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By John Ryan

SIR HUMPHREY DAVY'S epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demon¬strated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the work-men's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines has demonstrated some dan¬gers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but 1-potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Conse-quently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Dangerous coal mine gases may be placed in two groups: (1) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CHI) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture.

Jan 2, 1927

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By John M. Lovejoy

NATURAL resources become a source of wealth as they are exploited and made available to the people in usable form. Experience has taught us that Nature does not readily give up her treasures, but the ingenuity of man in the field of techologic progress is required to find and efficiently exploit these resources. History has also demonstrated that with advancing technologic knowledge the. world has become progressively richer in its resources. Those that could not be commercially exploited are now being turned to beneficial use. Through expanding technology and the use of substitutes and synthetics, availability of the world's sources of natural wealth is today many times that of a hundred or a thousand years ago. And so it is with petroleum. Technology is also the great multiplier of our petroleum resources. Through improvements in the art of finding, drilling, and producing, our ability to meet rapidly increasing demands over the last quarter century has been maintained. On the other hand, had our

Jan 1, 1944

By H. Jehn

Like some other Pt-group metals palladium shows a low but considerable solid solubility of oxygen, which was found already from oxidation studies. The oxygen solid solubility of palladium in equilibrium with gaseous oxygen has been investigated at 900 - 1300 °C in oxygen (665 mbar) and air by gassing and analyzing polycrystalline samples. The 0-concentrations range from 40 to 90 ppm and decrease with rising temperature. The isobaric solubility can be represented by the least-squares fit log c0 = 0.5 log p02- 0.32 + 920/T (c0 in wt. ppm, p02 in mbar, T in K). The thermodynamic data of the exothermic solution reaction are calculated to ?H°= -17.6 kJ?mol-1 and ?S° -76.5 J?mol ? K-1. The behaviour of palladium in an oxygen atmosphere is characterized by the simultaneous reactions of the solution of oxygen in the metal and the formation and evaporation of volatile oxides besides the pure metal evaporation.

Jan 1, 1984

By B. M. Larsen, J. W. Campbell

Several articles have recently been published discussing the conditions necessary for accurate measurements of temperatures in the open-hearth steel furnace. In the course of a study of refractories service conditions in steel furnaces, the present writers have taken temperatures in several open-hearth shops in the Pittsburgh district. The conclusions, as to conditions necessary for accurate measurements of temperature, are somewhat at variance with those of other investigators. The subject is closely connected both with the close control of steel-making and the prevention of overheating of the silica refractories used in roofs and walls. It is becoming more and more important to obtain furnace temperatures of fairly definitely known accuracy. At present, the most useful instrument for such measurements is the disappearing-filament type of optical pyrometer. This method of measurement has formed the basis of most other discussions on the subject and was also used by the writers. Previous Investigations In 1916, Burgess' made perhaps the first systematic series of measurements in steel furnaces. The emissivity figures of 0.40 for liquid steel and of 0.53 to 0.65 for liquid slags had been determined by the Bureau of Standards and were used by Burgess in this work. These correction factors are still being used and are regarded as fairly accurate, so that the tapping and teeming temperatures on metal streams given by Burgess should be very nearly correct. Most of his temperatures of furnace roofs and slag surfaces were taken while flames were present in the furnaces and include a few roof temperatures above 1700' C. (3100' F.).

Jan 1, 1927

PRESIDENT Willis McGerald Peirce New York City, N Y PAST PRESIDENTS D H McLaughhn, San Francisco, Calif L E Young', Pittsburgh, Pa VICE-PRESIDENTS A. B. Kinzell, New York, N Y H. W Thomas Ray, Arizona Philip Kraft, New York, N Y J L Gillsan Wilmington, Del M. L Haider, Toronto, Ont , Canada VICE-PRESIDENT and TREASURER Andrew Fletcher, New York, N Y

Jan 1, 1951

ARIZONA Tucson University of Arizona, Mining Engineering Society. B CALIFORNIA Berkeley University of California, Mining Asso. B University of California, Library. T Los Angeles Chamber of Mines and Oil. B Southern California Local Section. T Public Library. T Oakland Oakland Free Library. T San Francisco California State Mining Bureau. T Mining and Scientific Press. B Stanford University Stanford University Geological and Mining Society. B

