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By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By Robert D. Pehlke, Kazuhisa Okajima

ThE prediction of the activity coefficient for a solute in a multicomponent liquid metallic solution based on measurements in the related binary systems has been the object of study for some time, particularly in iron-base alloys.1,2 Very few measurements, however, have been made on nonferrous systems; furthermore, measurements made for the specific purpose of testing various prediction equations are almost nonexistent. The measurements here described of the activity coefficient of cadmium in liquid lead alloys were directed toward this goal. One of the most direct means by which the activity coefficient can be calculated has been based on the independent influences of each solute. When solute metals i,j, k, and so forth are present, the activity coefficient, y, of one of these (i for example) may be expressed as a product of factors which represent the effects of each of the other components:

Jan 1, 1964

By Luther B. Eames

The recovery of dissolved gold from slime pulp in the cyanide process was first accomplished by intermittent decantation. This simple process consists in mixing with the pulp containing the values in solution, a solution of lower gold content, settling the mixture in a tank and decanting the clear supernatant fluid. The thick pulp remaining in the tank is pumped to a second tank together with more barren-solution and again settled and decanted. After several repetitions of this operation, values are so far reduced that further washing is not profitable. The gold recovery of this process is high, but the plant required is bulky, labor cost is high and the amount of solution to be precipitated is excessive. Historical Data As early as 1901, a plant was built in the Black Hills of South Dakota by John Randall, employing the same principles but attempting to make the process continuous by substituting for flat-bottomed tanks, cones which operated continuously, receiving a constant feed and discharging a steady stream of thickened pulp. These cones were operated in series, the thick underflow of the first one forming, with a stream of diluting solution, the feed to the second cone of the series. Barren solution was added to the tank immediately preceding the discharge tank and, after being slightly enriched by the low-grade pulp in this tank, overflowed to form a diluting solution again for the richer feed entering the third tank from the end of the series, and so on back to the richest tank of the series. Clear water was used for the wash in the final tank. This is the principle on which all successful countercurrent decantation plants operate at the present time, but Randall's plant was not successful because of mechanical difficulties in getting a continuous thick discharge from his cone tanks. A similar plant was built in South Africa although there the washes were not repeatedly used, as in Randall's case, but were precipitated after each contact with the ore. This also was abandoned

Jan 1, 1918

By Luther Eames

THE recovery of dissolved gold from slime pulp in the cyanide process was first accomplished by intermittent decantation. This simple process consists in mixing with the pulp containing the values in solution, a solution of lower gold content, settling the mixture in a tank and decanting the clear supernatant fluid. The thick pulp remaining in the tank is pumped to a second tank together with more barren solution and again settled and decanted. After several repetitions of this operation, values are so far reduced that further washing is not profitable. The gold recovery of this process is high, but the plant required is bulky, labor cost is high and the amount of solution to be precipitated is excessive. HISTORICAL DATA As early as 1901, a plant was built in the Black Hills of South Dakota by John Randall, employing the same principles but attempting to make the process continuous by substituting for flat-bottomed tanks, cones which operated continuously, receiving a constant feed and discharging a steady stream of thickened pulp. These cones were operated in series, the thick underflow of the first one forming, with a stream of diluting solution, the feed to the second cone of the series. Barren solution was added to the tank immediately preceding the discharge tank and, after being slightly enriched by the low-grade pulp in this tank, overflowed to form a diluting solution again for the richer feed entering the third tank from the end of the series, and so on back to the richest tank of the series. Clear water was used for the wash in the final tank: This is the principle on which all successful countercurrent decantation plants operate at the present time, but Randall's plant was not successful because of mechanical difficulties in getting a continuous thick discharge from his cone tanks. A similar plant was built in South Africa although there the washes were not repeatedly used, as in Randall's case, but were precipitated after each contact with the ore. This also was abandoned

