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By S. K. Sahoo, S. K. Sharma, A. Yadav, B. Behera, G. S. P. Singh

A field representative modeling of the gob behavior is critical for the understanding of the associated mechanics of strata behavior in longwall workings. The findings of theoretical models and laboratory tests on the simulated gob material have shown the strain hardening behavior of the gob material. The double-yield material model, which is a built-in constitutive model in FLAC3D, has significant potential to simulate the gob compaction process as it represents materials which undergo irreversible compaction in addition to shear yielding. Apart from this, several researchers have attempted using modified elastic model or applied nodal force in reaction to the strain in the gob area as per the well-known theoretical relations to meet this requirement. Although these models can simulate the mechanical response of the gob for subcritical and critical extraction widths, they do not apply to supercritical extraction width as the gob stress may exceed the in situ stress level in such cases. For overcoming these limitations, a standard approach has been developed and validated in this paper, which can be used for simulating the gob behavior in supercritical longwall workings as well. The complete study is divided into two stages wherein the laboratory scale compression test on the simulated gob material has been numerically replicated to develop preliminary confidence followed by a parametric study of the double-yield constitutive parameters for a rational estimation of their values in different conditions. The calibrated model has been used for verifying its results by plane strain modeling of two different longwall workings, using well-established empirical and analytical findings and field observations. The approach suggested in this study can be used for the efficient modeling of the gob behavior of longwall panels under varying geo-mining conditions without compromising the accuracy of the numerical model. The meticulously validated model can be helpful in rational estimation of stress redistributions around the gob area apart from load transfer on the barrier pillar.

By M. I. Freeman

This paper point put if the companies will considerate large- scale mining in South Américan in the future. In this sense, the philosophy of an international mining company means that the company and the country working in the partnership and they can convince the outside world of the creditworthiness of the project. The mining company would be considering the account metal requirement in the future, the code of behaviour, the obligations and the rights among the employees, the shareholders, the customers, and to the State in wich its work. However, is not specially tailored philosophy for South America. The most important is the satisfactory agreement can be reached even with governments whose domestic laws preclude equity participation by the mining company.

Nov 20, 1969

By John F. O'Leary

The paper review the process the minerals industry and the materials revolution. For a long time, Latin América attemps at industrialization have been attempts in part, by need to important some of the many raw materials that industrial nations must have. However, the industrial sistem may be in for some of the many raw materials that drastic changes would increase the mineral self sufficiency of countries that are industrialized. In this way, the materials revolution would be a boom to Latin America, it would reduce some of the serious obstacles to the goals which all Americans seem to share.

Nov 20, 1969

By R. C. Head

The investigation describe the history of copper in the seventties, as well as indicates the forecast the probable trend of the Copper Industry over the coming decade, and second, to stimulate some discussion on what is a somewhat controversial subject. At the same point, the period of surplus production from about 1972 to 1976-1977, during part of which some voluntary restriction on output maybe necessary. In consecuence, its a necessity for forward planning so that, by 1973-1974, new mines maybe developing to preserve the continuity of supply .

Nov 20, 1969

The paper point out the way whereby the Canadian gobernment regulates and motivates mineral development. In this sense, its important the role of Gobernment policy in the development of the industry to its a stage. The progress of industry is due to a favorauble political climate which created an atmosphere of trust that has atracted foreing investment. Therefore, Canada's position owes much to sound legislation that recognizes the high element of risk in exploration and development and also the exhaustibility of mineral deposits.

Nov 20, 1969

By T. L. Gibbs

The paper describes the role of the State in the general regulation of the mining industry in the Republic of South Africa as well to refer briefly to some modern technological aspects in South American gold mining practice. In the same way, the paper categorizes it geographical, historical, the mineral and mining laws, lease consideration and taxation, the department of mines, atomic energy board and modern practices in the gold mining industry.

