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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

Jan 1, 1969

By R. E. Gilchrist, R. F. Nielsen

When a gas is displaced by mother in a porous medium, and there is a relative immobile liquid present. there is a transition zone in which the gas composition varies from essentially that of the original gas to that of the injected gas. The change in extent of this zone with time may be governed by a mixing process in the direction of flow and by the rate of establishment of gas-liquid equilibrium, if the gases are appreciably soluble in the liquid. The relative importance of these two factors in deterri~ining the growth of the transition zone is discussed, with appropriate equations and experimental data. INTRODUCTION The various solution methods of oil recovery involve a transfer of the components of a mixture, whether within a single phase or between a liquid and gas. The similarity of a natural porous medium to systems used in separation and chromatographic processes makes it seem reasonable that certain concepts used by chemical engineers in "mass transfer" might be applicable to petroleum reservoirs. One approach, the HETP (height equivalent to a theoretical plate), involves a distance or length of time over which equilibrium might be con. sidered as established. Another approach involves direct use of a rate of mixing or rate of establishment of equilibrium. The latter approach has been preferred in relation to production problems. DISCUSSION AND PROCEDURE When a gas or liquid in a porous medium is displaced by one of different composition but miscible with it there will be set up a transition zone in which the composition varies from cssentially that of the original fluid to essentially that of the injected fluid. If the fluid being displaced is a gas, and there is a relatively immobile liquid present, the transition zone may be

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By E. I. Larsen, F. R. Hensel

According to statements by Guertler1 Smith and Hamilton were the first to study the copper-titanium alloys, but owing to the presence of large amounts of impurities their data are inconclusive. M. A. Hunter and I. W. Bacon later investigated the electrical conductivity and the temperature coefficients at room temperature. The present writers reported their results2 in November, 1930. Recently Kroll published data on copper-titanium alloys3 which agree closely with those obtained by the authors. Material Tested The titanium used was in the form of square sintered rods, the analysis of which runs as follows: titanium, 95.4 per cent; silicon, 0.7; iron,l.8; aluminum, 1.4; copper, 0.1; manganese, 0.05. The ingots were prepared in a high-frequency induction furnace in air atmosphere. Their analyses are given in Table 1. Up to 5 per cent titanium the alloys could be forged. Above that amount they were red short and broke up easily. Owing to their rapid absorption of nitrogen and oxygen from the air, the alloys with the higher amounts of titanium tend to form surface films which greatly increase the casting difficulties, especially when small masses of metal are handled. It was, however, possible to prepare sound ingots up to 25 per cent titanium. Thermal and X-ray Investigation The cooling curves of some of the alloys are plotted in Fig. 1, and R tentative diagram constructed from these data is given in Fig. 2. From this it is evident that the solid solubility of copper for titanium is approxi-mately 4 to 5 weight per cent titanium at 878" C., which is the eutectic temperature. The melting point of copper is lowered gradually by adding

Jan 1, 1932

By Frank E. Woolley, Robert D. Pehlke

Jan 1, 1965

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

By P. C. Hodges

WHILE there is very little romance connected with the operation of a stone quarry, yet to those who have participated in the growth and development of a business that has been a pioneer in its field and that FIG. 1.-LOCATION OF PROPERTY OF MARBLE CLIFF QUARRIES COMPANY. has been in continual operation two-thirds of a century there is bound to be a background of experience, which if properly capitalized, brings progress as well as satisfaction in its accomplishment.

Jan 1, 1936

By L. Adler

Longwall caving, one of the most economical and attractive mining methods, is yet one of the most difficult and hazardous.1 This dualism is inherent in a method which manipulates the mine supports themselves to aid in excavation. The difficulty is further compounded by the lack of an analytical method to predict and control results. This paper is intended to meet this need by providing a first approximation to the mechanics involved. The analysis will be limited to materials which are linear-elastic, homogeneous and isotropic. The rock structure is assumed to consist of beds of uniform thickness with no interbed bonding.2 Consequently, the mine roof can be likened to a beam, in which the action characteristic of longwall caving is the controlled deflection of the barrier supports. This deflection causes load to be intentionally transferred from these barrier props to the working face.3 Two of the requirements of this method, shared in common with other mining methods, are the provision of (1) adequate and (2) safe working space. The third requirement is the one characteristic of longwall caving and is somewhat in conflict with the second; (3) the development of near-failure static loads at the face. Requirement (1) is handled by spacing the barrier props sufficiently far from the working face for efficient operation. Requirement (2) limits the static stresses in the structure to predetermined allowable values. This means that it is not desirable to induce a maximum load on the working face as requirement (3) may imply. Such a condition could produce collapse in the whole structure. It is the purpose of the undercut to limit the depth, and thereby control the failure of the face. Therefore, requirement (3) really means the development of an optimum, not maximum, load which, in conjunction with undercutting, produces failure at the working face, with minimum powder consumption. Stress analysis requires an exact delineation of the structure and loads. The structure will be defined as the immediate roof and its supports. Since the roof is severed at the caving line, the supports reduce to the barrier props and the working face, as shown in Fig. 1. The mechanics of failure within the working face itself are complex and beyond the scope of this study, since the face represents a typical mine invert structure.4 However, this lack can be made good by the judicious collection of field data. The primary load on the structure is its own weight or body load which can be considered uniformly distributed over its upper surface. Additional loading occurs due to interference of overbeds with the structure. Wherever this occurs, the effect can be approximated by a load uniformly distributed on the upper surface of the structure.5 When this interference is intermittent, as with a much thicker overbed, the elastic curve for the overbed is superimposed on that for the structure and the extent of interference noted, as Fig. 2 shows. However, for simplicity, this study will ignore such intermittent loads without impairing the generality of approach. Consequently, the free-body diagram is that of a uniformly loaded cantilever beam with an inter-mediate support, as shown in Fig. 3. For convenience of analysis, the diagram will be divided just to the

