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By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By Gearge C. Wallick

This paper describes experimental procedures for the calibration of capillary tubes to be employed as comparison standards in gas flow-rate measurements and considers several types of flow which were observed in the calibration of seven capillaries of varying diameter. It is shown that under certain experimental conditions deviations from Poiseuille flow are observed which may not be attributed to turbulence, and that this flow behavior may be described empirically by introducing the classical kinetic energy correction into the Poiseuille equation. INTRODUCTION Techniques have been developed for the measurement of the volume rate of flow of nitrogen through glass capillary tubes as a function both of the differential pressure applied and of the absolute gas pressure. Capillary tubes thus calibrated are frequently used to determine the rate of gas flow through a porous sample in the measurement of slip-corrected permeability. The purpose of this note is to describe the calibration procedure and to discuss some observed deviations from the ideal flow behavior predicted by the Poiseuille equation. EXPERIMENTAL PROCEDURE The volume flow rate of nitrogen as a function of the differential pressure was determined experimentally for a series of seven glass capillary tubes of varying diameter. As is shown in Table 1, the capillary radii in the series ranged from 0.004 cm for K1 to 0.07 cm for K7. The capillary tubes were cut from capillary tubing purchased on special order from several manufacturers and the bore radii were determined by microscopic measurement. The gas volume flow rate was measured for each capillary tube at a series of differential pressures in the range from 0 to 3 cm of mercury and at average absolute pressures of 1.0, 2.5, 4.0, and 6.0 atm. Experimental Procedure for Small Capillaries A schematic diagram of the apparatus used to calibrate the three smallest capillaries, Kl, K2, and K3, is shown in Fig. 1. By means of a standard Ruska Instrument Corp. volumetric pump (equipped with a synchronous motor drive, two stages of gear reduction, and a quick-change lathe gear box), nitrogen was displaced by mercury from a metal cell immersed in a constant-temperature bath. The pump, the line to the cell, and a part of the cell were filled with mercury. As mercury was forced into the cell, it displaced nitrogen which passed through the capillary tube being calibrated and into a large container with a volume of approximately 30 liters. Since the volume of this container was very large compared to the total volume change of the gas resulting from the action of the displacement pump, the absolute pressure of the system was essentially constant throughout any one run. Prior to any determination this pressure could be set at any desired level by means of an auxiliary nitrogen cylinder. The differential pressure across the capillary was measured with a Meriam Red Oil manometer and recorded together with the corresponding pump displacement rate which was equal to the gas flow rate. By repeating this process for a series of different displacement rates at each of the absolute pressures of interest, the data necessary for plotting the calibration curves for capillaries K1, K2, and K3 were obtained. All calibration measurements were made in a constant temperature room to minimize errors due to temperature fluctuations. In each run. the flow was maintained until equilibrium was established. Experimental Procedures for Large Capillaries The flow rates through Capillaries K4, K5, K6, and K7 required to obtain the pressure drops desired were larger than could be obtained from available constant displacement pumps, and it was thus necessary to employ an alternative calibration procedure. The arrangement of apparatus used in calibrating these capillaries at an average pressure of one atmosphere is shown in Fig. 2. Each capillary was calibrated by flowing nitrogen through the capillary and recording the differential pressure as a function of the flow rate. 'The differential pressure was measured with a Meriam Red Oil manometer and the flow rate was determined by collecting the effluent gas over water at constant pressure and recording the increase in volume per unit time after an equilibrium had been established. Appropriate corrections were made for the

Jan 1, 1953

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal' and by Chew and Connally' for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7' API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.' All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By M. Cross