Nov 20, 1969

By Joseph Cervik

Gas occurs in coalbeds in an adsorbed and a free gas state. Adsorbed gas is stored in the micropore structure and its transport is governed by Fick's law. The free gas occurs in the fracture system and flows according to Darcy's law. These two modes of mass transport are interdependent. Production decline curves of coal-gas wells are of the constant percentage decline type and, thus, show no indications of flow characteristics peculiar to coal-gas reservoirs. The effectiveness of surface boreholes as a degasification scheme depends upon both good fracture permeability and a high fracture density. Conventional methods of reservoir engineering analysis are not applicable to coalbeds

May 1, 1969

By John V. Beall, William F. Haddon

A long the mighty Andean Cordillera, there is splendor beyond imagination-in the natural beauty of the mountains and in daring engineering and lavish investment in the mines. This is the story of the great copper mines of Chile and Peru. Each mine has a special quality which has tested the physical and spiritual resources of the founder. In the early days of the older mines, the mining engineer of song and story was more the rule than the exception. He was physically tough, ingenious and a leader of men. In the current political and social environment of Chile and Peru, the foreign contract mining engineer is still needed; but he must be a different type of man. To John J. Selters at Cerro's Rio Blanco, the principal ingredient is still "toughness," but it is "toughness of mind" that is needed. "He probably should be a teacher." The copper mines are not new. They were, almost without exception, worked by Indians (La Exotica might prove the rule), and later by the intrepid Spaniards. Modern mining began after the turn of the century. In Chile, the first of the big ones was the Braden Copper Co. founded on the El Teniente deposit. This development was followed by Chile Exploration Co. at Chuquicamata and Andes Copper at Potrerillos. These properties have been developed over the years by vast expenditures of money and a monumental amount of labor. None was free of technical problems-metallurgy at Chuqui, marginal grade of the old mine at Andes, avalanches and the great fire at El Teniente. The evolution which has brought the established mines of Chile, and the new ones coming on stream, to their present state of development is in reality the work of wonders of input-money, engineering and responsible management in an atmosphere of political stability. Without any one of these, the result would have been failure.

Jan 11, 1969

By Behram H. Wadia, Robert S. Lehto

A new metallurgical treatment for capturing as much of the values as possible from zinc refinery feed has been devised by personnel in Cerro de Pasco's Peruvian operation at La Oroya. Results from a pilot test illustrate that 50 metric tons of throughput can be maintained whereby substantially all the silver and copper report in the sponge iron while zinc and lead with indium and cadmium volatilize in the fume. This new technique named the Zileret (zinc leach residue treatment) process complements the electrolytic system used in the refinery so that all values in a zinc concentrate are economically recovered. In the system, dried zinc leach residue is pelletized with soluble zinc sulfate which already exists in the leach residue and a finely divided reducing agent such as anthracite coal. Upon heat addition, the loose anthracite in the charge maintains a reducing atmosphere while the free space above the charge has an oxidizing nature. When the charge reaches the reaction zone at about 1100°C, metals such as zinc, lead, cadmium and indium volatilize from the pellets, are oxidized in the upper kiln atmosphere, and are then carried in suspension as an oxide fume to the cooler and baghouse. The copper and silver content in their reduced forms, along with the iron, discharge from the kiln as a calcined product which is then cooled to below 130°C before being exposed to the air.

Jan 9, 1969

By H. C. Rolseth, R. H. Kohler

Jet channeling made its entry into the granite industry in 1955 and quickly gained acceptance as an economical method of quarrying. Developed by the Linde Division of Union Carbide Corp., this method employs a small rocket-jet burner with a high-temperature, high-velocity exhaust flame that causes granite to disintegrate. It can thus make continuous vertical cuts to free large blocks from granite formations. The Thermal Spalling Process The effect of a thermal device on rock depends upon the rock's spallability. In simplest terms, spalling is the decrepitation resulting from differential expansion of rock crystals due to thermally induced stresses.1 the individual rock properties influencing the spalling characteristic are so numerous and their interaction is so complex that it has so far been impossible to predict with accuracy the reaction of any particular rock to a high-temperature source of heat. Perhaps computers will eventually make such predictions possible, but for the present it is necessary to impose the thermal shock conditions on a sample of the rock to establish its spalling characteristics. The properties most favorable to a high degree of spallability are: (1) Large linear thermal expansion at temperatures below 700º C. (2) High thermal diffusivity at temperatures below 400º C. (3) Equigranular interlocking structure with little or no fine-grained clay or mica alteration products. (4) No significant amounts of soft, low-melting, or elastic minerals or materials which yield after thermal decomposition.

