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By Frederic Dewey

IT IS common to blame irregular assay results upon volatilization and much has been written upon the subject, but there is no. real evidence that, in a properly conducted assay, the loss of either gold or silver by volatilization is sufficient to affect appreciably the result, even when, arsenic or antimony may be present. Bulk assays of flue dust from assay muffles have been published, but the data given are totally insufficient to even approximate the volatilization from a single assay; and such figures as we have indicate the volatilization to be extremely small. Diligent search in the literature and wide inquiry among assayers and instructors have failed to produce a single case where the litharge volatilized in making an assay has been collected and assayed for gold and silver. Having attempted to do this, with most indifferent success, I am not surprised that this has not been done. While various textbooks give volatilization as a cause of loss in cupellation, it may safely be said that in the rare cases where this volatilization is sufficient to affect appreciably the result it is due to excessive temperature. Percy1 says "The loss of silver by volatilization during cupellation is very slight (unless the temperature has been much too high), and may be disregarded." This statement is repeated by the Beringers2 and Smith,3 who includes gold with silver. Mitchell4 says the litharge fume rarely contains over one ten-thousandth of silver. Campredon5 says that at a proper temperature no silver is lost by volatilization.

Jan 2, 1920

By A. E. Jenkins, L. A. Baker, N. A. Warner

The electromagnetic levitation technique has been successfully applied to rate studies of the de-carburization of liquid Fe-C alloys from 5.5 to zero pct C at 1660°C using gas mixtures containing 1 to 100 pct CO2 with CO or helium as diluents. The rate was shown to be independent of carbon concen -tration in the melt and only slightly affected by total pressure. The results were shown to be consistent with control either wholly or predominantly by gaseous diffusion. As well as avoiding side reactions with the crucible, levitation allowed precise calculation of reaction rates since the geometry of the system was accurately known. It also enabled interpretation using the established mass-transfer correlations for a gas flowing past a single sphere, The existence of gaseous-diffusion control and the extremely high rates of reaction reported for gas flowing past small spheres are of great practical significance in relation to current investigations into the use of spray-refining techniques in continzcous steelmaking. PREVIOUS work on the kinetics of carbon removal from liquid iron has generally involved the use of oxygen as the gaseous oxidant. Investigations have been made on commercial steelmaking furnaces and in addition laboratory-scale experiments have been attempted with a slag phase present. The general lack of agreement and the obvious difficulty in interpreting the results is at least partly due to the complexity of the systems used. This work has been reviewed by carter1 and more recently by Bods-worth2 and ward.3 The gas-liquid metal reactions have also been studied with slag-free melts by the conventional technique of blowing oxygen onto the melt contained in a crucible. The reaction between the oxidant and carbon could be followed by sampling either the melt or the gas phase. Side reactions with the crucible material have precluded direct interpretation of the results. Fujii, 5-7 using O-A mixtures, attempted to correct for the crucible reaction and reported that the reaction between carban and oxygen occurred at the melt surface and was controlled by gaseous diffusion for carbon contents greater than a critical value and by carbon-diffusion control in the metal for carbon contents less than the critical. The critical value was given as approximately 0.15 pct C. However, whereas this was the case for oxygen contents in the gas stream up to 10 pct, between 10 and 20 pct the rate was found to be approximately independent of oxygen content, and Fujii attempted to explain this observation by postulating the presence of an oxide "film".7 Turkdogan et a1.' have studied iron fuming during decarburizing and suggested gaseous-diffusion control of the reaction above a critical carbon concentration, given as approximately 2 pct C. Filippov9-12 reports in a similar manner to Fujii but makes no mention of the crucible reaction with the carbon in the melt, even though this would be expected with the temperature, crucible material (MgO), and carbon contents used. Both CO2 and O2 were used as oxidant gases. In the present work the decarburization of liquid Fe-C alloys was studied using an adaptation of the electromagnetic levitation technique, and thus the complexities introduced by crucible side reactions were eliminated. In this technique a single sphere of the Fe-C alloy is freely suspended and heated by electromagnetic induction in a flowing stream containing the oxidant gas. The full range of carbon levels up to saturation was studied, the temperature of the melts in this instance being held constant at 1660°C. The oxidant was CO2 which was used either pure or in association with a diluent gas, the total gas pressure being maintained either at 1 atm or at a reduced pressure. Thus the reaction under study was:

