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By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By A. Gene Collins

This report discusses some of the chemistry and geochemistry of cesium and rubidium. Knowledge of the cesium and rubidium content of oilfield waters aids in resolving the origin of waters and petroleum, exploring for petroleum and other valuable minerals, discovering water pollution sources, and augmenting the knowledge of geologic formations. The methods described in this report permit the detection of less than 0.01 mg/l of cesium and/or rubidium in a complex oilfield brine or water. Solvents possessing high-dielectric constants were evaluated for their ability to extract cesium and rubidium tetraphenylboron from oilfield waters and for their flame emission characteristics. Nitroethane was selected and used for the extraction and flame spectrophotometric determinations because it gave the highest sensitivity. Cesium 137 and rubidium 86 were used to determine the extraction efficiencies, which were about 87 percent and 58 percent respectively using a single 10 ml nitroethane extraction from a distilled water matrix. The standard deviation of the determination was 0.0008 mg for cesium and 0.0007 mg for rubidium in the 0.01 mg range.

Jan 1, 1965

By W. S. Landers

This report presents a detailed study of low temperature, entrained-bed carbonization of an Australian coking coal. The coal studied was high-volatile B bituminous from the Foybrook mine, an open-cut operation in the Liddell seam, New South Wales, Australia. Carbonization was conducted in an 8-inch diameter, continuous vertical reactor at several temperatures from 960° to 1,300° F. It was demonstrated that this bituminous coal can be carbonized within this temperature range to produce tar and a nonagglomerated char, without prior oxidation or char recirculation. Carbonization rates from 138 to 287 lb/hr (as-carbonized basis) were investigated. It was found that the carbonization temperature and the air-to-coal ratio must exceed minimum values to insure continuous operation. At the higher air-to-coal ratios employed, all or most of the carbonization heat was provided by internal combustion with air in the reactor. At the lower air-to-coa1 ratios, part of the heat for carbonization was supplied externally. On the moisture-and ash-free basis, the yield of tar plus light oil ranged from about 26 to 44 gallons per ton, and the char yield ranged from approximately 1,160 to 1,370 pounds per ton. The heat in the gas ranged from about 900 to 3,000 Btu/lb of moisture-and ash-free coal. Carbonization product yields correlated well with air-to-coal ratio and carbonization temperatures. The volatile matter in the char was found to be temperature dependent. At 1,300° F carbonization, the volatile matter in the char was 8.7 percent (dry basis), whereas at 9600 F carbonization, the residual volatile matter was about 16 to 18 percent (dry basis).

Jan 1, 1965

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,' namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By Zoltan Hajnal

Magnetic studies have been carried out on 88 surface and 157 underground samples from the Coronation Mine area of northern Saskatchewan. The intensity of the surface samples was compared to trace element determinations from the same locality. A good correlation was found between the titaniferous constituent of the rocks and the intensity of magnetization. From the direction of the remanent magnetism, two virtual geomagnetic poles were determined -latitude 12° 54' North, longitude 158" 17' West; and latitude 23" 42' North, longitude 163° 45' West. The sulphide ore specimens showed anisotropic susceptibility characteristics. A relationship was found between the measured maximum susceptibility values of the ore specimens and the direction of the tectonic forces which are considered to have formed the structure at the Coronation mine. Introduction T HIS paper summarizes the results of a study of the magnetic properties of samples from well-known Precambrian formations. The observed data give information for an interpretation of the magnetic field conditions in Precambrian times. The high magnetic intensity values indicate the importance of the study

Jan 1, 1965

By Jr. Norman

Thermoelectric properties of depleted uranium selenides and tellurides were investigated from room temperature to 700 C. Several depleted uranium monoselenides and monotellurides were doped with selected cationic and anionic materials to determine the effect of impurity additions on the thermoelectric properties. The undoped uranium selenides and tellurides were semimetallic conductors exhibiting low Seebeck coefficients and electrical resistivities. Partial or complete degeneracy was in evidence, indicating a charge carrier energy distribution similar to that in a metal. Doping increased the Seebeck coefficients of the uranium monoselenides and monotellurides; however, the corresponding change in the power factor in the figure of merit was small because of the increase in electrical resistivity.

Jan 1, 1965

By Stephan Stecura

Crystallographic modifications and kinetics of solid-state phase trans-formations were determined for five rare-earth" sesquioxides--La2O3, Nd2O3, Sm2O3, Eu2O3, and Gd2O3. Oxides used for crystal modification studies were prepared by thermal decomposition of the following high-purity salts of the five rare-earth elements--carbonates, chlorides, fluorides, nitrates, oxalates, and sulfates. X-ray diffraction patterns of the cubic and hexagonal oxides were indexed by a graphical method and patterns of the monoclinic oxides by Ito's method. The kinetics of crystallographic transformation were determined by high-temperature X-ray diffractometry. The kinetic data were interpreted using a shrinking sphere model. All of the transformations followed first order kinetics. Activation energies were calculated by application of the Arrhenius equation. These solid-state phase inversions were concluded to occur by a reconstructive transformation mechanism.