Jan 7, 1969

By S. Terry, W. Callender, R. J. Cornelius

When a dry ball-mill grinding circuit was in- stalled at the pellet plant of Hamersley Iron Pty. Ltd., it was something of a pioneering venture, since this was one of the first instances where such a circuit had been applied to iron ore on a major scale. The Hamersley pellet plant is located in Dampier on the coast of Western Australia. The feed for it consists of -8mm fines produced as a screened product at the Mt. Tom Price mine 186 miles inland from Dampier. It was these fines that encouraged the choice of a dry grinding facility for the plant. At the outset, tests had shown that the fines could not be filtered satisfactorily with a wet grinding system. At the pelletizing plant, the fines are stockpiled, reclaimed, dry ground in ball mills, formed into pellets on balling discs, hardened on an indurating line, and stockpiled for shipment overseas. These operations are shown in Fig. 1.

Jan 7, 1969

By E. Pothas, P. R. Jochens, L. B. McRae, D. D. Howat

Discussion H. J. S. Kriek*: During 1956 Iscor became interested in the acid smelting in a blast furnace of siliceous ores containing 15 per cent silica. This interest was as a result of the successful acid smelting in Germany at a CaO/SiO2-ratio of between 0.4 and 0.8. Acid smelting can become an economic proposition due to a reduction in slag volume accompanied by a lowering of the coke rate. Paschke and Hannel1 found that a free flowing slag (i.e. viscosities of less than two poise) would not be obtained at C/S-ratios lower than 0.82 and that the addition of 3 to 4 per cent alkalies became necessary. In titanium bearing slags it was established that maximum fluidity is obtained with 10 per cent TiO2. Acid smelting resulted in increased sulphur pickup with decreasing O/S-ratio and desulphurization with soda-ash outside the blast furnace was necessary. At Iscor Mr B. B. Segal established that, for slags with (CaO+MgO)/SiO2-ratios of 0.5, 0.6 and 0.7, the addition of alkalies and TiO2 resulted in a substantial decrease in melting point and also of viscosity. At a (CaO+ MgO)/ ratio of 0.53 the addition of 10 per cent TiO2 is as effective as the addition of 3.75 per cent alkalies. This means that a blast furnace can be run without the addition of alkalies and consequently the detrimental effect of alkalies on the lining can be avoided; also that fluid slags with 5 to 15 per cent MgO and 8 to 10 per cent Al203 can be obtained with 10 per cent TiO present. (CaO+ MgO)/SiO2-ratios smaller than 0.5 the addition of titania resulted in a decrease in melting point and also in an increase in viscosity. In ceramic crucibles the slag did not become more viscous with time but thickened appreciably when held in graphite crucibles. No titanium carbonitride could be detected and only Ti20a was found. Prof Howat also did not obtain the TiC-TiN solid solution and therefore it appears that the thickening of the slag is not solely due to the formation of the titanium carbonitrides. This is in agreement with the work of Michailov and Belyakova2 who found that TiO2 decreased the viscosity of acid slags and increased the viscosity of basic slags; that titanium sesquioxide (Ti203) and titanium monoxide (TiO) increased the viscosity of both acid and basic slags and that titanium carbide, which is found in larger amounts in basic slags than in acid slags, considerably increases the viscosity of both acid and basic slags. Patzak et al3 describes the following oxygen deficient titanias, viz Ti2O, TiO, Ti203, Ti3O5, Ti4O7, Ti5O9, Ti6O11- Ti10O9,Ti7O13,Ti8O15 and Ti9O17. Until about 1959 a fair amount of data was available on the viscosity of normal slags to which titania was added2, 4, 5, 6, 7, 8, 9. At Iscor an electromagnetic viscometer based on the viscometer developed by Bockris10 was built. Progress was very slow as our main attention was centred around problems associated with the operation of the Rotor process. During 1962 and 1963 two papers containing fundamental work on the viscosities of slags in the systems CaO-SiO2-TiO211 and CaO-SiO2-TiO2 at 0 per cent A1203, 10 per cent Al203 and 20 per cent Al20312 appeared. The work of Ross and Ohno obviated the necessity of any further work by Iscor on the viscosity of blast furnace slags containing titania. Ross gave the following optimum compositions for blast furnace slags containing titania. Titania % Lime % Silica % Lime/Silica-ratio 20 30-42 38-50 0.6-1.10 30 27-36 34-43 0.63-1.06 40 24-32 28-36 0.66-1.14 The optimum temperature is 1,500°C because at this temperature the largest workable composition range exists. Higher temperatures result in narrower optimum composition ranges and in increased rates of thickening. The factors affecting the rate of thickening were also investigated by Ross and Ohno, as the main problem with slags containing titania is not finding compositions which are fluid at operating temperatures but the thickening due to a lack of oxygen. With these slags when there is insufficient oxygen to co-ordinate each silicon atom with its own individual shell of four oxygen ions, some sharing of oxygen ions must occur, resulting in the formation of large silicate ions and a rise in viscosity. The formation of oxygen deficient titania can be prevented as long as iron oxide or manganese oxide remain in the liquid slag. Iwase13 and also Viens, Camp bell and Rogers14 obtained in the experimental smelting of ilmenite ores fluid slags with more than 3 to 5 per cent manganese oxide and ferrous oxide in the slags. It appears that titaniferous ores can be smelted in blast furnaces under the following conditions: (1) Acid slag operation, i.e. at C/S-ratios from O.6-1.0. (2) Dolomite can be used as a flux as MgO is a network modifier. (3) The Al2O3-content must be less than 15 per cent as alumina promotes thickening of the slag and decreases the optimum composition range. (4) The hearth temperature must not exceed 1,500°C. According to Ross a definite amount of energy is required for each ton of iron produced and in order to increase production an increase in heat