INTRODUCTION The results of the Japanese dissective investigations have [l-4] transformed our understanding of how the blast furnace operates. These studies revealed an internal structure of the furnace burden with five main zones, as illustrated in Figure 1. In the granular zone the charged material retains its structure whereas in the cohesive zone the iron ore particles are at advanced stages of reduction and form a semi-molten mass with a relatively high flow resistance. In the active coke zone molten iron and slag flow through a matrix of loosely packed coke. The raceway is a relatively small void space generated by displacement of coke due to the hot blast momentum, whilst the hearth is packed with coke, slag and molten iron. [ ] It is now well appreciated that furnace control is largely achieved and maintained by using the burden charge distribution to determine the gas glow distribution within the furnace and, hence, the shape and extent of the cohesive zone. In fact, Wakayama et a1 [5] of Nippon Steel Corporation state that optimum furnace operation is synonomous with the formation of a desirable cohesive zone shape, which in turn is almost solely determined by the burden charge distribution and its mechanical properties [6]. Much of the development work on operating furnaces since the dissective investigations has been oriented towards the identification of external furnace measures which reliably predict the shape of the cohesive zone. Currently the most popular measures are top gas temperature, velocity and CO/CO, ratio profiles [5]. More recently pressure distributions as evaluated from a series of wall measurements down the height of the furnace are also being utilised [7] to identify the position and shape of the cohesive zone. A great deal of emphasis has been placed upon achieving a consistent quality in the burden charge materials, establishing a suitable set of operating conditions and only making changes when forced to, ie., the operation for some reason moves outside a desired operating range or the production requirements change. Operational control schemes based upon this philosophy (eg., Kawasaki's GO-STOP system [8]) have been remarkably successful at achieving both high production rates and relatively low fuel costs. Mathematical models have long been used as tools to assist in the analysis of the blast furnace process. Although, the models have been useful in post-operative analysis and for identifying trends, etc., they have not proved reliable for detailed design criteria or as the basis for effective control schemes. Such mathematical models have moved from simple statistical correlation, through overall and stagewise heat-and-mass balance calcu-

Jan 1, 1984

By N. A. Gokeen, M. Ohtani

EFFECT of elements on the solubility of carbon in liquid iron is useful in calculating and correlating a number of thermodynamic properties as shown elsewhere in detail.' Kitchener, Bockris, and spratt2, and later Turkdogan and Hancock3 have investigated the effect of sulfur on the solubility of carbon at various temperatures and concentrations. For any chosen sulfur concentration, the solubility of carbon reported by Kitchener et al. is considerably lower than that by Turkdogan and Hancock. It was therefore felt that a reinvestigation of this problem was necessary. EXPERIMENTAL METHOD An alloy of Fe-C-S .was prepared with electrolytic iron and ferrous sulfide melted by induction in a graphite crucible, 4 in. high 1 1/2 in. ID under a CO-atmosphere. The temperature, held at 1500" ± 5°C in all experiments, was measured with a Pt-Pt + 10 pct Rh thermocouple immersed into the melt. In order to assure saturation with carbon, the melt was stirred with a graphite rod. After approximately 1 hr at 1500 °C, a sample was obtained by sucking the melt into a silica tube, 4 mm ID. The sample was then analyzed for carbon and sulfur by usual methods. RESULTS The results are presented in Table I and plotted in Fig. 1 with the individual values of Turkdogan and Hancock.3 Scattering in the data is equivalent to 3 pct or less in carbon analysis. The broken line represents the empirical equation obtained by Kitchener et al. from their data. It is evident that the present data are in good agreement with those of the former investigators but in disagreement with the latter. The cause for this discrepancy cannot be readily offered since the experimental methods in the three investigations were nearly identical. Additional evidence corroborating the author's results may be presented in the following manner. The difference between the solubilities of carbon in the ternary Fe-C-X melt with a small concentration of any element X, and in the binary Fe-C melt is %?C = %CIII-%CII [1] where %?C is the change in solubility, and %CIII and %CII are the solubilities in the ternary and the binary systems respectively. The value of %Cii

