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By Charles E. Weaver

Discussion of the paper of CHARLES E. WEAVER, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1419 to 1427. MILNOR ROBERT, Seattle, Wash.-A year ago at this time, 12 wells were being drilled for oil in western Washington. Some excitement attended the operations; many thousand acres of land were leased to oil companies and stock was widely advertised. The location of the wells may be described by referring to the conclusions in Dr. Weaver's paper, in which the State is divided into four areas. In the area described first, which includes the Cascade Mountains and eastern Washington, where conditions are decidedly against the existence of commercial oil fields, no new drilling was reported. In the second area, the Puget Sound Basin, where conditions are unfavorable, but to a less degree, five wells were being drilled. The third region, covering certain parts of southwestern Washington, contained four drilling wells and several others projected or beginning operations, in spite of the absence of petroleum seepages. None of the wells mentioned is fully active today. On the western side of the Olympic Peninsula, along the Pacific Ocean, are three wells which have been the scene of operations for the past two to three years. The region they are prospecting contains seepages of light oils and is the fourth area described in the paper. The difficulties of transporting both men and supplies to the well sites have delayed operations and brought the costs up to high figures. The drilling of these three wells is interesting on account of the presence of oil in nearby seepages and its occasional appearances in the material penetrated. A. C. McLAUGHLIN, San Francisco, Cal.-The most important part of Washington is on the Olympic Peninsula. The geological conditions on the Peninsula are not similar to the conditions in California, and it would not prove to be a continuous belt of oil-bearing territory from there to here if oil should be found at either end.

Jan 12, 1915

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By Oliver Bowles

A NORTH CAROLINA miner dreamed that he found high-grade mica by excavating a certain corner of his mine. The next day he sank a hole on the exact spot and found mica of excellent quality. The dream came true. May not this be as good a method as any yet known for forecasting the valuable mineral content of pegmatites? The Federal Geological Survey has found in its recent detailed studies in New England that good sheet mica occurs most abundantly in zoned pegmatites, particularly in zones lying along the wall or contact of the pegmatite mass. Although this conclusion may be a valuable guide, pegmatite mining operations must still be classed as most uncertain and hazardous enterprises. Finding of the second largest diamond ever discovered in the United States-a stone of good gem quality weighing more than 34 carats-during the course of a horseshoe pitching contest at Peterstown, W. Va., is another example of unorthodox mining methods. These should not be considered, however, as characteristic mining methods developed in 1944.

Jan 1, 1945

By E. W. Davis

THIS nation has been depending upon the Lake Superior iron ranges for most of its iron ore requirements for over half a century. Furthermore, it can continue to draw the major portion of its ore requirements from the same source for another century or more, but to accomplish this, great changes must take place in the present ore mining industry. Preliminary preparations for these changes are now underway and in the next few years decisions of far-reaching importance must be made. But to understand the situation, it is first necessary to know something of the nature and occurrence of the Lake Superior iron formation. So far as is known, the merchantable grades of iron ore remaining in the various Lake Superior ranges are as shown in Table 1, which shows that

Jan 1, 1947

By W. L. Zeigler

THE Galena mill of the Callahan Zinc-Lead Co. is of 150 tons daily [ ] capacity and is situated at Lake Gulch, 2 miles west of Wallace, Idaho. (Fig. 1. It was constructed during the summer of 1926, work having been started late in June and the plant placed in operation Oct. 15, following.

Jan 1, 1928

By R. G. Fenish

THE B-Ni system was chosen for this study because of the great interest being shown in boron-fiber-strengthened composite materials. Boron fibers were obtained from Texaco Experiment, Inc. They average 4.2 mils in diam with a 0.5-mil tungsten wire in the center. In order to make the diffusion couple, the fibers were included in the nickel matrix by electroforming. The samples were placed in a preheated furnace for the desired temperature and length of time. Sectioning and polishing the samples revealed concentric rings as shown in Fig. 1. The average penetration distance, X, was calculated by measuring the radius of the second phase (the white shell in Fig. 1) and subtracting the original radius. The second phase was identified as NiB by X-ray diffraction. This allows the kinetics of the formation of the phase NiB to be calculated by Eq. [I], which is taken from Hoffman:"

Jan 1, 1967

By N. R. Adsit

THE B-Ni system was chosen for this study because of the great interest being shown in boron-fiber-strengthened composite materials. Boron fibers were obtained from Texaco Experiment, Inc. They average 4.2 mils in diam with a 0.5-mil tungsten wire in the center. In order to make the diffusion couple, the fibers were included in the nickel matrix by electroforming. The samples were placed in a preheated furnace for the desired temperature and length of time. Sectioning and polishing the samples revealed concentric rings as shown in Fig. 1. The average penetration distance, X, was calculated by measuring the radius of the second phase (the white shell in Fig. 1) and subtracting the original radius. The second phase was identified as NiB by X-ray diffraction. This allows the kinetics of the formation of the phase NiB to be calculated by Eq. [I], which is taken from offman:"