Jan 6, 1969

By I. R. Taylor

Union Carbide has recently developed two open- pit vanadium mines in the Wilson Srpings area of central Arkansas about five miles southeast of Hot Springs. The ores from these mines, together with those from a larger vanadium deposit at nearby Magnet Cove, are processed at a new 1600- tpd plant built by the company in the immediate vicinity (Fig. 1). The Wilson Springs vanadium deposits are associated with the Potash Sulfur Springs intrusive, a circular igneous complex which is exposed over an area that is somewhat less than a mile in diameter.1 The complex has a crude ring structure similar to that of the larger Magnet Cove instrusive six miles to the east.2

Jan 4, 1969

By F. F. Aplan

Mineral processing engineers have recorded an- other year of active research and development work. Most gratifying was the broadly based attendance at the Mineral Processing Fundamental (formerly Basic Science) Committee sessions at the 1968 Annual Meeting of the AIME. Because of the availability of good papers, the active discussion and the growing attendance, sessions have grown from one to three at the annual meeting. Prof. M. C. Fuerstenau of the University of Utah will chair the Mineral Processing Fundamentals Committee for the next two years and we may thus be assured of continued active leadership. The name change from "Basic Science Committee" to the more descriptive "Mineral Processing Fundamentals Committee" approved by the MBD executive council is a welcome improvement. Our profession continues to attract the interest and cooperation of those in other professional groups. The 1968 Engineering Foundation Particulate Matter Conference, under the chairmanship of John Karpinski of Bethlehem Steel, was devoted exclusively to comminution this year. It attracted conferees from five continents and served as a particularly stimulating source of interchange of knowledge from many technical fields. Next year's conference will be under the chairmanship of Professor L,. G. Austin of The Pennsylvania State University. This conference plus the Symposium on Wettability and Flotation to be held at the annual American Chemical Society meeting in Minneapolis in April indicates the success achieved in the inter-disciplinary approach to problems. Other evidence of this spirit of professional cooperation is the forth- coming book on Size Reduction edited by D. W. Fuerstenau. This is the outgrowth of an AIChE symposium on size reduction held in 1965.

Jan 2, 1969

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By P. T. Brooks

This Bureau of Mines study describes a process for recovering nickel, cobalt, molybdenum, and chromium contained in complex waste superalloy grindings that, for lack of an economical domestic recovery process, are being largely marketed abroad. The process, devised by laboratory scale operations, includes scrap preparation, dissolution of metallics in hot chlorinated acidic liquor, carbon adsorption, three successive solvent extraction separations, and selective chemical precipitations. Nearly 90 percent of the nickel, cobalt, molybdenum, and chromium were separated and recovered as oxides, carbonates, and basic sulfate products.