Jan 1, 1917

A self-appointed, committee consisting of J. Waldo Smith, Chairman, Richard S. Buck, J. J. Carty, J. Parke Channing, E. L. Corthell, Alfred Craven, Thomas Crimmins, Gano Dunn, George Gibbs, Alex. C. Humphreys, F. L. Hutchinson, Charles Warren Hunt, D. S. Jacobus, John W. Lieb, William Barclay Parsons, George H. Pegram, Charles F. Rand, Calvin W. Rice, Robert Ridgway, William L. Saunders, Merritt H. Smith, Bradley Stoughton, and William H. Wiley, organized a course of seven free lectures on military engineering, which were given by Captains Thomas M. Robins, Richard T. Coiner, Edward D. Ardery, Corps of Engineers, United States Army, and which was under direction of Major General Leonard Wood. The United Engineering Society presented, without charge, the use of the auditorium for the purpose of these lectures, but the interest proved to be more than three times as much as had been expected, and it was therefore necessary to divide the courses into three parts, one of which was given in the afternoon in the auditorium of the United Engineering Societies Building, one in the evening in the same place, and another in the evening in the auditorium of, the American Society of Civil Engineers. These lectures occurred on Mondays, from Feb. 14 to Mar. 27, 1916. The subjects and speakers were as follows: Feb. 14, 1916: Organization and Duties of Engineers in War, and what Engineers in Civil Life will be called upon to do in the Defence Of the United States. Captain Thomas M. Robins, Corps of Engineers. Feb. 21, 1916: The Service of Reconnaissance Including Surveying, Mapping and Sketching, Photography and Map Reproduction. Captain Richard T. Coiner.

Jan 5, 1916

By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of' solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van't Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.'' In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By R. G. Knickerbocker

A STURDY and consistent expansion of the metal industry occurred in 1947 exemplified by an increase of approximately 30 per cent in steel consumption over 1946. For this major reason, ferroalloy metals have seen their most useful and important peace-time year. The current domestic rate of consumption of high-grade ferroalloy ores, together with added consumption of new foreign producers as well as for eign nationals' restrictions on high-grade exports, makes very evident the increasing difficulties of obtaining sufficient high-grade ores. This accentuates the need for new and less expensive methods of production of ferro-alloy metals of higher purity from lower-grade domestic resources. As an important factor in preparedness, procurement of these high-grade, -critical ferroalloy minerals and metals for our nation's stock piles is a most important task. Also, this stock-piling can be the means of supplying incentive for the industrial development of the new metallurgical processes and plants necessary for the recovery of ferroalloy metals from our domestic low-grade deposits.

Jan 1, 1948

By R. D. Fisher, A. G. Metcalfe, F. A. Crossley

AN investigation of the application of magnetic stirring to the consumable arc melting of aluminum and nickel demonstrated that grain refinement could be obtained when there was sufficient stirring force. Also, it was found that grain refinement could be obtained in aluminum by alternately reversing the polarity of the current through the magnetic stirring coil. The effect of the latter was to periodically reverse the direction of rotation of the molten metal.' Because of their promise, these findings were applied to conventionally cast aluminum. Shortly after this work was begun, Kondic2 reported experiments in which aluminum cast with 40° C (72° F) of superheat exhibited a grain size of 10 to 20 grains per cm2. When interrupted rotation was applied during solidification by mechanical means, a grain size of 800 to 1000 grains per cm2 was obtained. Magnetic Stirring Applied to Conventional Casting— The applicability of magnetic stirring to producing grain refinement in conventionally cast metal was evaluated in the following way. Three pounds of aluminum were cast into a clay-bonded graphite mold. The mold was surrounded by a magnetic stirring coil of 1000 turns. A direct current of 200 amp was passed through the casting by means of a graphite electrode which was immersed from the top. A current of 5 amp was passed through the stirring coil. The aluminum (1100 or 25) was superheated to 1600° F (871° C) and fluxed by passing chlorine gas through the melt for 2 min prior to casting. Two additional castings were made for comparison: 1) a conventional casting of metal superheated to 1600° F and 2) a similar casting through which 200-amp current was passed during solidification, but without current in the magnetic coil. Macrosections of these three ingots are shown in Fig. 1. Very remarkable grain refinement resulted in the magnetically stirred casting. It may be noted that the casting through which 200-amp current was passed has a coarser structure than the conventional casting. It would appear that this is due to the additional heat input generated by the current to the former casting. Mechanical Rotation Applied to Conventional Casting—A casting temperature of 1600° F was used throughout. Some 1 1/2 -lb castings rotated at 150 rpm were predominantly columnar with small areas of coarse, equiaxed grains close to the lower mold wall. Following these, a series of 3-lb castings was made. Macrosections of these ingots are shown in Fig. 2. The imposed rotational speed was 250 rpm. Turbulence or acceleration in the solidifying liquid was the significant factor. Fine grain size resulted in the material solidified during the period of acceleration of the liquid to the imposed rotational speed. When uniform rotational motion was achieved, the grain structure reverted to columnar. The final casting shown in the lower right-

Jan 1, 1962

By Martin F. Milligan

THIS short discussion of the effects of deoxidation on the mechanical properties of cast steels is intended to serve as general introduction to the subject of this afternoon's session. The subject is covered in detail in Mr. Carter's excellent paper. My material has been collected from the works of various investigators, several of whom are present today. For a definition of deoxidation, as applied to steel-furnace melting practice, we can best go to Briggs' book, "The Metallurgy of Steel Castings." Briggs says that deoxidation "includes all the phenomena in the final preparation of steel that would permit it to solidify free from gas cavities and from dissolved oxygen of all kinds." Various practices are used by welters to produce these end results.

