Search Documents

By Akira Yazawa, Alžbeta Gubcova

RECENT lead-smelting techniques have tended toward use of high-grade concentrates with minimum amounts of flu, accompanied by profitable employment of roast reaction.1-5 In order to better understand these smelting processes, thermodynamical calculations have been carried out on the Pb-S-0 system, and the results obtained have been presented in isothermal reaction diagrams in which log Ps, and logPo, were the axes. The diagram thus constructed seems to be more convenient to grasp the equilibrium aspect than those published hitherto.6-8

Jan 1, 1968

Jan 1, 1917

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By R. H. Cox, A. S. Allen, James Paone

The southwestern Illinois communities of Belleville and Maryville lie within the greater metropolitan area surrounding St. Louis, Missouri. They also lie within that part of the Illinois coal basin where the Number 6 coalbed has been mined for more than a century. About half the coal was left as pillars to support the ground surface. Years later, however, damaging movements are affecting buildings, streets, and public utilities in some areas. They are generally believed to be related to abandoned mine workings. The threat of continued or increasing incidence of damage raises the need to explore other subsidence-control measures for protecting affected areas with high population density.

Jan 2, 1978

By R. S. Hadi, L. Svarovsky

SUMMARY This is a report of a new development in on-line particle size measurement of fine powders in dust-laden gases. A continuous sample of the solids-air suspension is drawn from the process stream via a sampling probe by means of an air operated ejector into a cyclonic separator whereby the sample is subjected to a particle size dependent separation process and split into two streams, "overflow" and "underflow". The overflow stream carries most of the fines at a relatively low concentration and the underflow stream carries the coarse particles at a relatively higher concentration. The concentration of solids in the two streams is detected by electrostatic noise level technique which utilises the electrostatic charge accumulated on the solid particles due to their high velocity in the turbulent air stream, for the mass concentration measurement. The ratio of the solids concentration of the fines stream to that of the coarse stream is then correlated against the average particle size in the main process stream by a calibration curve. The in-plant tests clearly indicate that this relatively simple instrument offers good sensitivity in the size range from 2 to 6 µm, and is capable of giving a continuous indication of average particle size for process control purposes. Although the instrument was developed for a particular application, it may be used in other situations where fine powders are conveyed in gas streams. British and foreign patents are applied for.

Jan 1, 1980

By T. K. Prentice

ABSTRACTED AND REVIEWED BY E. W. DAVIS,* MEMBER A.I.M.E. THE January-February number of the Journal of the Chemical Metallurgical and Mining Society of South Africa is made up entirely of a discussion of Ball Wear in Cylindrical Mills. Following the principal paper by T. K. Prentice are several remarkably pertinent and carefully prepared discussions. Few persons in this country would be likely to see this publication, and since the information presented is new and of current interest, it seems desirable to abstract and review this publication for the benefit of the members of the A.I.M.E. The purpose of the investigation is stated in the first two paragraphs of Prentice's paper, as follows: Early in 1941, The Chamber of Mines Steel Products, Limited, initiated a series of tests under semi-working scale conditions to determine, if possible, those physical and chemical properties of a ball which make it resistant to wear when used in a cylindrical mill as a grinding medium, with the primary object of incorporating those beneficial qualities in the balls being produced at their works. This paper describes the tests carried out and discusses the results obtained. From these results it was possible to formulate a new theory relating to ball wear in cylindrical mills. This theory is presented in the second portion of this paper. PRACTICAL BALL-MILL TESTS IN A CYLINDRICAL MILL Part I of the paper begins with a discussion of the methods used for the manufacture of grinding balls in South Africa. The following paragraph is of particular interest. The cast steel ingots, 4 ¼ - in. square by 3 ft. 6 in. long, are re-heated in a gas-fired sloping stationary-hearth furnace and then rolled in a six-pass continuous mill into 2 5/8 in. round billets. Some of these billets are then removed and cut into suitable lengths for forging into 4 in., 3 ½ in., 3 in. or 2 ½ in. balls by means of three Drop and two Beché hammers, but the greater number, whilst still at about 1,000 ºC., pass directly into a set of scroll rolls which produce, in an ingenious manner, finished 3 in. balls direct from the 2 5/8 in. billets. Except in special cases, all balls are allowed to cool in the atmosphere and are not water quenched. Details of the Tests In order to enable the reader to evaluate properly the results and conclusions in the rest of the paper and in the discussions following the paper, most of the information presented by the author under this heading is quoted: ….. The testing unit was a nominal 30 in. diameter and 18 in. long centre discharge Denver Ball Mill. The ore pulp to the ball mill comprised a small portion of the normal feed to one of the fourteen City Deep 5 ft. 6 in. X 22 ft. tube mills, and the grinding media consisted of the balls under test plus other balls to give the desired load. The running time of the test-mill was divided into approximately equal periods of five days 13 ½ hours each. The usual procedure was to examine and make up the load