Jan 1, 1961

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InAs and GaAs were measured over the temperature range 400°K to temperatures above the melting points using a di-phenyl ether drop calorimeter. Smoothed values of the thermal properties have been derived and tabulated at even temperature interuals . The heats of fusion of InAs and GaAs were determined as, respectively, 8790 ± 200 and 12,590 ± 300 cal per g-atom at the respective melting points of 1210º ± and 1513º ± 1°K, yielding entropies of fusion of 7.26 * 0.16 and 8.32 ± 0.20 cal perºK per g-atom, respectively. A general discussion of the thermal properties of III-V com-pounds is given. THE low-temperature heat capacities of InAs and GaAs have been determined by Piesbergen.1Using a dynamic temperature modulation technique, Miller2 has determined the heat capacities of the compounds as well as GaSb and Ge between room temperature and 650°K; however, it has been observed that values determined by drop calorimetry for GaSb3 and for germanium4 are consistently about 5 pct lower than Miller's results. Cox and Pool10 report values for the heat content of InAs and GaAs and the heat of fusion of InAs. No value for the heat of fusion of GaAs appears to have been previously reported. This paper reports results of high-temperature heat content investigations of InAs and GaAs measured in the range 400" to above 1500°K employing a diphenyl ether drop calorimeter. These results, together with our previous results on III-Sb compounds3 as well as heat-content measurements5 of solid InP and Gap, are used in a general discussion of these compounds. EXPERIMENTAL PROCEDURES High-purity samples of the compounds, stoichio-metric to ±0.1 at. pct, were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories. The sample preparation, description of the calorimeter, and details of the heat content measurement have been previously described.3 Samples were sealed in evacuated silica capsules and suspended by a Pt-Rh wire in a Pt-wound vertical tube furnace, heated to temperature

Jan 1, 1970

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

Beyer Barometric Condenser The Ingersoll-Rand Co. is now offering to the trade complete steam­condensing plants for all service conditions. This equipment includes the Beyer barometric condenser, for' which the company has secured the patent rights, Imperial duplex and Ingersoll-Rogler straight-line reciprocating dry vacuum pumps and, where required, Cameron simplex and centrifugal pumps. The Beyer barometric condenser is of the counter-current type, in which air and cooling water flow in opposite directions. The steam inlet is at the bottom of the condensing v el, the water inlet above and the air-removal opening at the top. The sheets of cooling water over owing the pool at the inlet point meet the entering steam. The two are brought into intimate contact by conical baffle plates which assist the water to absorb to its full capacity the latent heat of the steam. The non-condensable air liberated in the condensing action rises through the falling water to the removal point at the top, being cooled to practically the temperature of the incoming water. It is also to be noted that ample opportunity is given for the removal of the air content of the water before

Jan 8, 1916

By W. L., Yerkes

AN interesting study of the application of air-, conditioning to the problem of mine ventilation and cooling can be found on the Witwatersrand in South Africa. Here there are a large number of deep mines in a relatively small area. Due to the nature of the reef, many mines are working at a depth of 6000 ft. and some have gone down to 8000 and 9000 ft. below the surface. At such depths, even in a country geologically as old as Africa, the virgin rock temperature approaches 110°F. The flow of heat from the- rock to the ventilation air is tremendous though the shaft or drift may have been open to ventilation for some years. In addition, there is the heat produced by machinery, lights, and men at work and the heat of adiabatic compression of air introduced into the mine. The difference in atmosphere pressure between the collar of a shaft and a level 6000 ft. below is nearly 3lb. per sq. in., resulting in an increase in heat content of nearly four B.T.U. per pound of air delivered to the mine at surface. Further the exclusive use of wet mining to reduce the incidence of miner?s phthisis increases the latent- heat content of the air.

Jan 1, 1941

Jan 1, 1967

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.' Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,' with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By M. J. Pool, R. K. Saxer, J. R. Myers, D. S. Dickson

ThE equilibrium phase diagram of the Mo-Cr system, described by anssen,' indicates that chromium and molybdenum form a continuous series of solid solutions above 1673K. The liquidus and solidus have been reported to have a minimum at about 12 at. pct Mo and 2133°K by Bloom and Grant2 and by Putnam, Potter, and Grant.3 X-ray studies by Trzebiatowski and ploszek4 and Baen and Duwez' revealed no indication of solid solution decomposition after long anneals at 1473", 1273", 923", and 873°K. However, Bloom and rant' by means of cooling and heating curve analysis of alloys containing up to 45 at. pct Mo found thermal effects at temperatures approximately 100" * 30°K below the liquidus. The only previous thermodynamic study of the Cr-Mo alloy system was made by Laffitte and Kuba-schewski6 who used the Knudsen effusion method at 1471°K. These investigators reported the possibility of a miscibility gap because they observed positive deviations from ideality in their chemical activity

