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The Students' Organization of the Michigan College of Mines was recognized as an Affiliated Student Society by the Board of Directors of the Institute, at a meeting held on April 28, 1916. At the College of Mines, University of Washington, 30 students and instructors took part in the annual spring excursion early in April. Studies were made of the new reverberatory and casting furnaces at the Tacoma smelter, the Du Pont powder works located on Puget Sound and the Britannia Mining and Smelting Company's mine and mills on Howe Sound, near Vancouver, B.C. The Britannia mills are using Hancock jigs, Burchart tables and Minerals Separation flotation cells to effect a high recovery on low-grade chalcopyrite ore. The Mining Club, University of. Wisconsin, elected the following officers for the second semester of the present school year: J. G. SKIRM, President, H. L. RAU, Vice President, T. C. SHERWOOD, JR., Secretary-Treasurer, H. E. HODGSON, Mucker, , F. M. WOLVERTON, Assistant Mucker. Theo. C. SHERWOOD, Jr., Secretary.

Jan 6, 1916

By Ian M. Thomson, Robert W. Greene

Last August, American Commercial Barge Line Co. (ACBL) began moving coal from mines on the old Camp Breckinridge property in Western Kentucky to TVA's new 2600 MW steam plant at Cumberland City, Tenn. By April of 1973, this movement will reach a level of 7 million tpy. TVA bought the coal rights to this property from the General Services Administration in 1965 for approximately $7 million and is now in possession of reserves containing about 120 million tons of recoverable No. 9 coal, and about the same recoverable amount of No. 11 coal. TVA then contracted through competitive bidding with Peabody Coal Co. to mine the No. 9 seam through two slope shafts. The mines are about 300-ft deep and are separated by the one major fault on this property. The mine portals are approximately 3 ½ mi apart, with the northern portal being over nine miles distant from the Ohio River.

Jan 1, 1971

By A. N. Diehl

IT is the object of this paper (1) to deal with the elements in blast-furnace gas from the standpoint of their importance, and the part they are to play in future consumption, and (2) to give detailed information about the construction and operation of a plant designed among the first in this country for washing gas on a large scale.

Jan 5, 1914

By Dan McLachlan

EXPERIMENTS on ionic solids,1 Cu-A1 alloys,2 and Fe-Si alloys3 have suggested that the ability of dislocations to cross-slip is one of the most important factors governing the nucleation and growth of fatigue cracks. These experiments necessarily had to be made on materials of different composition in order to vary the propensity for cross slip. However, re-

Jan 1, 1967

By Charles R. Keyes

PAGE I. Introductory............ 140 II. Location and History...........140 III. Surface-Relief of the District....... 141 IV. General GeoloGic Features........ 142 1. Main Relationships and Map....... 142 2. Résumé of Geologic History..143 V. Geologic Formations Represented...144 1. Broader Considerations......... 144 2. Geologic Section.......... 145 3. Nomenclature.......... 146 4. El Pasan Limestones..146 5. Santa Rita Limestone.... 146 6. Silver Shales........... 147 7. Bella Shales........... 147 8. Berenda Limestone..147 9. Grande Limestone... 148 10. Lake Valley Limestone........ 148 11. Sierra Limestone.......... 149 VI. Unconformities........... 149 VII. Geologic Structure.......... 150 1. Main Characteristics......... 150 2. Folding........... 1.50 3. Faultings........... 150 4. Relations of the Eruptives...153 VIII. Geologic Relations OF the Ore-Bodies...... 154 1. Governing Factom......... 154 2. Position.......... 154 3. Relations to Foldings...155 4. Relations to Lines of Dislocation... 15.5 5. Relations to Present Surface.Relief..156 6. Relations to Eruptive Rocks...157 7. Relations to Lithologic Nature of the Rocks.... 158 IX. MINERALOGIC CHARACTER OF THE ORES...... 158 X. Origin of the Ore.Deposits..159 1. General Statement......... 159 2. Original Source of the 0re.Materials...160 3. Contact-Metamorphism of the Region... 161 4. Process of 0re.Concentration..162 5. Lowering of Ground-Water Level..162 6. Formation of Cerargyritic Ores...163 XI. Recapitulation........... 168

Jan 1, 1909

By J. J. Bodmer

The four different modes, more or less practiced for subdividing slag (that is, producing slag sand), are the following: 1. Crushing the slag from the lump in Blake's crusher, by edge runners or other suitable means. 2. Blowing water, steam, cold or hot air, into the stream of viscous slag whilst it runs from the furnace. So treated, the slag takes

By A. K. Bhasin

A. K. Bhasin, (Development Engineer, Marcona Corp., San Francisco, Calif)-The author suggests the use of the term "consistency" for apparent viscosity and accordingly calls his viscometer a "consistometer." However, he goes on to refer to "consistency" as a combination of plastic viscosity, yield stress, and stability (p. 104, col. 2, line 6). Unfortunately, such conflicting terminology is encountered too often in rheological

Jan 1, 1973

By Magnus Troilius

The following is a very rapid method for determining copper in steel. I have found it to give results very closely agreeing with those obtained by galvanic precipitation of the copper. Five grams of steel are dissolved in a mixture of 100 C.C. of water and 10 C.C. of sulphuric acid. When all is dissolved, add 2 C.C.