Jan 1, 1944

By T. K. Prentice

The January-February number of the Journal of the Chemical Metallurgical and Mining Society of South Africa, 1943, is made up entirely of a discussion of Ball Wear in Cylindrical Mills. Following the principal paper by T. K. Prentice are several remarkably pertinent and carefully prepared discussions. Few persons in this country would be likely to see this publication, and since the information presented is new and of current interest, it seems desirable to abstract and review this publication for the benefit of the members of the A.I.M.E. The purpose of the investigation is stated in the first two paragraphs of Prentice's paper, as follows: Early in 1941, The Chamber of Mines Steel Products, Limited, initiated a series of tests under semi-working scale conditions to determine, if possible, those physical and chemical properties of a ball which make it resistant to wear when used in a cylindrical mill as a grinding medium, with the primary object of incorporating those beneficial qualities in the balls being produced at their works. This paper describes the tests carried out and discusses the results obtained. From these results it was possible to formulate a new theory relating to ball wear in cylindrical mills. This theory is presented in the second portion of this paper. Practical Ball-mill Tests in a Cylindrical Mill Part I of the paper begins with a discussion of the methods used for the manu- facture of grinding balls in South Africa. The following paragraph is of particular interest. The cast steel ingots, 4¼ in. square by 3 ft. 6 in. long, are re-heated in a gas-fired sloping stationary-hearth furnace and then rolled in a six-pass continuous mill into 25/8 in. round billets. Some of these billets are then removed and cut into suitable lengths for forging into 4 in., 3¼ in. , 3 in. or 2½ in. balls by means of three Drop and two Beche hammers, but the greater number, whilst still at about 1,000, pass directly into a set of scroll rolls which produce, in an ingenious manner, finished 3 in. balls direct from the 25/8 in. billets. Except in special cases, all balls are allowed to cool in the atmosphere and are not water quenched. Details of the Tests In order to enable the reader to evaluate properly the results and conclusions in the rest of the paper and in the discussions following the paper, most of the information presented by the author under this heading is quoted: The testing unit was a nominal 30 in. diameter and 18 in. long centre discharge Denver Ball Mill. The ore pulp to the ball mill comprised a small portion of the normal feed to one of the fourteen City Deep 5 ft. 6 in. X 22 ft. tube mills, and the grinding media consisted of the balls under test plus other balls to give the desired load. The running time of the test-mill was divided into approximately equal periods of five days 13½ hours each. The usual procedure was to examine and make up the load

Jan 1, 1947

By T. K. Prentice

The January-February number of the Journal of the Chemical Metallurgical and Mining Society of South Africa, 1943, is made up entirely of a discussion of Ball Wear in Cylindrical Mills. Following the principal paper by T. K. Prentice are several remarkably pertinent and carefully prepared discussions. Few persons in this country would be likely to see this publication, and since the information presented is new and of current interest, it seems desirable to abstract and review this publication for the benefit of the members of the A.I.M.E. The purpose of the investigation is stated in the first two paragraphs of Prentice's paper, as follows: Early in 1941, The Chamber of Mines Steel Products, Limited, initiated a series of tests under semi-working scale conditions to determine, if possible, those physical and chemical properties of a ball which make it resistant to wear when used in a cylindrical mill as a grinding medium, with the primary object of incorporating those beneficial qualities in the balls being produced at their works. This paper describes the tests carried out and discusses the results obtained. From these results it was possible to formulate a new theory relating to ball wear in cylindrical mills. This theory is presented in the second portion of this paper. Practical Ball-mill Tests in a Cylindrical Mill Part I of the paper begins with a discussion of the methods used for the manu- facture of grinding balls in South Africa. The following paragraph is of particular interest. The cast steel ingots, 4¼ in. square by 3 ft. 6 in. long, are re-heated in a gas-fired sloping stationary-hearth furnace and then rolled in a six-pass continuous mill into 25/8 in. round billets. Some of these billets are then removed and cut into suitable lengths for forging into 4 in., 3¼ in. , 3 in. or 2½ in. balls by means of three Drop and two Beche hammers, but the greater number, whilst still at about 1,000, pass directly into a set of scroll rolls which produce, in an ingenious manner, finished 3 in. balls direct from the 25/8 in. billets. Except in special cases, all balls are allowed to cool in the atmosphere and are not water quenched. Details of the Tests In order to enable the reader to evaluate properly the results and conclusions in the rest of the paper and in the discussions following the paper, most of the information presented by the author under this heading is quoted: The testing unit was a nominal 30 in. diameter and 18 in. long centre discharge Denver Ball Mill. The ore pulp to the ball mill comprised a small portion of the normal feed to one of the fourteen City Deep 5 ft. 6 in. X 22 ft. tube mills, and the grinding media consisted of the balls under test plus other balls to give the desired load. The running time of the test-mill was divided into approximately equal periods of five days 13½ hours each. The usual procedure was to examine and make up the load