Jan 1, 1970

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896

Jan 1, 1923

Oct. 8 to 13, inclusive, 1917 COMMITTEES Committee on Arrangements H. A. BUEHLER, Chairman W. E. MCCOURT, Secretary C. J. ADAM L. L. HUTCHISON VICTOR RAKOWSKY J. A. CASELTON EUGENE MCAULIFFE J. D. ROBERTSON .F. W. DEWOLF P. N. MOORE ARTHUR THACHER E. F. GOLTRA MRS. P. N. MOORE H. A. WHEELER Committee on Ladies', Entertainment MRS. PHILIP N. MOORE, Chairman MRS.. W. E. MCCOURT, Vice-Chairman MRS. D. M. ARMISTEAD MRS. R. G. HALL MRS. A. A. BONSACK . MRS. J. W. HEGELER MRS. B. F. BUSH MRS. J. N. HOUSER MRS. G. 0. CARPENTER MRS. EUGENE MCAULIFFE MRS. F. V. DESLOGE MRS. RUDOLPH PORTER MRS. F. W. DEWOLF MRS. N. P. ROOD MRS. A. W. DICKINSON MRS. ARTHUR THACHER

Jan 12, 1917

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896

Jan 1, 1923

By M. Prats

Most of the information available on the heat efficiency of hot fluid injection processes, both water and steam, has been obtained from calculated temperature distributions in the pay zone and adjacent formations. The usual approach has been to write the heat balance equations in terms of the temperatures, and then to introduce whatever simplifications are necessary to help obtain an analytical or a numerical solution. In either case, the assumption has often been made that the vertical thermal conductivity in the flooded interval is infinite, so that the temperatures within the flooded interval are then independent of vertical position. Because it was first made by Lauwerier,l and has been used extensively since, this assumption will be referred to as the Lauwerier assumption. Excellent reviews of the literature on the heat efficiency of hot fluid injection processes have been given by Spillette,2 Flock et al.,3 and Ramney.4 Of course, the most significant contributions take into account the effect of a finite vertical thermal conductivity on the vertical temperature profile. The most general analytic expression for the heat efficiency of a hot fluid injection process is that of Antimirov5 who considers injection of a heated incompressible fluid into a reservoir through an arbitrary number of wells. The rate of heat injection into the reservoir, as well as the injection temperature, is an arbitrary function of time. The geometry of the horizontal flow is arbitrary, although the reservoir is considered to be of uniform thickness and properties and to be of infinite areal extent. Heat transfer within the reservoir is by horizontal convection and conduc- tion, and by vertical conduction. In the formations adjacent to the flooded interval, heat transfer is by conduction in any direction. Thus, the available expression for the heat efficiency due to hot water injection has been developed for rather general conditions. This degree of applicability has not been obtained for other thermal recovery processes. By making the Lauwerier assumption we have been able to obtain expressions for the heat efficiency that are essentially independent of the thermal recovery process, be it steam, hot-water, or underground combustion. Clearly, then, the approach followed here is more restrictive than that of Antimirov5 in that it uses the Lauwerier assumption. At the same time less restrictive assumptions are made about the horizontal heat transfer mechanisms, either in the flooded interval or in the formations adjacent to it. The main difference between our approach and that of other investigators is that the heat balance in the pay zone is expressed for the pay zone as a whole rather than for a volume element within it. The Lauwerier assumption is introduced after the problem is developed along these lines as far as possible. The details of the development of the heat efficiency are given in the Appendix, while the main features of the model are discussed in the next section. Results and their implications are discussed later in a separate section. The Model Certain assumptions have been made to determine

Jan 1, 1970