Jan 12, 1916

By T. Szaplonczay, D. E. Light

The auto-oxidation of sulfur dioxide to form sulfuric acid in commercially produced barren and recycle liquors, containing 1.66 and 4.56 gpl Fe respectively, from Elliot Lake was studied. A gas mixture, containing 3.5% SO2 and air was introduced into these liquors through a frit at a rate of 6.0g SO2 per hour per liter of solution. The barren and recycle were heated to 60°C. At the end of the first 24 hours of the process the concentrations of acid produced were 158 and 220 gpl H2SO4 for the barren and recycle respectively. Corresponding conversion efficiencies were 70 and 83%. In the period from 24 to 36 hours the rate of acid production decreased so that the H2SO4 concentrations at the end of 36 hours were 180 gpl for the barren and 260 gpl for the recycle; average conversions for the initial 36 hours were 55 and 68% respectively. Many investigators1'2'3 have considered the oxidation of sulfur dioxide to form sulfuric acid in aqueous solutions containing metallic ions. A summary of the work performed on this subject prior to 1946 has been presented by Keyes4 who described the auto-oxidation process as follows. Keyes also suggested that in this second reaction ferric ion serves as a catalyst for the conversion of sulfur dioxide to sulfuric acid. Neytzell-de Wilde and Taverner5 have reported on the use of auto-oxidation to produce a 4 to 5% sulfuric acid solution for use in a cyclic leach process at South African uranium plants. This paper describes investigations carried out to determine the feasibility of using the auto-oxidation process to produce sulfuric acid solutions of as high concentration as possible using commercially produced uranium plant barren and recycle liquors from the Elliot Lake region of Ontario. These liquors contained 1.66 and 4.56 gpl respectively of iron, chiefly in the ferrous state. This investigation is of particular interest to the uranium producers in Elliot Lake where the ores contain 3 to 4% sulfur, as sulfides. Flotation of these sulfides and roasting of same to produce SO, bearing gases have been successfully demonstrated using conventional methods.6'7 Barren and recycle solutions, as described previously, are also produced in large tonnages by these uranium producers. The experimental method and apparatus used to examine the auto-oxidation process will be described first. Then the tests carried out on laboratory prepared aqueous solutions containing ferric sulfate to determine optimum conditions will be presented. The next section will describe the tests using the commercial barren and recycle liquors. A final section will summarize the conclusions of the work. EXPERIMENTAL APPARATUS AND PROCEDURES Two types of solutions were used in the tests, a laboratory prepared aqueous solution containing definite amounts of ferric sulfate, and commercially produced iron bearing solution obtained from a uranium leaching plant in the Elliot Lake area. Two liters of a solution to be examined were placed in a 3 in. diam by 30 in. long glass cylinder with a cross-sectional area of 7 sq in. A mixture of air, and SO2 supplied from a lecture bottle for convenience, was introduced into the bottom of the vessel through a standard 30 mm glass frit, 700 sq mm in area. The temperature of the apparatus was controlled by a heating tape and variable transformer. Exhaust gases were vented to atmosphere. At the end of the test period the gas flow was shut off and the solution was analysed for H2SO4, Fe ++, and Fe +++, by conventional means. Four variables were examined using the laboratory prepared aqueous solution of ferric sulfate. First, the effect of SO2 concentration, from 1 to 1076, in the feed gas mixture was considered. Second, the temper-