Jan 1, 1967

By H. F. McCullough

THE success of a coal-mining venture as relates to operations at the gob or break-line, such as the drawing of pillars or the working of long-faces, depends upon the control of face conditions. The measures required to control the latter are dependent upon the action of the coal seam, roof and floor at and in the vicinity of the faces, but the manner in which these will act is dependent upon the rate of face movement as well as upon the face characteristics and upon the forces exerted. Yet the merits of a method of working-the practicability of controlling face conditions and the means required for such control when applied to any particular case-are usually judged only upon a consideration of the characteristics of coal seam, roof and floor, and the manner in which they have been observed to act. Practically every coal-mining man knows that face conditions are influenced by the rate of face movement, but few have appreciated that this is as much of a factor in the control of face conditions as are the face characteristics and the forces exerted. Fewer yet have recognized or taken advantage of faster rates of face movement as one of the principal means of establishing control of face conditions or of securing more favorable face conditions. Seemingly inherent difficulties, particularly in the control of roof conditions, but also in the control of conditions of the coal seam and floor, are frequently mitigated or disappear when the rate of movement of the faces is sufficiently increased. The characteristics of the coal seam, roof and floor and the forces exerted upon them do determine the general trend or tendency of face action, but the manner in which the coal seam, roof and floor will act and be acted upon and the magnitude of the action during the time the site of mining operations remains at any particular point is very largely determined by the rate of movement of the faces.

Jan 10, 1926

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

By George C. Toland

In 1950 the phosphate fertilizer market warranted the design and construction of a new fertilizer plant by Cominco at Kimberley, B.C. The initial rated capacity of the plant was 70,000 tons per year of high- grade ammonium phosphate. The plant was placed on-stream in 1953. One of the major problems in operating the fertilizer plant was the disposal of the gypsum tailings slurry which was a by-product of phosphoric acid manufacture. The original weight of dry tailings produced by the mill was 500 tons per day. This quantity increased over the years until a projected 2200 tpd was selected for the pond design described in this paper. The original gypsum tailing area was located south of the fertilizer plant and adjacent to the St. Mary's River. By 1965 the original disposal area had proven inadequate and Cominco's engineering staff had selected a 500 acre disposal site to the east of the plant.

Jan 1, 1971

By F. L. Grammer

THE analyses given in Table I. were made several years ado at my request at a plant using Lake ores. The, are of two furnaces, one making basic, the other Bessemer pig-they gave 6 casts each in 24 hr., also two flushes of cinder between each cast. They- are offered simply for the sake of reference as, so far as I know, it is unusual to find so frequent fall analyses made and none are on record. The variations iii manganese-content in the first and second flushes on the basic furnace are interesting, if no more than a freak-the first flash being invariably higher in manganese. The iron-content of the two slugs from an. average of 12 flushes shows: Basic. Bessemer. Per Cent. Per Cent. Total iron 2.55 1.70 Combined iron 0.72 0.52 Free iron 2.13 7.15

Jan 3, 1913

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAID;1 NEW YORK N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 3, 1915

By CHARLES F. RAND

PRESIDENT CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N.. Y. FIRST VICE-PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER. W. RAYMOND, NEW. YORK; N. Y. SECRETARY BRADLEY- STOUGHTON NEW YORK, N. Y.

Jan 2, 1914

By D. W. Brunton

Discussion of the paper of D. W. Brunton, presented at the Spokane meeting, September, 1909, and published in Bulletin No. 33, September, 1909, pp. 837 to 855. WILLIAM' KENT, New York, N. Y.:-The Institute may congratulate itself on the opportunity of reading the splendid address of President Brunton. It is au admirable summary of the progress that has been made in the mining and metallurgical arts in recent years. The paper rightly give's the chief credit for this progress to the aid which has been rendered to these arts by the advances in mechanics, chemistry, and electricity. It is notable that most of the headings in Mr. Brunton's address refer to the work of the mechanical engineer, the electrical engineer, and the chemist, rather than to that of the specialist in mining-operations. It seems that. the most successful mining engineer of the present day is the one who makes the most intelligent application of the inventions and designs of engineers and others who are not directly engaged in mining. A tabulation' of the headings of the address, grouped as below, shows this most clearly. Work of the Mechanical Engineer-Rock-drills, hoisting-machinery, tramming, pumping, ventilation, dredging, sampling, concentration, briquetting, fume-recovery. Work of the Electrical Engineer-Electric machinery for hoisting, pumping, tramming, lighting and signaling, electric . transmission, electric smelting. Work of the Chemist and Metallurgist-Explosives, chlorination, cyanidation, roasting, lead-smelting, and copper-smelting. Work of the Geologist-Economic geology. Work of the Mining Engineer-Mine-mapping, surface-mining, timbering, tunneling; and planning and supervision of the work in general. The mining engineer of the present day, who is in responsible charge of a large plant, finds his chief work not in doing

