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By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954

By Carlton D. Hulin

The usual concurrence in time and space of intrusive igneous activity, favorable structural disturbance and mineralization, which is so manifest in the mineralized district necessarily indicates a close interrelationship between these events. Evaluation of available evidence leads to the recognition that an appreciable time interval exists between the emplacement of the igneous intrusive and the formation of associated ore deposits. During this interval known portions of the intrusive are completely solidified, highly differentiated magma facies are injected as dikes, and important faulting occurs, which may fracture and shatter the solidified intrusive body. The highly differentiated dike types could only have originated in some deep portion of an underlying plutonic body that had reached an advanced stage of magmatic differentiation. Appearing after these dikes, the mineralizing solutions may likewise be presumed to have originated at great depth. Certainly no source for these solutions can be found in near-by portions of the intrusive igneous body. The association of igneous intrusives and clustering ore deposits must be recognized as resulting from structural control. The emplacemerit and the subsequent solidification and cooling of the intrusive set in operation forces that are responsible for the favorable structural disturbances that control the mineralized district. The emplacement of the body of fluid magma weakens the crustal rocks to the extent that failure due to strains originally present in the rock body may occur. Faulting of any type and of any magnitude may be the result. Subsequently, owing to the change of state from fluid magma to crystalline granitic rock, volume decreases approximating 10 Per cent may Occur, with resultant shrinkage and collapse within the rock body. Following solidification, thermal contraction, induced by cooling of the rock body, causes a further volume reduction of 6 per cent. This thermal contraction, extending over a lengthy period of time, results in a succession of minor fault movements. These small fault movements, occurring progressively throughout the period of mineralization, are responsible for maintaining the permeability of the rock body, without which access of the mineralizing solutions and the formation of the ore deposits of the mineralized district would be impossible. Introduction A proper understanding of the causes that have localized our mineralized districts should be of considerable value to geologist and engineer alike. under current conditions the known ore reserves of productive mining camps are being rapidly depleted. Although ore of the future will be derived in part from deposits now known and from Ore bodies that are still to be discovered within the limits of productive mining districts, in part at least it must come from mineralized districts whose existence or importance yet remain to be recognized. The mining geologist is thus faced with two problems of paramount importance: (I) the location of new ore bodies within known mineralized areas and (2) the location of new mineralized districts within whose confines, previously unknown, valuable Ore deposits may occur. Any contribution to our knowledge concerning the causes for the localization of mineralized districts

Jan 1, 1949

By Carlton D. Hulin

The usual concurrence in time and space of intrusive igneous activity, favorable structural disturbance and mineralization, which is so manifest in the mineralized district necessarily indicates a close interrelationship between these events. Evaluation of available evidence leads to the recognition that an appreciable time interval exists between the emplacement of the igneous intrusive and the formation of associated ore deposits. During this interval known portions of the intrusive are completely solidified, highly differentiated magma facies are injected as dikes, and important faulting occurs, which may fracture and shatter the solidified intrusive body. The highly differentiated dike types could only have originated in some deep portion of an underlying plutonic body that had reached an advanced stage of magmatic differentiation. Appearing after these dikes, the mineralizing solutions may likewise be presumed to have originated at great depth. Certainly no source for these solutions can be found in near-by portions of the intrusive igneous body. The association of igneous intrusives and clustering ore deposits must be recognized as resulting from structural control. The emplacemerit and the subsequent solidification and cooling of the intrusive set in operation forces that are responsible for the favorable structural disturbances that control the mineralized district. The emplacement of the body of fluid magma weakens the crustal rocks to the extent that failure due to strains originally present in the rock body may occur. Faulting of any type and of any magnitude may be the result. Subsequently, owing to the change of state from fluid magma to crystalline granitic rock, volume decreases approximating 10 Per cent may Occur, with resultant shrinkage and collapse within the rock body. Following solidification, thermal contraction, induced by cooling of the rock body, causes a further volume reduction of 6 per cent. This thermal contraction, extending over a lengthy period of time, results in a succession of minor fault movements. These small fault movements, occurring progressively throughout the period of mineralization, are responsible for maintaining the permeability of the rock body, without which access of the mineralizing solutions and the formation of the ore deposits of the mineralized district would be impossible. Introduction A proper understanding of the causes that have localized our mineralized districts should be of considerable value to geologist and engineer alike. under current conditions the known ore reserves of productive mining camps are being rapidly depleted. Although ore of the future will be derived in part from deposits now known and from Ore bodies that are still to be discovered within the limits of productive mining districts, in part at least it must come from mineralized districts whose existence or importance yet remain to be recognized. The mining geologist is thus faced with two problems of paramount importance: (I) the location of new ore bodies within known mineralized areas and (2) the location of new mineralized districts within whose confines, previously unknown, valuable Ore deposits may occur. Any contribution to our knowledge concerning the causes for the localization of mineralized districts