Jan 1, 1964

By J. E. House, J. L. Drobnick, R. R. Swanson, D. W. Agers

The paper describes an improved process for the recovery, purification, and concentration of copper values from acidic dump leach liquors. The process employs a new liquid ion exchange material (LIX® 64 reagent) capable of separating copper values from iron and other impurities common to dump leach liquors in the typical pH range of 1.4-3.0. Properties and performance of the reagent are discussed. Design scale-up information for both pilot plants and commercial installations, including preliminary economics, are presented. Economic considerations include the production of electrolytic copper from the purified copper aqueous concentrate. INTRODUCTION Since the commercial acceptance of the liquid ion exchange process in the mineral processing industry, it has been predicted that a wide selection of chemical reagents to efficiently and economically separate many metals in solution under a wide range of conditions would be commercially available. Several years ago, General Mills began a basic research and development program to determine if it were possible to develop a reagent to extract economically metallic ion from existing process streams. Progress toward reaching this objective was reported in late 1963, when development of quantities of LIX -63 reagent, a highly selective reagent for the extraction of copper, was introduced. The properties of this reagent are described in a previous paper.' The development work with this reagent indicated that perhaps the largest potential application for a copper extractant, the treatment of acidic dump leach liquors, would not be economically possible with LIX-63 because of limitations of the reagent to extract copper below a pH of 3.0. The relatively small pH adjustment required with LIX-63 would result in a significant processing cost and the undesirable precipitation of ferric hydroxide from the liquor. This pointed to the need for another copper extractant which would extract copper from dump leach liquors without pH adjustment. General Mills was successful in synthesizing a molecule which does not have the pH limitation of the LIX-63, yet possesses the selectivity-solubility properties required of a metallic extractant. The resulting LIX-64 reagent broadens the pH range from which copper can be effectively extracted and separated from other metallic impurities. Of special significance is the fact that the reagent, LIX-64 was developed by combining the technical requirements of a specific problem in hydro-metallurgy with theoretical organic and physical chemical principles.

Jan 1, 1967

By Harry Huntington Miller

In spite of its recognized irregularities, the cyanide-assay for copper has always been popular among volumetric methods, being easy and rapid, and reasonably accurate when the solution tested contains nothing but pure copper and ammonium salts. In order to secure this condition, however, especially in operati~ig on low-grade ores, tailings and slags of complex composition, it is the practice to precipitate the copper from the ore-solution,—usually by means of metallic zinc or aluminum. The copper thus precipitated in the metallic form must be dissolved again; and the separa tion is never, in practice, complete, since an appreciable amount of the copper remains behind in the first solution, and the second solution always contains some of the other metals of the gangue; so that the result is at best but partially satisfactory. On the other hand, if this course is not pursued, but (as is

Jan 1, 1902

By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By Fred Beasley

METALLURGISTS have, in the past ten years, overcome many difficulties of high zinc in lead blast-furnace slags. This problem was brought to the front at the close of the late war, by the price obtained for lead and the high cost of labor, fuel, and flux. The Port Pirie plant of the Broken Hill Associated Smelters, Australia, early in 1919 had increased the zinc oxide in its blast-furnace slags from 13.5 to 20 per cent., at the same time reducing the iron oxide in the slag from 33.5 to 25.6 per cent. These results were obtained by the following proceduret the addition of granulated slag to the roaster charge, 10 to 12 per cent., improved conditions of the crushing and mixing and roasting of the constituents of the sinter. By experiments and improve-ments the practice at this plant has developed a normal slag that carries 22 per cent. zinc oxide, and at times runs as high as 33 per cent. zinc oxide, with only slight furnace trouble. The granulated slag is used not, only as a diluent to the sulfur in the roaster charge, but also on account of its value as a slag-forming material and on account of the physical properties it imparts to the finished sinter. The ore is mixed with flux and given a double roast. All the first roasting is by sintering with the Dwight & Lloyd machines. The final roasting is performed partly by Dwight & Lloyd machines and partly by H. & H. pots. The charge to the blast furnaces consists chiefly of the final sinter, slag shells, siliceous and non-bearing sulfur, lead ores. High blast and ore columns are the practice. The greatest care is taken to obtain in the final sinter as low a sulfur content as possible.