Jan 1, 1965

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By I. G. Bowen

The pumping of abrasive and sometimes corrosive slurries is normally carried out at modest heads (say 100 ft) with specially designed centrifugal pumps. When heads become higher than this, two or more pumps are used in series but ultimately the system requires staffed pumps with consequent increase of costs. The only other type of pump suitable for high heads is the Ram pump but this is notoriously subject to wear. The paper describes a novel application of the so-called "lock hopper" principle to continuous pumping of slurries. The pump itself is never in contact with the abrasive slurry nor is it subject to head or capacity limitation. It works by displacing slurry with the clear fluid component of the slurry (in most cases water) through cylindrical vessels fitted with plug valves to control the discharge and filling operations. Two such vessels are used and the scheme is completed with a liquid clarifier which allows the pipe flow to be maintained continuously. The paper describes experience on the prototype unit used to discharge tailings from a coal washery in Scotland. A tentative evaluation is also made of the economics of this pump against conventional equipment.

Jan 1, 1965

By C. O. Hawk

A PART of the Bureau of Mines effort to improve the conversion of coal to liquid fuels, batch autoclave tests were made on the hydrogenation of bituminous coal by a dry method, which featured charging the autoclave with dry ingredients only-coal, catalyst, and hydrogen. This innovation, which omitted the liquid vehicle used in earlier work, limited the products to those made from the coal charged. The effects of the common process variables (catalyst, hydrogen pressure, temperature, and residence time) were studied. Tin catalysts showed the highest activity in the widest variety of forms and were the easiest to disperse; dry mixing in the autoclave during the heating-up period usually sufficed. Ammonium molybdate, on the other hand, was inactive when dry mixed, but it compared favorably with the best catalysts known when applied by impregnating the coal with a solution of a molybdenum compound. As a group, metal naphthenates were the most effective; in fact, molybdenum naphthenate was the most active catalyst the Bureau tests disclosed. One-hundredth of a percent of molybdenum in this form (calculated as the metal in weight-percent of maf coal) induced 90-percent conversion of coal. However, because of their high cost, naphthenates have as yet only technical significance in coal hydrogenation. Long residence time and high reaction temperatures tend to increase the amount of thermal decomposition products formed (light hydrocarbon gases and/or char). High hydrogen pressure favors the production of liquids.

Jan 1, 1965

By K. C. Dean

This report is the first of a series concerned with processes for producing magnesium. These reports will evaluate metallothermic, carbothermic , and electrolytic production methods, and will furnish a cost basis for comparing the processes. Areas deemed most promising for future research will be delineated for each procedure. This report presents briefly the history of the metallothermic process, and describes the operations of the Defense Plant Corp. (DPC) plants that employed the process. A hypothetical plant designed to produce 12,000 tons of magnesium per year, using ferrosilicon as a reductant, is described, and raw materials, energy, and major equipment requirements are estimated. Several process modifications are suggested for future research.

Jan 1, 1965

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By A. T. Harris

Ground quartzite, known in the industry as amorphous silica, is produced from a quartzite deposit near Honey Brook, Pa., by George F. Pettinos, Inc., of Bala-Cynwyd, Pa. The quartzite is mined by the open pit method and processed in a mill at the mine. The operation regularly produces five standard grades of sand and one grade of crushed stone; however, the company accepts special orders and will produce material to meet the customer's specifications. Beneficiation (chiefly crushing and screening) is controlled by laboratory screen tests on samples taken during preparation of the sand. The chief uses of the sand are for foundry operations, furnace lining, concrete aggregate, and Other specialized uses. The quartzite in this deposit is of uniform composition and does not require control by chemical analysis. However, for special purposes, analysis will be furnished.