Jan 1, 1883

By J. J. Bodmer

THE four different modes, more or less practiced for subdividing slag (that is, producing slag sand), are the following : 1. Crushing the slag from the lump in Blake's crusher, by edge runners or other suitable means. 2. Blowing water, steam, cold or hot air, into the stream of viscous slag whilst it runs from the furnace. So treated, the slag takes

Jan 1, 1874

By Charles H. Kline

Industrial minerals are the Cinderella of the mining I industry. Often considered as just dirt by traditional hard-rock miners and oil drillers, these products nonetheless comprise the second largest segment of the industry and the fastest-growing one. With annual sales of $5.7 billion, industrial minerals make up 22% of the dollar value of U.S. mineral consumption. By contrast, metals account for only 11%. Fuels, of course, are dominant, representing 67%. The dollar values of production and consumption for the three segments of the industry in 1968 are shown in Table I. The growth rate of industrial minerals is shown in Table II. From 1953-1968, the current-dollar value of all U.S. mineral production increased at the average annual rate of 3.8% while that of the gross national product increased at 5.9%. Industrial minerals are the only segment of the mining industry that approached the growth of the overall economy in this period, with production values increasing 5.1% a year and apparent-consumption values 5.6% These data, expressed in current dollars, include the effects of inflation. The growth in U.S. industrial minerals production is even more striking when expressed in indexes of physical production. As shown in Table III, production of all U.S. industries increased by 4.1% a year from 1953 to 1968. The growth in production of stone and earth minerals just matched this figure. By contrast, the average annual increase for oil and gas was 2.2%: for metals, 1.6% : and for coal, only 0.6 %.

Jan 1, 1970

IF you do not make the disc at the same time as the core and as part of it, it is necessary to make it by itself. This is done by spreading on a board or other flat surface a layer of clay as thick and wide as [88] the disc that you made at the feeding head of the first pattern of the gun. When it is dry, mark it exactly with compasses and then, cutting with a chisel or rasp, make it fit exactly into the empty space at the head. Likewise, make a hole just as wide as the thickness of the core exactly in the middle of this clay disc. When you have put the disc in its place in the mould and then pass the core through this hole, it passes exactly through the center of the mould in such a way that it meets the iron ring that you put at the foot of the mould for this purpose. As I said above, if' you do not make it as part of the core, it is necessary to proceed in the aforesaid way. But if' you wish to make it attached to the core (which I like better because it can be done more accurately) make a

Jan 1, 1942

By Herbert J. French

Herbert 1. French (Member 1934), vice president of the International Nickel Co. Inc., assistant vice president of the International Nickel Co. of Canada Ltd., and AIME Howe Memorial Lecturer for 1956, died in Rochester, Minn. on Aug. 17, 1955, after a long illness. Before his death, Mr. French had laid the foundation of research on which the Howe Memorial Lecture (p. 770) was based. His associates at Inco, 0. 0. Miller and J. W. Sands, were able to complete the project, present the lecture, and prepare it for publication, following Mr. French's general outline. Born in New York on May 27, 1893, he graduated from the School of Mines, Columbia University, with a degree in metallurgical engineering in 1915. Mr. French gained his early engineering experience with the American Smelting and Refining Co., serving as a chemist and as-sayer at the company's Murray, Utah, installations. He later returned east and became a metallurgical engineer for the General Vehicle Co., Long Island City, IT. Y., a subsidiary of the General Electric Co. In 1917 Mr. French was appointed civilian inspector of materials for the U.S. Army Signal Corps, and continued this work when it was later absorbed into the Bureau of Aircraft Production. Subsequently he was appointed district inspector in Philadelphia for the Pittsburgh (Ordnance Metallurgical) office, later transferring to Pittsburgh. After World War I Mr. French became an assistant physicist on the metallurgical staff, U. S. Bureau of Standards, Washington, D. C. During his years with the Bureau, he was successively associate physicist, metallurgist, senior metallurgist, and assistant chief, division of metallurgy. In 1929 Mr. French joined International Nickel as a metallurgist at the company's Bay-onne, N. J., research laboratory. Transferring to the development and research division, New York, in 1931, he took charge of alloy steel and iron development, becoming assistant manager of this division in 1943. Mr. French's appointment as an Inco vice president came in March 1947. Previously, he was appointed assistant vice president of the International Nickel Co. of Canada Ltd. in January 1947. Mr. French served the War Production Board during World War II as senior technical consultant in charge of the metallurgical and specifications section of the iron and steel branch. When this section of the WPB was organized into the steel division, he was appointed chief of the metallurgical branch. From March 1944 to September 1945 Mr. French served as assistant director. Herbert French was well known not only for his prolific contribution to the metallurgical literature, for which he received numerous awards, but also for his prolonged service to the profession through its technical societies. He was a past president of ASM, and was the Campbell Memorial Lecturer for that group in 1933. Mr. French was honored by the American Society for Steel Treating in 1931 when he was awarded the Henry Marion Howe Medal. A series of lectures he gave in 1941 before the Fourth Western Metal Congress in Los Angeles was later published in book form under the title Alloy Constructional Steels.