Jan 1, 1949

By Oliver B. Knight

The producing formation in the South Field, or "Golden Lane" structure of Mexico, is a buried ridge of reef limestone of Comanchean age overlain unconformably with sediments of Upper Cretaceous, Eocene and Oligocene. The structure extends in a long sweeping arc, with the convex side toward the west, from San Geronimo, Vera Cruz, to San Isidro, south of the Tuxpam River, which it crosses at the town of Alamo. It is 52 miles long and averages 3/4 mile in width. The surface of the producing formation of El Abra limestone consists of a series of minor parallel highs which are separated longitudinally by synclinal troughs and laterally by structural saddles. The presence of these highs has been of utmost importance in the development of the field, especially in recent years when the salt-water level has risen above the synclines and confined the oil to the isolated highs. In many cases, faulty information and interpretation of the subsurface has resulted in drilling costly dry holes and salt-water wells. Development The development of the Golden Lane was started by the Mexican Eagle Oil Co. in 1906. San Diego No. 3, usually known as Dos Bocas, the first producing well on the structure, was completed on July 4, 1908. This well came in unexpectedly for an estimated daily production of 129,000 bbl., and, as the casing was not properly set, the well flowed wild into the Tamiahua Lagoon, causing a loss of several million barrels of oil. In flowing wild the well formed a crater which covers an area of 48 acres, out of which salt water and small quantities of gas still flow. Casiano No. 2, the Huasteca Petroleum Co., which yielded 200 bbl. of oil daily, and which was completed in November, 1909, was the next producing well to be drilled on the structure. In 1910, the same company completed Casiano No. 7, with an initial production of 50,000 bbl. daily, and Casiano No. 1, which produced 200 bbl. daily. In the same year, the Mexican Eagle Oil Co. completed its Potrero del Llano wells 1, 2 and 4, with initial productions of 500, 400 and 100,000 bbl. respectively. From 3910 to the latter part of 1919, development proceeded

Jan 1, 1931

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.'' Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystal-line powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.' There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.' There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By J. L. Rodda, M. L. Fuller

In connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segregate structures of the Widmansttten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith' the plane of segregation in the matrix contains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the 1iternture.l The increasing commercial importance of zinc alloys containing copper makes this fundamental study of value to the metallography of zinc alloys. Zinoeich Copper-zinc Alloys Copper enters into solid solution with zinc to at least 1.8 per cent at 400" C., according to W. M. Peirce.3 The solubility is less at lower temperatures. Thus a solid solution of copper in zinc, saturated at an elevated temperature, will precipitate the excess copper in a separate phase at a lower temperature, conditions of concentration, time, and temperature being suitable. The nature of these two phases has been established by the X-ray method of crystal analysis. Westgren and Phmgmén4 and also Owen and Preston5 have shown that the solid solution eta (7) is of the substitu-tional type with copper atoms replacing zinc atoms on the hexagonal