Jan 1, 1965

By F. W. Jessen, R. W. Durie

The dissolution of salt in the development of salt cavities is controlled by free-convection boundary layer flow along the salt surfaces. It is the purpose of this paper to expand upon results published previously, and primarily to illustrate the influence of surface features on the boundary layer and hence the dissolution process in the development of underground salt cavities. General dissolution equations are presented that apply to a surface inclined to the vertical. A salt surface inclined so as to be overlain by water is dissolved by boundary layer flow, while an inverted surface is dissolved by a combination of boundary layer and cellular flow. Detailed investigation of the boundary layer was limited to laminar free-convection flow. Truly laminar free-convection boundary layer flow may be encountered only in laboratory solution cavities, but the boundary layer will control dissolution even where cavity dimensions are such that free-convection turbulence will occur. The factors found to significantly affect the laminar boundary layer will affect dissolution with a turbulent boundary layer. INTRODUCTION Underground salt cavities have been used extensively for the storage of LPG products, and the use of these cavities is expanding each year. The increasing requirements for such cavities suggest the need for a better understanding of the mechanisms involved, for the purpose of the control of cavity geometry and the most effective use of the injected water. A previous paper outlined a quantitative approach to the determination of salt dissolution rates in the laminar free-convection dissolution of salt. It is the purpose of this paper to expand upon the results previously published and to point out significant factors in the application of these results to the dissolution of field cavities. The dissolution of salt in laboratory scale cavities is controlled by the free-convection boundary layer, which is the region of flow along the salt surface caused by the difference in buoyancy forces resulting from the salt dissolution. The transfer of salt into solution at the salt face causes an increase in salinity, and hence a greater density, in the water at the salt surface. The region of higher density tends to fall through the lighter, less saline water and a flowing boundary layer is the result. The water remains stationary at the contact with the salt surface,l so the resulting velocity profile is such that the influence of gravity is opposed by a viscous shear force at the salt surface. For salt to be transferred into solution from a solid surface to a boundary layer of fluid, it must diffuse through a stationary film of water at the salt contact. According to Fick's first law, the rate of mass transfer by diffusion is the product of the diffusion coefficient and the concentration gradient, with diffusion transfer in the direction of decreasing salinity. Once the salt has passed into the boundary layer, it will be transferred by a combination of molecular diffusion and convection. The convection transfer will in turn affect the rate of dissolution by influencing the gradient of the salt concentration at the surface. In the previous investigation by the authors to determine the basic mechanism of the salt dissolution process, an equation was developed that agreed very well with the experimental rates of free-convection salt dissolution from a smooth vertical surface. The technique was taken from the work of Eckert2 in the analogous heat transfer system and will be referred to as the integral method. The rate of salt transfer from a vertical section of height H was found to be:

Jan 1, 1965

By Tilman M. M.

The effects of substituting cobalt for nickel on the acid corrosion resistance of two types of austenitic stainless steel were determined. Cobalt substitutions to a maximum 2.2 weight-percent were made in types 302 and 309 stainless steels. Total immersion corrosion tests were made in 10 volume-percent hydrochloric acid, and boiling-acid tests were conducted in 65 weight-percent nitric acid and in undiluted glacial acetic acid. For modified type 309 in acetic acid, corrosion rates decreased for additions greater than 0.57 weight-percent cobalt. Corrosion rates increased as cobalt was increased up to about 1 weight percent for modified type 302 in nitric and hydrochloric acids and for modified type 309 in nitric acid, but these rates decreased with a further increase in cobalt content. A gradual increase in corrosion rates with increasing cobalt content was shown for type 302 in acetic acid and for type 309 in hydrochloric acid. Cobalt substitutions in larger amounts (above a ratio of 8 Ni to 1 Co) may increase the corrosion resistance of the austenitic stainless steels.

Jan 1, 1965

By L. B. Pankratz

Heat contents, measured above 298.15° K, and derived entropy increments are presented in tabular and equation form for the two crystalline forms of zinc sulfide (sphalerite and wurtzite) and for four solid solutions of iron and zinc sulfides having the compositions Zno.,,6Fe0.302S, Zno.750Fe0.250S, Zno.650Fe0.3505, and Zno.498Feo.502S.

Jan 1, 1965

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By J. B. Gayle

The Bureau of Mines studied the effects of air oxidation on the recovery of float coal. Both batch-and continuous-type tests were made on six bituminous coals, representing the range in rank of coals now commercially used for carbonization, and on one anthracite coal. The effects on flotation recovery of oxidation at 1000 C for periods up to 50 days were investigated using an alcohol-type frother and a kerosine-pine oil reagent. Two series of release analysis tests were made, using one medium-volatile bituminous coal. Float coal recovery was adversely affected by oxidation in all tests where the alcohol-type frother was used. Conversely, a small degree of oxidation improved recovery with kerosine-pine oil frother for some of the coals in continuous tests. Prolonged oxidation (beyond about 14 days) adversely affected float coal recovery for all coals, the effect being more pronounced for batch-type tests and for tests using alcohol-type frother. Reagent selectivity for the rejection of both ash forming and sulfur bearing minerals was reduced by oxidation. Severe reduction of reagent selectivity required only about 3 days' oxidation for alcohol-type frother but more than 10 days' oxidation when the kerosene-pine oil reagent was used.

Jan 1, 1965