drops to 1.2 x107 g per sq cm (-6 x 106 g per sq cm—resolved). This twinning stress is about five to ten times larger than the value for bulk single crystals of copper deformed at 77°K (-106 g per sq cm—resolved). Twinning models based on Cottrell-Bilby's pole mechanism are discussed in detail by Venables.' In the present work a mechanism based on the idea of failure of a Lomer-Cottrell barrier by recombination will be proposed. An L-C barrier may fail either by recombination or by dissociation.3 Fig. 2 provides the necessary information. It shows that the stress necessary to break such a barrier is about 1.8 x 107 g per sq cm by recombination and 4 x 107 g per sq cm by dissociation at 77°K. The twinning stress reached by whiskers is comparable to the stress level required for failure of an L-C barrier by recombination. (Stroh himself points out that his calculations should not be taken too literally.) We consider a segment of the L-C dislocation which has recombined (AB in Fig. 3) over a length to form the total dislocation which then glides in the

Jan 1, 1965

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By David Schroeder, John Chipman

Jan 1, 1964