Jan 1, 1947

By A. P. Herring, S. F. Ravitz

Manganese dioxide reacts with sulfur dioxide solution in the absence of oxygen to form manganous ion and dithionate ion, together with a small amount of sulfate ion. The effects of SO, concentration, hydrogen ion concentration, stirring speed, and temperature on the rate of the reaction were studied. If it is assumed that undissociated SO2 molecules react rapidly with MnO, at active surface sites and that bisulfite ions react slowly, an equation can be derived that satisfactorily represents the observed reaction rates. For solutions in which the reaction with undissociated SO2 predominates, reaction rates and activation energies estimated from diffusion theory agree well with those found experimentally. Manganese dioxide dissolves readily in aqueous solutions of sulfur dioxide. The nature of the dissolution reaction was first investigated by Gay-Lussac and welter1 in 1819; they identified a new oxysulfur radical, the dithionate ion, S2O6, as one of the reaction products. Since then, the reaction has become a standard method of preparing dithionates in the laboratory and one of the more promising methods of leaching manganese from low-grade ores. In the "dithionate process" developed by the U.S. Bureau of Mines2,3, manganese-dioxide ore is suspended in a solution of calcium dithionate and leached with gas containing sulfur dioxide. The manganese is dissolved and the sulfur dioxide is oxidized according to the reactions:

Jan 1, 1965

By Robert Glass Cleland

[Incorporated under the laws of the State of New York OFFICE, 41) WALL STREET, NEW YORK 5, N. Y. Authorized4,000,000 shares $150,000,000.00 Outstanding-5,071,260 shares 126,781,500.00]

Jan 1, 1952

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By J. C. Sullivan, W. A. Knoll

The sinking of a new shaft at the Newport mine, Ironwood, Mich., was started in May 1931 and completed on Aug. 3, 1932. During this period, 2665 ft. of shaft in granite was completed, at an average advance of 6 ft. per 24 hr. In Novernber of 1930, experimental work was conducted on 65 ft. of shaft through 22 ft. of overburden where ledge was encountered, and this work convinced the operators that all drilling could be done with vertical holes with the blasting relief to a 4½-in. hole drilled vertically in the center of the cut. The reason for not adopting the conventional V-cut was to get away from damaging the shaft steel. The blasting in a V-cut naturally tends to throw the broken material upward, but with the cut as adopted the relief was in a horizontal direction to a large extent. The scheme of mucking employed made it necessary to keep the steel shaft sets within 50 ft. of the bottom at all times. This could not be done without serious damage with a V-cut when blasting in granite. The cut as drilled also broke 10.83 ft. per round of drilling, which was considerably more than the experience with a V-cut in the same material. The extended cut reduced proportionately the delays for charging, blowing smoke and handling drilling equipment in the shaft. Another advantage was the ease in drilling vertical over inclined holes, and the preservation of the proper spacing of the drill holes at the bottom of the cut. Drilling Air was carried down the shaft in an 8-in. flanged pipe line at a pressure ranging from 95 to 100 Ib. This line was extended to within 100 ft. of the bottom, where a valve and a 4 by 4 by 6-ft. tee was connected to it. To each side of the tee was connected a nipple and elbow, the resulting span of the two elbows being about 4 ft. Lengths of short 3-in. hoses