Jan 1, 1964

By R. W. Parsons, P. R. Chaney

Oil recovery by the imbibition mechanism can be important in fractured carbonate reservoirs with a bottom water drive. Laboratory experiments were performed on water-wet carbonate rocks to model this process. The results are interpreted in light of the applicable scaling laws. The imbibition production behavior of a pillar of rock subjected to a slowly rising water table can be synthesized from data on total immersion experiments on small rock samples. If the rate of water table rise is slow enough and if the physical properties are such that the imbibition zone is of a small vertical extent, then only the final oil recovery on the small samples need be known. Applying laboratory imbibition data to a real reservoir should be done with caution because of possible wettability problems and the unknown behavior of two-phase flow in fractures. INTRODUCTION The spontaneous taking up of a preferential wetting fluid into a porous medium with the simultaneous expulsion of the contained fluid is termed imbibition. One of the many physical imbibition processes is the production of oil by the taking up of water into a water-wet reservoir rock. In certain types of heterogeneous reservoirs, e.g., fractured, it is realized that imbibition alone may be the dominant mechanism. Theoretical studies of imbibition oil recovery have followed several lines of attack. The behavior of certain mathematically tractable and conceptually simple models have been analyzed. Birks1 considered a bundle of vertical capillaries model, while Perotti et al.2 and Kelemen3 used a model of a series of vertically oriented fractures. If the oil production behavior from a block of reservoir rock is known, then the cumulative behavior of a vertical stack of these blocks subjected to a rising water table can be determined by a method outlined by Aronofsky et al. 4 Knowing the capillary pressure and relative permeability functions should uniquely set the imbibition behavior for a given sample. Solutions of the partial differential equations describing the process, however, present some formidable problems. Digital computer techniques have been applied to displacement processes in which the capillary pressure has been included.5"8 More recently, similar techniques have been used by Blair 9 to calculate countercurrent imbibition behavior. The fact that imbibition behavior is described by the usual fluid flow equations (Darcy's Law and continuity equation) implies that the derived scaling laws should apply equally to this situation. Use of model experiments to study imbibition has been employed by Graham and Richardson 10 and Mattax and Kyte,11 who actually tested the scaling law applicability. This study is concerned with scaled model imbibition experiments on water-wet carbonate rocks. Of particular interest is the slowly rising water table experiment. This simulates a highly fractured reservoir with the water table rising uniformly through the vertical fracture system. Experiments were performed on different sized samples and with different rates of rise of the water-oil interface surrounding the rock pillar. Total immersion imbibition experiments on smaller rock samples were performed to test the basic linear scaling laws and to see if these simpler tests could be used to synthesize the rising water table experimental results. THEORY IMBIBITION SCALING LAWS Scaling laws for the flow of two incompressible immiscible fluids in a porous medium have been presented by Rapoport.12 These are derived directly from Darcy's Law for the individual phases and the continuity equation. Results from a laboratory model experiment will duplicate those from some reservoir prototype if a constant proportion is maintained among the three forces acting on the fluids — the capillary pressure gradient, the gravitational gradient and the flowing pressure gradient. Operation of the model (i.e., fluid injection or withdrawal) must be conducted in accordance with specific equations. If the