Jan 2, 1925

By L. B. Ticknor, M. B. Bever

An isothermal calorimeter suitable for measurements of heats of solution in liquid tin as solvent is described. Measurements of the heats of solution of gold, silver, copper, and a gold-silver alloy are reported. The heat of formation of this gold-silver alloy is also reported. HEATS of solution in liquids can be determined directly, but few such data have been published for metals as solvents. Knowledge of heats of solution is desirable because it contributes to the general understanding of energy relations in metallic solutions. Thermochemical measurements of this type also furnish answers to specific problems: For example, from the heats of solution of an alloy and of a mixture of its constituent elements in a given solvent, the heat of formation of the alloy may be found. Similarly, differences in the energy content of samples of the same metal in two different states, such as the annealed and cold worked states, may be determined. In the work reported here, gold, silver, and an alloy of gold and silver were dissolved in liquid tin at 240°C and gold, silver, and copper were dissolved in tin at 300 °C. The experiments yielded the heats of solution of these metals in tin. The heat of formation of the gold-silver alloy was also determined. The same calorimetric method is being used to measure the energy stored in metals during cold working and preliminary results have been published.' Equipment and Experimental Procedure The isothermal calorimeter used in this work, Fig. 1, consisted of a Dewar flask completely immersed in a constant-temperature salt bath. A long neck provided space for thermocouple leads and a stirrer shaft and permitted the injection of solute samples. The metal bath in the calorimeter flask was stirred at about 100 rpm by a small glass impeller driven by a constant-speed motor. The shaft of the stirrer passed through a Wilson vacuum seal.2 All measurements were made under vacuum in order to eliminate temperature disturbances resulting from gas convection and to prevent the oxidation of tin. The calorimeter flask was joined by an all-glass connecting line to a gas-control system which made possible the use of a protective atmosphere of deoxidized and dried hydrogen. At the operating temperature of the calorimeter tin oxide was not reduced by hydrogen, presumably because the reaction rate was too slow. Part of the closed system was a removable side tube through which the solute sample could be introduced and in which it was held at a temperature of 0°C prior to injection into the metal bath. The salt bath containing a mixture of sodium, lithium, and potassium nitrates was similar to that described by Beattie3 and was equipped with a stir-

Jan 1, 1953

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,' it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.' A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970

By Thomas M. Drown

The use of bromine as an oxidizing agent, particularly for sul phur, has become very general in analysis, replacing the stronger oxidizing acids. The object of this paper is to describe briefly the experience which we have gained with this reagent in the laboratory of Lafayette College in the oxidation of metallic sulphides. Most of the simple sulphides, as blende, pyrite, etc., when exposed to the combined action of an alkaline hydrate and bromine, and finally to hydrochloric acid, are completely and promptly dissolved. The procedure is as follows: The very finely pulverized mineral is first treated, in a beaker, with a solution of sodium hydrate of a spe cific gravity of 1.25, and heated ; bromine is then cautiously added to supersaturation, and finally hydrochloric acid to acid reaction. If any of the sulphide is not taken up, the same operation may be re peated. It is necessary, however, that the mineral be very finely pulverized. Instead of using the pure bromine, a saturated solu tion of bromine in potassium bromide may be used with equally good effect. The process is advantageously simplified by making a saturated solution of bromine in the concentrated alkali. This is done by pouring bromine into a solution of sodium hydrate, of the above given specific gravity, until no more is taken up, and then adding a little of the sodium hydrate solution until the liquid does not give off free bromine. The procedure with this solution is as follows: The pulverized mineral is moistened with, say, 10 cc. of the solution, and heated, then hydrochloric acid added to just acid reaction. Two more additions of the alkaline solution, in amounts of 20 cc. each, are added at intervals of about ten minutes, each addition being followed by hydrochloric acid. The total amount of the alkaline solution (containing the bromine) used is, therefore, 50 cc., and the amount of hydrochloric acid should not exceed that necessary to make the solu tion acid after each addition of the alkali. The mixture should be kept hot. After the final addition of acid, the contents of the beaker is taken to dryness and heated in an air-bath to 110° to 115°C., to render silica insoluble. The dry mass is then taken up by hydro' chloric acid and water and, after filtration, the sulphuric acid is pre