Jan 1, 1940

By J. C. Sullivan, W. A. Knoll

The sinking of a new shaft at the Newport mine, Ironwood, Mich., was started in May 1931 and completed on Aug. 3, 1932. During this period, 2665 ft. of shaft in granite was completed, at an average advance of 6 ft. per 24 hr. In Novernber of 1930, experimental work was conducted on 65 ft. of shaft through 22 ft. of overburden where ledge was encountered, and this work convinced the operators that all drilling could be done with vertical holes with the blasting relief to a 4½-in. hole drilled vertically in the center of the cut. The reason for not adopting the conventional V-cut was to get away from damaging the shaft steel. The blasting in a V-cut naturally tends to throw the broken material upward, but with the cut as adopted the relief was in a horizontal direction to a large extent. The scheme of mucking employed made it necessary to keep the steel shaft sets within 50 ft. of the bottom at all times. This could not be done without serious damage with a V-cut when blasting in granite. The cut as drilled also broke 10.83 ft. per round of drilling, which was considerably more than the experience with a V-cut in the same material. The extended cut reduced proportionately the delays for charging, blowing smoke and handling drilling equipment in the shaft. Another advantage was the ease in drilling vertical over inclined holes, and the preservation of the proper spacing of the drill holes at the bottom of the cut. Drilling Air was carried down the shaft in an 8-in. flanged pipe line at a pressure ranging from 95 to 100 Ib. This line was extended to within 100 ft. of the bottom, where a valve and a 4 by 4 by 6-ft. tee was connected to it. To each side of the tee was connected a nipple and elbow, the resulting span of the two elbows being about 4 ft. Lengths of short 3-in. hoses

Jan 1, 1940

By J. C. Sullivan, W. A. Knoll

THE sinking of a new shaft at the Newport mine, Ironwood, Mich., was started in May 1931 and completed on Aug. 3, 1932. During this period, 2665 ft. of shaft in granite was completed, at an average advance of 6 ft. per 24 hr. In November of 1930, experimental work was con- ducted on 65 ft. of shaft through 22 ft. of overburden where ledge was encountered, and this work convinced the operators that all drilling could be done with vertical holes with the blasting relief to a 4%-in. hole drilled vertically in the center of the cut. The reason for not adopting the conventional V-cut was to get away from damaging the shaft steel. The blasting in a V-cut naturally tends to throw the broken material upward, but with the cut as adopted the relief was in a horizontal direction to a large extent. The scheme of mucking employed made it necessary to keep the steel shaft sets within 50 ft. of the bottom at all times. This could not be done without serious damage with a V-cut when blasting in granite. The cut as drilled also broke 10.83 ft. per round of drilling, which was considerably more than the experience with a V-cut in the same material. The extended cut reduced proportionately the delays for charging, blowing smoke and handling drilling equipment in the shaft. Another advantage was the ease in drilling vertical over inclined holes, and the preservation of the proper spacing of the drill holes at the bottom of the cut. DRILLING Air was carried down the shaft in an 8-in. flanged pipe line at a pres- sure ranging from 95 to 100 lb. This line was extended to within 100 ft. of the bottom, where a valve and a 4 by 4 by 6-ft. tee was connected to it. To each side of the tee was connected a nipple and elbow, the resulting span of the two elbows being about 4 ft. Lengths of short 3-in. hoses

Jan 1, 1938

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a' martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a' martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,' Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