Jan 1, 1967

By G. B. Kasik, George Sachs, George Espey

IT has been reported frequently that the hardness and strength vary over the cross section of cold-worked, particularly cold-drawn, material. Brass rod and wire usually has been found to possess a maximum strength and hardness near the surface.1,2 According to Sachs,1 the center fiber has about the same strength as a wire stretched by the same amount in a tensile-test machine, the strength increasing toward the surface (Fig. I). These differences are particularly large for wire given a small reduction on drawing through a die with a wide opening. However, with increasing reduction and hardness, a tendency to form a thin soft surface skin becomes apparent. On the contrary, copper wire has usually been found to possess a soft surface skin" and it has been reported by Harris3 that during the cold-drawing of hot-rolled wire the surface layer becomes increasingly softer than the core, while the layer of maximum strength moves toward the core, it being found near the surface at first. The increase of strength and hardness from the core to the skin is readily explained by the observation that, in addition to the stretching, the layers of a rod or wire are sheared more the closer they are to the surface.1,6-8 However, the presence of a soft surface layer can be attributed only to an annealing effect. The source of such a softening might be the extremely high temperature that originates from the friction between [ ]

Jan 1, 1941

By M. H. Waxman, L. J. M. Smits

A simple physical model was used to develop an equation that relates the electrical conductivity of a water-saturatedshaly sand to the water conductivity and the cation-exchange capacity per unit pore volume of the rock. This equation fits both the experimental data of Hill and Milburn and data obtained recently on selected shaly sands with a wide range of cation-exchange capacities. This model was extended to cases where both oil and water are present in the shaly sand. This results in an additional expression, relating the resistivity ratio to water saturation, water conductivity and cation-exchange capacity per unit pore volume. The effect of shale content on the resistivity index - water saturation function is demonstrated by several numerical examples. INTRODUCTION A principal aim of well logging is to provide quantitative information concerning porosity and oil saturation of the permeable formations penetrated by the borehole. For clean sands, the relationships between measured physical quantities and porosity or saturation are well known. However, the presence of clay minerals greatly complicates log interpretation, particularly the electrical resistivity and SP logs, and considerably affects evaluation of hydrocarbon-bearing formations. The conductance and electrochemical behavior of shaly sands and their relation to log interpretation have been studied by many workers. wylliel and Lunch2 reviewed this work in some detail. Virtually all laboratory measurements of electrical resistivity and electrochemical potential of shaly sands published to date are the work of Hill and Milburn.3 Their measurements were made on about 300 cores covering a large variety of sedimentary rocks, and a wide range of equilibrating NaCl solution concentrations. Hill and Milburn described their conductivity data by an empirical equation in which the shaly sand conductivity Co was expressed as a function of the solution conductivity C and two parameters b and F01 . The quantity b was shown to be a measure of the effective clay content of the rock, being approximately proportional to the cation-exchange capacity of the rock divided by its pore volume. The latter ratio is designated as 9, in this paper and has the dimensions meq/ml or equiv/liter. Qv is identical with the term representing the concentration of fixed charges in the Meyer-Sieved and Teorel15 theory of permselective membrane behavior. F01 is a formation resistivity factor referred to a hypothetical equilibrating solution resistivity of 0.01 ohm m at 25C,* where clay effects presumably are minimized. F01 was correlated to porosity by an Archie-type equation.6 The Hill-Milburn equation describes their data with a standard deviation of approximately 1 percent and a maximum deviation of + 10 percent. Shaly sands behave as permselective cation-exchange membranes, their electrochemical efficiencies increasing with increasing clay content. The electrochemical potential data of Hill and Milburn were expressed graphically, and demonstrate that the membrane efficiency (or cation transport number) of these sands is a function only of the b value (i.e., Qv) and the respective salt concentrations of the two solutions forming the liquid junction in the sand. The diffusion potentials are not dependent on F01 or any parameter relating to the porosity or pore geometry of the rock. The Hill-Milburn resistivity equation correctly predicts a decreasing sand conductivity Co with decreasing solution conductivity C?. However, at some low value of C,, the calculated Co-C, function goes through a minimum; with further decrease in C?, the predicted sand conductivity increases sharply. As pointed out by Hill and Milburn, an increasing value of Co with decreasing C, is physically meaningless. Since this occurs below the range of practical values of C,, the usefulness of the empirical equation is not affected when