Jan 1, 1933

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 C. A. Pierce

UNDERGROUND operations of the United States Potash Co. at its mine near Carlsbad, N.M., have been continuous since the property was opened about five years ago. Approximately one million tons of potash has been mined and two shafts have been sunk, each to a depth of about 1000 ft. Outstanding in the company's operations is the fact that not a single blasting accident has occurred during the aforesaid period. The purpose of this paper is to describe the blasting practice that has made possible the achievement of this accident-prevention record. The mining method employed in extracting the thick horizontal bed of potash may be described as a double-entry room-and-pillar system. Mine development is kept well in advance of extraction operations, and a three years' supply of ore, at least, is always available. Limits of the orebody have not been determined, and in the present system of mining headings are advanced by a "shortwall" method. This was the first potash ore bed developed in the United States. The nature of the deposit, therefore, was unknown, and it was deemed expedient to outline a conservative mining policy. Later, when more is known about the deposit and certain control ascertained, a "longwall" panel retreating method may be found advisable. The necessity for a domestic supply of potash became a national issue previous to and during the World War. The United States Govern-ment came to realize that this country should not be dependent upon foreign sources of potash, and began extensive explorations in many parts of the country, seeking an orebody that would meet the exacting require-ments of the domestic market. The Department of Interior, through the Geological Survey and Bureau of Mines, made every effort to determine the location of potash deposits and encouraged their exploitation by private capital. Through the combined efforts of the Department of Interior and private industry, the deposit now being worked by the United States Potash Co. was discovered and brought into production.

Jan 1, 1936

By J. Chipman, N. J. Grant, H. L. Bishop

In a recent review1 of the iron-oxide activity of simple open-hearth type slags containing lime, magnesia, silica, and iron oxide, it was established that activity values were lacking in the range of slag composition most interesting to open-hearth operators. That is, laboratory experimental results were not available for simple slag compositions having basicity ratios ranging from about 1.5 to 4.0 and iron-oxide concentrations ranging from about 10 to 30 pct. However, in order to estimate iron-oxide activities for the range of slag compositions of interest to open-hearth operators, activity values were calculated using ionic concepts of slags by following the treatment of Flood and Grjotheim.2 A study of these data indicated that the desired slag compositions were probably not obtained due to the limited solubility of the basic constituents lime and magnesia. Thus, it was decided to make additional heats equilibrating molten carbon-free iron with slags containing MnO, P2O5, and A12O3 in percentages commonly found in open-hearth refining slags, and to examine the liquid slag field over a greater composition range than that of the simple slags studied previously. The ranges of the constituents used in the present study are summarized as follows: Metal Pct 0 0.070-0.201 PctMn 0.005-0.142 Slag Pet CaO 24.45-41.90 Pct MgO 3.23- 9.21 Pct MnO 1.13- 9.62 Pct FeO 20.08-48.7 Pet Fe2o3 2.23-10.14 Pct SiO, 3.51-28.50 Pct P2O5 0.23- 3.65 Pct A12O3 0.43- 3.38 The experimental procedure consisted of equilibrating the slag and metal in an induction furnace provided with a carbon-arc slag heater as described previously by Winkler and chipman.3 The data obtained were used to establish both the iron-oxide activity values and the activity coefficients for FeO and MnO in the open-hearth type slags. RESULTS AND DISCUSSION I) Iron-Oxide Activity of Open-Hearth Type Slags—The iron-oxide activities of various iron-oxide contents of the open-hearth type slags, as calculated from the oxygen content of the metal by the method of Taylor and Chipman, 4 are plotted against the molar ratio of bases to acids in Fig. 1. The data represent slag-metal studies carried out in the temperature range 1530" to 1700°C. For the purpose of this study, the constituents CaO, MgO, and MnO are assumed equal on a molar basis in their effect on the iron-oxide activity; and, PO2,5 is calculated as an equivalent to SiO2 and A12O3 on a molar basis. The total iron content of the slag is calculated to FeO and is represented by the symbol (FeO) The points presented in Fig. 1 represent the results of this investigation for iron-oxide slags containing between 1 and 8 mol pct MnO and less than about 2 mol pct each of A12o3 and PO2,5 The curved lines shown in Fig. 1 represent the results of the summary1 of the iron-oxide activities of simple slags of the system (CaO + MgO) - SiOz - (FeO),. The solid portions of the curved lines represent experimental data, and the broken portions represent iron-oxide activities calculated from ionic concepts of slags. The iron-oxide values of the open-hearth type slags of this study are in good agreement with the values of the simple iron-oxide slag system. Only a slight modification is indicated. The results of this study suggest that the line for 20 mol pct (FeO), should be lowered slightly in the basicity range 1.5 to about 3.