By Arthur Winslow

Introductory.—The following paper is based upon a report on the lead- and zinc- deposits of Missouri, prepared for the State Geological Survey, which is now being printed. This report is the outcome of work prosecuted by the writer, assisted by Mr. J. D. Robertson, during the past five years. The studies in the State were supplemented by examinations of the similar ore deposits in Wisconsin and Arkan- sas. The report will contain in all about 800 pages, and the aim has been to make it complete and exhaustive, especially in descriptive matter. Naturally, only a brief outline can be presented here, and the reader is referred to the report itself for further details. Contents. I.—History and Statistics, . . 636 II.—Topography of the Region, . 639 III.—General Geology, . . .639 The Archean, . . .639 The Algonkian, . . 640 The Silurian, . . .640 The Devonian, . . 640 The Lower Carboniferous, 641 Tie Coal Measures, . 641 The Tertiary, . . .641 Structural Geology,. . 642 IV.—The Ore-Deposits, . . .643 Geologic Distribution, . 643 The Forms of the Ore-Bodies, . . .641 The Composition if the Ore-Bodies, . . .645 Gangues, . . . 645 Minerals, . . .618 Paragenesis of Minerals, . . . 651 The Structure of the Ore-Bodies, .... 651 V.—Descriptions of Types, . . 652 The Eagle Mines, . . 652 Shaft No. 23, . . 652 The Western Zinc Company or Oswego Lands, 651 The Gobar and Tomlinson Shaft, . 655 The Alba Company's Mine, 656 The Victor Mine, . . 658 The Bonne Terre Mines, . 660 General Geology, . 660 The Ore-Bodies, . 661 The Vallé Mines, . . 664 The Garatee Mines, . 664 The Corn-Stalk Diggings, . . .665 The Virginia Mine, . 666 The Conlogue Mine, . 667 VI.—The Mode of Formation of the Ore-Bodies, . . 670 The Formation of the Cavities. . . . 670 The Filling of the Cavities, . . . .675 The Formation of the Breccia Deposits, . . 673 The Formation of Circle Deposits, . . .674 The Impregnated Deposits of the Southeast, . 676 VII.—The Origin of the Metalliferous and Other Minerals, 676 1. Originally Deposited in Concentrated Condition, 676 2. Derived from Great Depths, . . .677 3. Original Diffusion, Supplemented by Lateral Secretion, . . . 678 4. Concentrated Through Surface Decomposition, 681

Jan 1, 1895

By J. H. Frye, J. L. Scott, J. W. Woods

THERE are at least two effects of temperature on the stress required to produce plastic flow. 1) Metals plastically strained for the same amount at different temperatures possess different stress-strain curves and different internal structures (e.g., nature and density of imperfections). 2) There is both experimental and theoretical evidence that the stress necessary to produce plastic flow may vary with temperature even though the internal structure remains constant.1-5 Much of the data in the literature is difficult to interpret because these two effects are simultaneously present. In the work reported here, they are considered separately. Standard 0.505 in. tensile specimens were prepared from high-purity Mond nickel and OFHC copper. Nickel specimens were annealed in hydrogen at 1150°C for 30 min and furnace cooled. This produced an average grain diameter of 1.4 mm. Copper specimens were annealed in vacuum at 525°C for 6 hr and furnace cooled. This produced an average grain diameter of 0.11 mm. Nickel tensile specimens were prestrained in tension at 500°K, whereas copper tensile specimens were prestrained in tension at room temperature. All specimens were cooled to 74°K and heated to room temperature. After these treatments all of the tensile specimens of a given set possessed identical structures. All specimens were returned to the tensile machine and tested at various temperatures and constant cross-head speed. Many of the tensile curves showed well defined yields but, in order to minimize personal judgment, the yield was always chosen as the stress corresponding to 0.2 pct plastic deformation. Results are summarized in the graph of yield vs temperature of test, Fig. 1. All of the specimens corresponding to any one line have had identical treatments and, therefore, have identical internal structures. Thus, each line gives the relation between yield stress and temperature for one constant internal structure. The lowest line, which is for annealed nickel, shows no measurable variation of yield with temperature. This is similar to Blewitt's6 results on copper single crystals, but a variation in yield with temperature was found by Andrade and Henderson' in single crystals of nickel, and by Car-recker and Hibbard8 in annealed polycrystalline copper. The three other lines, which are for prestrained materials, show that there is a linear relation between yield stress and temperature when the internal structure remains constant. Such a relation might be expected from a rate equation such as that of Kauzmannl on the assump- tion that the activation energy is either independent of or linear with temperature. These results would also be expected if the shear moduli of copper and nickel are linear functions of temperature for, as Cottrell and Stokes have pointed out," in all dislocation theories of strength the flow stress appears proportional to the shear modulus of the material. In copper and nickel, since the modulus of elasticity decreases roughly linearly with increase in temperature," it is probable that the modulus of shear also decreases approximately linearly with increasing temperature. A detailed discussion of the effect of these and other factors on the temperature dependence of flow stress in face-centered-cubic metals has recently been given by Seeger.4

Jan 1, 1958