Jan 1, 1969

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By R. P. E. Hermsdorf

THE electrolytic refining of metals for the removal of undesirable impurities has become a recognized necessity in the nonferrous field. Copper, lead, zinc, nickel, silver and gold have been produced in this manner for years. The United States Metals Refining Co., realizing that considerable quantities of lead and tin could be made available to the trade if a satisfactory method of purification of these metals could be established, decided to investigate the possibilities of electrolytic solder. In cooperation with Dr. Edward F. Kern, of the School of Mines at Columbia University, the company developed a process of electrolytic refining of lead-tin alloys using a tin-lead fluosilicate electrolyte. A pilot plant was installed in November, 1927, and the commercial unit was put in October, 1929. Since that time thousands of tons of electrolytic solder have been produced in this plant and consumed by all branches of industry that use solder.

Jan 1, 1936

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

References are in all cases to the earliest known editions. In the few cases where the first edition has been unavailable for consultation, the particular one studied is indicated. English translations are included when known, but not others. [ ]

Jan 1, 1942

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By H. M. Beatty, T. L. Joseph, Gust Bitsianes

SUCCESSFUL blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blast- furnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO ? 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which C02 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature com- bustion of carbon above the tuyeres. Assuming that 1000 lb. of limestone is used per ton of pig iron, about 435 lb. of C02 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb. would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1942

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington&apos; have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4&apos; and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick&apos;s law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.&apos; By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.&apos; (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick&apos;s law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,&apos; is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By Frank Kneeland

SAFETY FIRST is a popular motto-most mining companies have adopted it. It is probable, however, that in the majority of cases it is only a motto and gets no further than the office stationery or the bulletin board at the mine&apos;s entrance. In but few industries is there employed a greater diversity of machinery and mechanical devices than in coal mining. The list ranges all the way from mechanical stokers to wood-working machinery and undercutters. Many of these devices, particularly those employed in wood working, are extremely dangerous. In 1913, 23 per cent. of all fatalities occurring in coal mining in the U. S. were caused by machinery of some sort or other. Although the forms of accidents occurring with mining machinery are legion, they generally arise from one or more of five causes: (a) Falls from ladders, platforms, etc.; (b) coming in contact with moving machines or parts thereof; (c) electric shocks; (d) failure of some machine part; (e) mismanipulation of valves, levers, switches or other hand-operated controlling devices. The steps which may be taken to prevent accidents from the above causes are almost as numerous as the accidents themselves. There is, and can be, no panacea for all mishaps, nor for any one class of accidents. There is no mathematical or other formula that will bring immunity under any set of conditions. Common sense is the only guide. The remedy for the first-named class of accidents is simple and generally effective-namely, make the staging, ladder, platform, or other support, abundantly strong to carry any possible weight that it may be called upon to bear; provide ample railings on platforms or runways, and non-slipping feet on movable ladders.