Jan 1, 1959

By F. R. Archibald, C. M. Nicholson

The present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay, There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity hut they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the Property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time priding review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3,460,000 The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time Operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1949

By Y. Nakada, B. Chalmers

The work-hardening behavior of surface layers of aluminum and gold single crystals was investigated by alternately deforming and then removing a thin surface layer by electropolishing or by etching. Aluminum crystals exhibited lower flow stresses after the surface removal; gold crystals did not. Abrasion of surface eliminated easy glide in both gold and aluminum crystals. By alternately deforming and removing the surface layer, it was shown that the abraded crystals work-harden preferentially under the abraded layer. It is suggested that this phenomenon is caused by the difficulty of propagating dislocations through the abraded layer. It has been demonstrated in numerous cases'-3 that the plastic behavior of metals in either single-crystal or polycrystal form is sensitive to the environment and to the condition of the surface; it has also been reported4-6 that single crystals of some metals, when deformed in tension, exhibit more work hardening near the surface than in the interior. A third type of effect that has been attributed to the special part played by the surface in plastic deformation is the influence of the dimensions of the specimen on the various parameters that define its plastic-deformation characteris- tics.?-'' Many of these experiments were made on aluminum, on which an oxide film is always present under available experimental conditions; many of the effects have been attributed to the oxide film, either in terms of its higher elastic moduli, which would cause local stress redistribution, or its higher strength, which would oppose the escape of dislocations at the surface of the metal. On the other hand, it has been suggested II,12 that the mere presence of a surface should be sufficient to produce the observed results. A rigorous examination of this question could, in principle, be carried out by comparing the behavior of aluminum with its oxide film with that of the same material without oxide. This experiment would present great difficulties. The most practical alternative is to compare aluminum with gold, which has no crystalline surface film at room temperature, and to study the effects of various surface treatments on gold. The experiments described in this paper fall into two groups, the objectives of which were to determine 1) whether single crystals of gold shared the property of aluminum that the removal of a surface layer after some plastic deformation reduced the flow stress for further deformation and, since the result of this was negative, 2) whether a surface treatment could be found that caused gold to behave in this way. I) EXPERIMENTS AND RESULTS All the tests described below were carried out on single crystals of about 6 by 6 mm cross section and of sufficient length to provide a gage length of about 10 cm.

Jan 1, 1964

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By H. L. Sheakley, D. J. Coolidge

This paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is cornrnonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. I). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. Properties of the St. Peter Sand From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1948

By D. J. Coolidge, H. L. Sheakley

This paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is cornrnonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. I). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. Properties of the St. Peter Sand From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1948

By W. R. Crane

The effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. Drainsge in these mines has been discussed in papers on mining practice,' but the fact that water, varying from 0.16 to 3.46 and averaging 1.43 times the amount of ore mined, has to be pumped from the mines daily, indicates the importance of the problem and the advisability of making a thorough investigation of the source of mine water, its mode of entry into the mines, its effect upon mining conditions, and consideration of means of improving the conditions.

Jan 1, 1927