Jan 1, 1961

The following is an incomplete list of members and guests who called at Institute headquarters during the period Feb. 10, 1918 to Mar. 10, 1918: W. G. Anderson, St. John, N. B., Canada. Charles E. Locke, Boston, Mass. L. M. Banks, Camp Meade, Md. E. T. Lednum, Joplin, Mo. P. E. Barbour, Albany, N. Y. C.' K. McDonald, Washington, D. C. Alan M. Bateman, New Haven, Conn. C. T. Malcolmson, Chicago, Ill. Graham Bright, Pittsburgh, Pa. Stuart B. Marshall, Badin, N. C. J. F. Callbreath, Washington, D. C. T. C. Merriman, New Haven, Conn. J. E. S. Clark, Riverside. Cal. Arvid E. Nissen, Gary, Ind. G. H. Clevenger, Palo Alto, Cal. Herbert G. Officer, Conway, S. C. George C. Crossley, Trenton, N. J. J. E. Parker, Bulawayo, Rhodesia, S. Afr. R. H. Eagles, Palmerton, Pa. Francis R. Pyne, Elizabeth, N, J. Charles Enzian, Pottsville, Pa. Alfred Hull Ramage, Joplin, Mo. Albert H. Fay, Washington, D. C. H. H. Stoek, Urbana, Ill. David B. Gemmill, Crown King, Ariz. G. M. Taylor, Colorado Springs; Colo. Ronald Harris, London, Ont., Canada. Charles Tubby, St. Paul, Minn. Wm. J. Hayes, Colombia. So. America. J. B. Tyrrell, Toronto, Canada. B. B. Hood, Chrome, N. J. Edmund W. Westervelt, Ymir, B. C. 0. P. Hood, Pittsburgh, Pa. Carl Zapffe, Brainerd, Minn. H. M. LaFollette, LaFollette, Tenn. W. S. Boyd, formerly superintendent of mines of the Ray Consolidated Copper Co., has been appointed assistant general manager. William Campbell, Professor of Metallurgy, at Columbia University, is acting as metallurgist at the New York Navy Yard.

Jan 4, 1918

By J. C. Martin

Equations for three-phase, three-dimensional, compressible flow (including capillarity) are reduced to two-dimensional relations by a partial integration. This reduction allows three-dimensional flow problems to be treated with mathematics for only two spatial dimensions. The results can be used to formulate flow equations for two-dimensional reservoir simulators in which the effects of capillarity and fluid segregation in the third dimension are represented. Such reservoir simulators would retain many of the aduantages of two-dimensional simulators while simulating three-dimensional effects. The principal restriction of the method is that the thickness of the reservoir should be small, compared to the distance across the reservoir. INTRODUCTION In recent years, computers have been used to calculate the performances of many reservoirs. Most of the detailed calculations, however, are based on finite difference solutions of the flow equations, and present day computers are seldom able to handle a sufficient number of cells to produce entirely satisfactory solutions, even for reservoirs represented by two-dimensional arrays of cells. The situation becomes much worse when one wishes to approximate the reservoir by a three-dimensional array. A great saving in computation or a more detailed solution can be obtained for many reservoirs by using the partial integration of the equations of flow presented in this paper. The integration reduces the three-dimensional equations to two-dimensional relations; and, for studies of two-dimensional flows in vertical cross-sections, the equations are reduced to one-dimensional relations. Most reservoir performance calculations currently are based on one- or two-dimensional flow re1ations.l-3 In some cases flow in the third dimension is approximated by assuming a particular type of vertical saturation distribution, such as gravity segregation.l.2. The relations developed in this paper approach those for segregated flow as the capillary pressures approach zero, and they approach those for uniformly distributed saturations as the capillary pressures are increased. For this analysis, the ratio of the reservoir's thickness to the maximum distance across it must be small. The capillary pressures between the oil and water should also be small compared to the maximum pressure difference in the reservoir. This requirement is met by most reservoirs. It is assumed that the capillary-pressure curves are well defined, whether or not hysteresis effects are included. Also, the reservoir must have sufficient vertical permeability to allow the fluids to segregate. The results presented here provide a firm theoretical foundation to Coats' et aL5 assumption of vertical equilibrium and extend the relations to three-phase flow. Coats' assumption of vertical equilibrium, which he verified by calculations and experiment, is developed here mathematically from basic flow equations. DISCUSSION SATURATION AND PRESSURE DISTRIBUTIONS Appendix A presents a mathematical analysis of fluid flow in reservoirs where the ratio of thickness to maximum distance across the reservoir is small. The results indicate: (1) that the fluids along any line perpendicular to such a reservoir's upper surface are in static capillary equilibrium (vertical equilibrium); (2) that, to a first approximation, the fluid pressures and properties are functions of only areal position in the reservoir and time; and (3) that hydrostatic pressure gradients exist along any line perpendicular to the reservoir's upper surface. The results might be expected after studying several physical considerations. First, no flow is allowed normal to the upper and lower reservoir boundaries, which are relatively close together.