Jan 1, 1915

By R. J. Wygal

A method is presented by which homogeneous, isotropic, and reproducible aggregates of particles such as glass beads, sand, ground glass, etc., may be prepared simply and quickly by using a "particle distributor". Several applications of the packing method to the construction of model reservoirs are described. The flow characteristics of these packings me given. Some factors which limit the usefulness of unconsolidated packs for simulating reservoir rock are overcome through artificial cementation of the aggregates. INTRODUCTION Many laboratory studies of porous media are based on experiments using test packs of sand, glass beads and other granular materials. More confidence can be had in the results of such studies if the test packs are known to have uniform properties throughout, to be mechanically stable and to be accurately reproducible. This paper presents a method by which such packs of a variety of shapes and sizes may be constructed using a particle distributor. Some factors which limit the usefulness of unconsolidated packs as a means for simulating reservoir rock are described. A method of overcoming these limitations, which involves artificial cementation of the packs, is presented. DEVELOPMENT Particles packed by the tamping or vibrating techniques are usually either non-uniform or mechanically unstable. An invention by Currie and Gregoryl overcomes these difficulties to some extent. The invention is based on the use of a stream of falling particles impinging on and passing through a distributor matrix of several layers of closely spaced spheres. The particles are well dispersed by numerous collisions with the spheres. They become homogeneously distributed at some distance below the distributor matrix and at that position are collected in the sample container. This apparatus, however, was found to be ineffective when small particles were used since small particles accumulate on the top surfaces of the spheres. An improved distributor matrix was made, first in the form of a stack of five sieves, and then in the more adaptable form of spaced layers of wire screen. Fig. 1 shows a longitudinal view through a five-layered distributor of eight-mesh wire screen. This device gives excellent results.* Fine particles pass through the distributor with very little hold up. The fine structure of the wire matrix with its many deflecting surfaces ensures good particle distribution. There are no dead areas immediately below the screen as were sometimes observed to occur below a matrix of spheres. Using such a device, 20-30 mesh sands were packed to a porosity of 32.1 per cent at rates varying from 0.17 to 6 lb/rnin. The lowest porosity achieved by tamping small increments of similar sands into a container was 33 per cent. Motion pictures at 3,000 frarnes/sec of the surface of a growing pack of 2-3/4 mm glass beads have helped to show the mechanism by which packs of low porosity are obtained. The beads, although packed at the rate of 5 lb/min, were observed to hit the pack surface singly, for the most part, and at well spaced points of impact. Part of their energy is transferred to surface beads which are thereby

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG&apos;s ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid&apos; have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey&apos; presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By E. Gybbon Spilsbury

(Pittsburg meeting, March, 1910.) THE recovery of gold and silver from their ores by means of the cyanide process has been so successful in the last few years that any radical improvement would seem impossible; yet the appliance to which I wish to call attention in this paper is really a radical departure from the methods now in general use. The most modern and approved of these, known as the all-sliming method, depends for its success on the grinding of the. ore so fine that practically 90 per cent. of it will pass through a 200-mesh screen. The slimes thus produced are then agitated and aerated in tanks of various types. The main object of this treatment is to insure such a thorough admixture of the pulp and solution that every particle of the ore is surrounded by a volume of solution sufficient to insure the dissolving of the whole of the gold- and silver-content. In addition, in order to expedite the action of the cyanide, and to oxidize such elements as would, if left in their active state, become cyanicides, air is blown in under pressure. In the Pachuca tank, this air is the active and sole means of agitation. The chief objections to all the methods off agitation used heretofore are the expense of operating and maintaining the mechanical devices for keeping the pulp in suspension, and the length of time required to obtain a fairly complete extraction. of the values. These objections are inherent to any method of agitation effecting a circulation of the pulp and the solution together, by giving the whole mass a circular movement, as in the low-tank system, or a vertical circulation, as in the Pachuca-tank system. In both methods, the particles of ore are kept traveling in the same direction as the solution, and with very little difference of speed; so that, while the whole mass is in

May 1, 1910

By R. W. Raymond

The death of the eldest of the honorary members of the Institute was not unexpected. Ritter von Tunner had never recovered from the effects of a paralytic stroke received in 1892, and when the same enemy struck again in February of this year the blow was plainly mortal. He passed away June 9th, gently and without pain. Thus ends a career of great distinction and fruitfulness, crowned with fame and love. This pioneer of the age of iron and steel had lived so long and wrought so much that the present generation could scarcely recall the whole category of his services. There can be no more appropriate use of the pages of these Transactions than to honor them with a record of such a life and work, for the inspiration of other lives to other labors. Peter Tunner was born May 10, 1809, near Peggau, in Styria.† In the same province, his grandfather, Josef Tunner, had purchased a primitive nail-forge and enlarged it to a ham

Jan 1, 1898