Jan 1, 1969

By L. F. Haven

"The desirable shovel speed-torque curves are described, along with the characteristics of the more important electrical components used to approximate these curves. A particular shovel regulator system combining these components is discussed in detail and some of the advantages and disadvantages of the system are given.INTRODUCTIONIN 1959, STATIC CONTROL was for the first time successfully applied, installed and operated on a mining machine in North America. Since that time, a great deal has been learned about this control by the people maintaining these machines as well as by the de-signers.In 1961, the first SCR (Silicon Controlled Rectifier) or thyristor control system was installed on an excavator. This control differed from the earlier static control in that thyristor excitors supplied the generator fields directly. The development of thyristors of a sufficient rating to supply amounts of phase-controlled power to the generator fields eliminated the bulky Mag. Amp. -Rectifier combination previously used."

Jan 1, 1969

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.' The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7'8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.'l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By John E. Kelley

The Bureau of Mines conducted a study to determine the feasibility of joining refractory metal compounds to each other and to oxide ceramics by a vacuum hot press-diffusion bonding method. Very satisfactory joins were made of ZrC to ZrB2, ZrN to ZrB2, ZrC to ZrN, and of ZrC, ZrN, and ZrB2 to Al203. Each of these join assemblies contained a mixture layer comprising 50 weight-percent each of the two end compounds. The mixture layer, sandwiched between each end compound, enhanced bonding and smoothed out the thermal expansion gradient between the two end members. Strength and thermal shock tests showed that the join areas of the ZrC, ZrN, and ZrB2 joins were stronger and more shock resistant than the parent materials. Also included in the joining tests was one each of TiC to TiB2, TiC to TiN, TiB2 to TIN, and TiC to ZrB2 joins. Each of these was well bonded, showing that the vacuum-hot-press method can be used for a variety of systems.

Jan 1, 1969

By R. D. Pehlke, J. V. Gluck, R. L. Louvet

A study has been made of the effect of small additions of bismuth on the activity of zinc in dilute solution in molten tin. Free-energy interactions have previously been determined between zinc and various third elements where the solvents were molten bismuth or molten lead.'-4 In both of these solvents, the activity of zinc exhibits a strong positive deviation from ideal behavior (at 550°C y° for zinc in lead is 11.4 and for zinc in bismuth is 3.0). The present work, using tin as the solvent, is an extension to a case where the positive deviation is considerably diminished (y°Zn at 550°C is 1.63). Several previous investigators have studied the Zn-Sn binary system; however, little data is available in the range below 0.1 mole fraction zinc.5= Previous high-temperature galvanic cell studies in the Sn-Zn-Bi ternary system included the determination by Gluck and Pehlke of interactions in the bismuth-rich corner1 and separate investigations of the central region by Oleari and Fioriani6 and by Ptak and Moser.7 Yokokowa et al.8 conducted Knudsen effusion studies in the central region; however, their experiments at 625°K were conducted somewhat below the present experimental temperature range. Their results indicated an increase in zinc activity with the addition of bismuth. The present series of experiments was conducted in galvanic cells represented as follows: Zn Zn++ in LiCI-KC1 eutectic Zn + Bi in Sn (pure reference (fused salt electrolyte) (molten alloy) standard) The experimental apparatus. a multi-electrode system employing alumina crucibles and contained in a Vycor tube under a helium atmosphere, has been described previously, as have been the experimental procedures, precautions, and the methods of data reduction.1-4,- The experimental measurements were made over the range from 450° to 650°C. Between thirty and forty measurements were made in each run. The linearity of the electromotive force vs temperature relations was verified by linear regression techniques. The correlation coefficients exceeded 0.99. The experimental results summarized in Table I include the interpolated electromotive force at 550°C and the temperature dependence of electromotive force. Only results from stable and consistent cells containing more than 0.025 mole fraction zinc are reported. Attempts to run cells at 0.01 or 0.02 mole fraction zinc were not satisfactory. This is attributed to the closeness of the free energies of formation of the chlorides of tin and zinc. Calculations employing Wagner and Werner's criteria for displacement reactions10 indicated that reduction of the zinc content to 0.01 mole fraction places the cell near the borderline concentration for a 1 pct error in measured potential. The compositions shown in Table I are the actual weighed-in amounts. Previous experience has indicated that compositional changes during the running of a stable cell are negligible.' Over the range of compositions studied for the binary alloys, the activity coefficient of zinc was essentially constant indicating that Henry's law is followed to 0.05 mole fraction zinc. The temperature, OK, de-

Jan 1, 1969