Jan 1, 1910

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 3, 1914

By J. G. Benford, E. B. Stanley

THERE have been numerous papers in the literature1 on the subjects of secondary and tertiary recrystalli-zation in silicon steels. Secondary re crystallization is believed to occur in silicon steel by either a surface-energy phenomenon such as in the usual development of cube texture or by a second-phase phenomenon such as in the usual production of cube-on-edge texture, (110)[001]. Tertiary recrystallization in silicon steel is thought to be a surface-energy phenomenon in which, for example, grains having a (110) plane parallel to the sheet grow at the expense of other grains in the matrix including those having a (100) plane parallel to the plane of the sheet. In all these instances, the orientations involve either a preferred (100) or (110) plane in the plane of the sheet. Until very recently, there had been no experimental evidence reported of the occurrence of a texture by secondary or tertiary recrystallization that involves a (111) plane in the plane of the sheet, although Kohler reported that grains having the (111) plane parallel to the sheet surface can also grow by a surface energy mechanism. Stickels observed a secondary texture in iron described as "near {554}(225)" about 5 deg from {lll}(211).3 Mee reported that in a vacuum-remelted commercial 3 pct Si steel {lll}(hkl) secondary recrystallization took place in a high vacuum and in pure hydrogen.4 Recently in our Laboratory, large-grained structures such as shown in Fig. 1 having an orientation near (111)[211] or (111)[2ii] have been observed. The arrows point to areas of relatively small matrix grains of the kind that the much larger (111) grains consumed while growing. It is of interest that the matrix grains of samples annealed at 2000°F were essentially the same size as those in samples annealed at 2200°F, a matrix-grain-size stability that is characteristic of secondary recrystallization processes. A torque disc taken from Grain 4 of the sample shown in Fig. 1 revealed a very flat magnetic-torque curve, as expected, with a maximum torque of 7000 dyne-cm per cu cm compared to the typical 180,000 dyne-cm per cu cm observed for conventional (110)[001] textured material. A back-reflection Laue pattern for Grain 4 is shown in Fig. 2 and indicates a near-perfect (111)[211] orientation. The other six numbered grains in the sample of Fig. 1 had a similar orientation. The small circles next to each number were the target areas for the X-ray beam. The starting material was an 0.011-in.-thick oriented silicon steel, (110)[001] texture, containing 3 pct Si. It was lightly pickled, cold-rolled to 0.005 in., and annealed 4 hr at 2200°F within a nickel box (not gas-tight) inside a tube furnace through which dry hydrogen was flowing. The samples were heated to 1500°F in 1 hr and then at 60°F per hr to 2200°F. There were other

Jan 1, 1969

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

Discussion of the paper of EDGAR L. NEWHOUSE, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin: No. 92, August, 1914, pp. 1801 to. 1806. G. C. RIDDELL, East Helena, Mont.-As nearly as I can recall at the present moment, there are only four or five large plants on the continent where the lead on charge is carried in the neighborhood of 40 per cent. These are at Herculaneum, Collinsville, and Federal, Ill.; Trail, B.. C.; and East Helena, Mont. Our object at the latter point is to smelt a maximum amount of Coeur d&apos;Alêne lead sulphides in as compact and self-fluxing a charge as possible, and to this end we are now smelting a mixture that at times carries up to 42 per cent. lead. The monotony of producing the 7,000 tons of bullion shipped each month to. the Omaha and Chicago refineries is relieved somewhat by the fact that the 15,000 tons monthly of Coeur d&apos;Alêne ores that are com-ing to us carry enough zinc to provide the one-half slag used with from 6.5 to 7.5 per cent. zinc clay after day. During the month of March, 1914, three lead furnaces in continous operation, each 136 in. long, averaged 249 tons per furnace clay, exclusive of coke and slag shells, which is smelting at the rate of 5.5 tons per square foot of tuyère area. The

Jan 11, 1914

By W. L. Zeigler

The Galena mill of the Callahan Zinc-Lead Co. is of 150 tons daily capacity and is situated at Lake Gulch, 2 miles west of Wallace, Idaho. (Fig. 1. It was constructed during the summer of 1926, work having been started late in June and the plant placed in operation Oct. 15, following.

Jan 1, 1928