Jan 1, 1947

By Henry D. Hibbard

FoR the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seem to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machincry, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume. Into which class an ingot will fall depends on the gases of the steel,

Jan 1, 1920

By B. H. Lehnhard, C. J. Cecil

The paper describes the use of the Electric Pilot in the Permian Basin for making permeability surveys of wells and for the selective acidization of wells. A general summary of the information obtained from the many permeability surveys run in this area is given, and the possible application of this information to reservoir control problems is discussed. The application of the Electric Pilot on specific wells, involving well completion, acidizing and workover operations is also included. Introduction The Electric pilot is a comparatively new tool in oil-producing areas. From the beginning, the possibilities of this new service caught the imagination of many of the oil operators and acidizing engineers. Through the continued and ever increasing use of the pilot during the past year, and the close cooperation of the oil operators who have used this service, the efficiency and utility of the Electric Pilot service has been increased to a point where it is now a well established and recognized service. There are two major uses for the Electric Pilot: (I) permeability survey; (2) selective acid treatments. Permeability surveys are made to determine the thickness of the various permeable sections at the borehole, the vertical position of these zones at the bore hole, and the relative capacities of the various zones. Nomenclature Data obtained from the permeability survey are used to calculate three different indexes that pertain to the volume of fluid injected into the various permeable zones. A nomenclature for these various indexes has been set up, which correspond with the various productivity indexes, except that they are a measure of injected fluid rather than produced fluid. The nomenclature and definition of the indexes used in connection with a permeability survey by the Electric Pilot are as follows: 1. Capacity.—The volume of water injected into an individual permeable zone, in gallons Per minute. 2. Capacity Index.—The volume of water injected into an individual permeable Zone, in gallons Per minute Per pound Per Square inch differential Pressure. 3. Specific Capacity Index.—The volume of water injected into an individual permable zone in gallons Per minute Per pound per square inch differential per foot of thickness of the zone at the borehole. Capacity is the most generally used index, and for planning initial acidizing procedures and most workover jobs it is sufficient. For comparing permeability surveys on the same well before and after

Jan 1, 1945

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By Clyde E. Williams

MUCH has been said recently concerning the depletion of the Lake Superior iron ore re- serves. Estimates given indicate a total life of the present known reserves of twenty to thirty years. Some argue that there is no need to concern ourselves about the possible depletion of the Lake Superior iron ore supply because foreign ores can be brought in to this country at a lower price than rich agglomerated ore can be produced from the lean domestic ores. Some fear, as a result of this, a displacement of the steel business from present districts to the Atlantic seaboard. Others show that foreign ores will be brought to interior points via the projected Great Lakes-St. Lawrence waterway. Others believe that the South, given better freight rates, will extend its iron and steel market into northern territory.

Jan 1, 1931

By W. F. Stowasser

Robert E. Hagen (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Stowasser and his associates are to be congratulated on their achievements in developing the design of a pilot agglomerating plant, based on information obtained from experiments made in a laboratory sinter pot, and subsequently constructing and successfully operating this plant. In his Transactions article, May 1955 (vol. 201) Mr. Stowasser stated that the output of his heat treating strand was about 2 Lt per sq ft of grate area per day and that the fuel consumption was 0.7 to 0.8 million Btu per Lt of product. If it is assumed that the burning zone extends from the back of the ignition furnace to the beginning of the recuperation windbox, only about 1/3 of the grate area over the windboxes is utilized for burning pellets, and the actual rate at which partially dried pellets are burned is about 6 Lt per sq ft of grate area per day. It may be interesting to compare the above operating data with that obtained at the Extaca plant, where taconite concentrate is treated on a conventional sin- tering machine using limestone or hydrated lime additives with no recuperation of heat. The entire windbox area is used for burning, and a production rate of 2.5 Lt per sq ft of windbox area per day has been attained at a fuel consumption of 1.8 to 2.0 million Btu per Lt of product, the latter being considerably in excess of that reported by Mr. Stowasser, partly because a circulating load of returns amounting to 28 to 30 pct of the machine feed is used and because no attempt is made to recuperate heat from the waste gases. With the high capital and labor costs prevailing today, it seems that future development of the downdraft grate pelletizing process should be directed toward taking advantage of the high burning rate of predried pellets and increasing capacity, perhaps at the expense of fuel economy, by decreasing the proportion of grate area utilized by ancillary functions. For example, eliminating the cooling zone and using this area for burning would increase the proportion of grate area available for burning from 33 to 50 pct of the total windbox area, and a proportionate increase in capacity would result.

Jan 1, 1956

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

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

Jan 1, 1967

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967