Jan 1, 1880

By F. M. Doyle-Garner, A. J. Monhemius

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are hydrolyzed by water, typically at 130°C to 200°C (265°F to 392°F). Equilibrium hydrolytic stripping tests were done on Versatic 10 solutions containing various metals, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated [a]Fe2O3 Ni(OH)2 Cu2O + CuO, Mg(OH)2 and [?]Mn203 respectively, during hydrolytic stripping. Several mixtures containing iron precipitated magnetic spinel ferrites, MFe204. No other combinations formed mixed oxides. It is proposed that the mechanisms for hydrolysis and precipitation of iron in loaded Versatic solutions are similar to those for iron hydrolysis in aqueous solutions. Magnetic interactions between mixed carboxylate complexes are thought to be responsible for the homogenous nucleation of magnetic mixed oxides in preference to single oxides.

Jan 1, 1986

By T. Kilner, A. Plumtree

DURING an investigation of electro-deposited silver structures, samples were prepared for metallographic examination by cold mounting in plastic, grinding on successive grades of emery paper down to 3/0, and chemically polishing by swabbing using the chromic acid solution described by Gilpin and Worzala.1 Attempts to etch these samples using the standard solutions described for silver (e.g., 5 pet KCN-5 pet Na2S2O8, H2O2-NH4OH, and various potassium dichro-mate solutions) all failed to give good results due to staining of the samples and to rapid etching. The staining was caused by the chromic acid polishing solution being trapped in small fissures between the sample and the mounting plastic, and also in small fissures in the sample itself. To overcome these difficulties, an etchant was developed which prevented staining at the same time as it slowly etched the sample. This resulted in a very clean, crisply etched surface as shown in Figs. 1 and 2. This etch consisted of 10 ml of orthophosphoric acid, 10 ml of distilled water, and 2 drops of the polishing solution noted above,' which is made by mixing 100 ml of saturated CrO3 solution, 45 ml of 10 pet HC1 solution, and 800 ml of distilled water. The etching procedure involved taking the final polished sample, either immersing or swabbing in the etchant for a period of 1 to 2 min, rinsing as quickly as possible in distilled water, alcohol, and ethyl ether in that order, and then immediately drying. This etch is easily controlled due to its slow rate of etching, and produces samples with clean, sharp surfaces. Pits due to overetching produced varying contrast effects when viewed under polarized light, and are therefore obviously useful for revealing many structural details within the sample. Another effect of overetching was to produce a height varia-

Jan 1, 1968

By B. K. Larkin

Solutions to the diffusion equation for a line source located anywhere in a region bounded by a circular discontinuity are presented. Such solutions follow automatically from the Green&apos;s function presented by Jaeger.4 Petroleum industry applications of this problem would include transient compressible fluid flow in porous media bounded by a discontinuity. Since several recent papers have treated the subject in less general form, it would appear that many workers in this area of the petroleum industry are not aware of Jaeger&apos;s work. STATEMENT OF THE PROBLEM In several trearments1,2,3 of the transient flow of compressible fluids in porous media it was convenient to consider a region to be bounded by a circular discontinuity. In such a region (Fig. I), the properties in Region 1, r < a, are constant but different from the properties in Region 2, r > a. Hurst, l using the Laplace transform, obtained solutions for a line source located in the center of such a porous medium. The purpose of this work is to point out that a much earlier paper by Jaeger4 presents the solution for a line source located anywhere inside the discontinuity. The assumption is made that a line source may be used to approximate a well. In the following material it is convenient to use the terms source and well as being equivalent; however, the reader should remember the distinction in applications. SOLUTIONS Jaeger presented the Green&apos;s function for a line source, or well, in the composite region shown in Fig. 1. In the most general form, the solution for a system of j wells in Region 1, each producing at a time varying rate, qi (t), is

By B. N. Thompson

Main industrial minerals produced in New Zealand are nonmetallic - clay, dolomite, limestone, pumice, salt, serpentine, and silica sand. Other minerals, some with minor production, include diatomite, feldspar, magnesite, sulfur, asbestos, and perlite. Energy and metallic minerals and aggregate are excluded from this account. These industrial minerals occur in a wide range of rock types and geological ages. For example, clays are known from the weathering products of Cretaceous rhyolite and leaching of Eocene coal measures; from Quaternary weathering of contemporary loess and shallow marine sediments, and of greywacke of Triassic-Jurassic age; and from the hydrothermal alteration of late Cenozoic acidic volcanic rocks.