Jan 1, 1969

[ ] [LOCAL SECTION CODE (Numbers indicate Sections) No. Section LI Alaska L50 Adirondack L2 Arizona L58 Arkansas L84 Balcones L66 Billings Petr. L3 Black Hills L4 Boston L76 Caracas L5 Carlsbad Potash L6 Central Appal. L60 Central N. Mex. L7 Chicago L79 CIM-AIME Calgary L82 CIM-AIME Edmonton L8 Cleveland L9 Colorado]

Jan 1, 1961

By J. C. Bokros, A. S. Schwartz

The irradiation-induced densification of pyrolytic carbon has been shown to take place by a simple first-order rate process. The values of the densification constant, kd, for isotropic carbons are 1.0 x 10-22, 1.4 X 10-22 and 2.8 X 10-22 (nut)-1 at irradiation temperatures of 520o, 670°, and 1000oC, respectively. The apparent activation energy obtained from the temperature dependence of kd for isotropic carbons is about 0.2 ev. Estimates of the maximum stresses that develop in isotropic carbons owing to shrinkage onto an unyielding support show that stresses in excess of 15,000 psi may be avoided during irradiatian at 600" and 1000°C if the initial coating density is kept above 1.5 and 1.9 g per cu cw, respectively. If a carbon coating on an unyielding support is not completely isotropic, stresses may continue to build up at high neutron exposures after densification is complete because of continued anisotropic distortion. Stresses in excess of 15,000 psi from this source may be avoided during irradiation at 1000°C if' the Bacon anisotropy factor is kept below 1.3. A variety of applications of carbon and graphite in nuclear technology has stimulated numerous studies of the effect of neutron irradiation on these materials One of the most interesting problems associated with the use of carbons and graphites in the high fast neutron fluxes of nuclear reactors arises as a consequence of the neutron-induced dimensional changes that occur during irradiation. Energetic neutrons displace car- bon atoms from their lattice positions; and, depending on the temperature, the interstitials and vacancies produced migrate to form clusters, recombine, or are annihilated at dislocations or crystallite boundaries. The competition of various sinks for the point defects results in structure-sensitive bulk-dimensional changes that vary with temperature in a complicated way. This paper deals with the neutron-induced dimensional changes in turbostratic carbons that are being used as coatings on nuclear fuel particles. Details of the structure of these carbons and the variations of their structure with deposition conditions have been reported.'-3 It has been shown in previous work that the neutron-

Jan 1, 1968

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral'iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,' while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By C. G. Dunn

James, Jones, and Leak (JJL) conclude that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally produced recrystallization textures. I agree. However, it is not clear whether they conclude a) that the orientation dependence of rate of growth of secondaries in (commercial) silicon iron depends on both temperature and a temperature gradient or b) that, in applying rate data obtained in a steep thermal gradient, the isothermal annealing temperature must be close to the temperature for which the rate data apply. Also, it is not clear what tem-

Jan 1, 1967

By Cyril Smith

THE following table, which is composed of data given in the author's first paper on the thermal conductivity of copper alloys1, contains the results which have been obtained by previous workers on the thermal conductivity of the copper-tin, the copper-phosphorus and the copper-tin-phosphorus alloys (the phosphor bronzes). TABLE 1.-Previous Investigations Composition, Per Cent. by Weight Thermal Conduc¬ Investigator tivity, Cal/Sq. Cm./ Copper Tin Phosphorus CM./Sec.. °C. Hardebecka 95.0 5.0 0.176 (20° C.) Grossmanb 90.1 9.9 0.105 75.5. 24.5 0.059 24.9 75.1 0'.139 (13° C.) 9.7 90.3 0.131 0.0 100.0 0.142 Griffiths and Schofieldc 91.7' 8.0 0.30 0.108 87.2 12.4 0.40 0.087 (20° C.) 90.0 10.0 Small amt. 0.100 Donaldsondd: 87.8 1 11.3 0.35 0.128 Pfleiderere 99.4 1 0.63 0.250 (30° C.) 98.0 1.98. 0.125

Jan 1, 1930

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968