Jan 1, 1957

Noranda Mines, of Quebec, signed a contract for construction of a $20 million copper refinery at Gaspe, P.Q. The plant is expected to have a 65500-ton daily capacity for both concentrator and smelter. Extensive drilling. around Gaspe has revealed more than 65 million tons of 1 to 2 pct copper in several deposits. Cerro de Pasco Corp. has called a special stockholders meeting for August 19 to obtain permission to engage in the oil and natural. gas business, in addition to its present production of zinc, lead, copper, silver and other metals. St. Joseph Lead Co. recently entered the oil development field. The United States, Canada and Great Britain have agreed to establish a permanent organization to work on unification of engineering standards. General accord has been reached on drafting standards and practices, screw threads, fittings for gas cylinders, and fits and tolerances. Permanent committees will study these fields. Reconstruction Finance Corn approved the largest sum in its history. for a mining enterprise when it loaned $94 million to San Manuel Copper. Corp., of Pinal County, Ariz. The loan will be used to increase production of copper and molybdenum, in what was described as-the biggest copper deposits in the country. Three large gold mining concerns operating in the Philippines told the Philippine Wage Board that they would be forced to close if they had to boost miners' wages 500 to $2 per day. The companies are Mindanao Mother Lodes, Benguet Consolidated, and Balatoc Mining Co.

Jan 1, 1952

By Michael Tenebaum

IN a previous investigation1 the authors studied the effect of pressure on the reduction of iron ores by hydrogen. With hydrogen as a reducing agent, the rate of reduction was increased substantially by increasing the pressure from 1 to 2 atmospheres. The results with hydrogen prompted the present study of the effect of pressure on reduction with carbon monox-ide and with mixtures of carbon monoxide and nitrogen. FEATURES OF REDUCTION PROCESS The gas stream in the lower part of the blast furnace always contains sufficient concentrations of reducing gases to complete reduction provided sufficient time is allowed for the reaction to proceed. Reducing gases react immediately with the iron oxide on the surface of lumps of ore. However, as the unreduced surface recedes from the easily accessible exterior of the lump, the reaction proceeds by virtue of the diffusion of the gases into and out of individual pieces. The rate of diffusion of gases, which undoubtedly plays an important role in the reduction of iron ores, depends on several factors, most impor-tant of which are: (1) molecular weight or density, (2) pressure, (3) tem-perature, (4) concentration gradient. Thus, the rate of reduction of a lump of iron ore at any temperature will depend not only on the specific reaction rate but also upon: (1) available surface of unreduced iron oxide, (2) rate of diffusion of the reducing gas to the reacting surface, (3) rate of effusion of the gaseous products of the reaction from the reacting surface, (4) adsorption of the gases on the reacting surface.

Jan 1, 1939

By Svend Rordam

THE development of a cement that will resist the destructive action of sea water and other corrosive waters is a problem that has occupied cement chemists for the past one hundred years. It has been found that of the various salts that commonly occur in corrosive waters, sodium sulphate, magnesium sulphate and magnesium chloride are most destruc-tive to cement. Many investigations have been carried out in the United States, in Canada, and in Europe to solve the problem of what constitutes a sulphate-resistant cement, and during the past 10 years some of the findings give definite information in this respect. COMPOSITION OF CEMENT Portland cement is composed of four major compounds: 1. Tricalcium silicate 3CaO.Si02 (C3S) 2. Dicalcium silicate 2CaO.Si02 (C2S) 3. Tricalcium aluminate 3CaO.Al203 (C3A) 4. Tetracalcium aluminoferrite 4CaO.Al203.Fe203 (C4AF) The two calcium silicates are the main contributors of strength. The tricalcium aluminate contributes some to the early strength of the cement but has the least resistance of the four compounds toward the attack of sulphate waters. The tetracalcium aluminoferrite does not contribute very much to the strength, but is far more resistant to sulphate waters than the tricalcium aluminate. When hardened cement is exposed to water containing sodium or magnesium sulphates, these salts will react with the hydrated tricalcium aluminate in the cement and form compounds that will cause a swelling, disruption and crumbling of the hardened cement.

Jan 1, 1939

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.' The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" ' were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,' the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O'Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie' has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By Harry Seltz

INTERMETALLIC compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dis-sociated in the liquid state, as indicated by the continuous for in of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455° C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a =6.52, b = 8.60, c = 4.16 A.2 There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO2 = CdO + CO + Sb From the known free energies of formation of CdO, CO2 and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell

Jan 1, 1935