Jan 1, 1984

By L. F. Wright

Operations of these two mining companies have some superficial similarities-geographical location, production rates, comparatively large ore reserves; but any critical comparison of mining and milling procedures or of economics must take into account the striking differences in geological environment and mineralogy of the respective ore deposits. The properties are only about 20 miles apart on an upland surface of moderate relief (part of the Interior Plateau of central B. C.) which occupies an area east of Thompson River between the towns of Ashcroft and Merritt. Being in the "dry belt" of British Columbia, water conservation is necessary at both operations.

Jan 12, 1963

By W. J. Sharwood

IN the cyanide process, gold and silver are dissolved from crushed ore as double alkali-metal cyanides, from which they may he precipitated by such positive metals as sodium (amalgam), aluminum, or zinc, or by electrolysis. Two extreme conditions may he noted. Some works, especially slime plants practising decantation, use a relatively large volume of solution-possibly 4 or 5 tons per ton of ore-nearly all of which may require precipitation, so that the solutions handled are of much lower value per ton than the ore. On the other hand, in some leaching plants it is possible to extract with very little solution, and to percolate some of this more than once through the charge before precipitation, so that the solution to be precipitated may he much less than half the weight of ore, and proportionally richer. Solution intended for further use need not have all its precious metal removed, but any that has to be thrown away should be impoverished as far as is economically possible. In spite of certain advantages possessed by other precipitants, zinc in some form has been almost universally used. In some of the first attempts to utilize cyanides as gold solvents, a "piece or plate of zinc" was suggested as a precipitant, but extension of surface was early recognized as a desideratum. Macarthur and the Forrests adopted a "metallurgical filter" of zinc shaving, turned from disks or rolled sheets. They had previously experimented on other forms of zinc, and Macarthur records having tried zinc dust, which had of course been long known as a general reducing agent. It had also been known and used as a precipitant of precious metal from plating and photographic solutions, and comminuted zinc had been patented for recovering copper, etc., from ore leaches. Other inventors proposed the virtual making of zinc powder by the attrition of balls of zinc, and by similar means, during the passage of a stream of gold-bearing solution.

Jan 9, 1917

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting Cu, Ni, Co, and S from high grade Ni concentrate produced from Lynn Lake ores and describes in some detail the chemistry of the process. In the leaching stage air, ammonia, and sulphide minerals react in a sequence of inter-related steps to produce soluble amines of Ni, Cu, and Co in a solution containing sulphate, thiosulphate, polythionate, and sulphamate ions and a controlled amount of free ammonia, the iron and other components of the concentrate remaining as an insoluble residue which is separated from the leach solution by filtration. The pregnant solution produced in leaching is further treated by boiling to precipitate and remove Cu as cuprous sulphide, leaving a copper-free solution with a composition suitable for subsequent precipitation of Ni and Cu by H,

Jan 3, 1955

By S. E. Clay, G. P. Martins, P. R. Taylor

A grain model for gas-solid reactions in cylindrical pellets is formulated and solved numerically. The numerical solution demonstrates when it is safe to assume either a thin disk or a long cylinder geometry, and when the more general two dimensional geometry must be used. The numerical solution also demonstrates the solution of a two-dimensional moving boundary problem (i.e., when the reaction is diffusion controlled and the ratio of the height to diameter dictates two dimensions).

Jan 1, 1986