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By Daniel C. McLean

Copper concentrates produced by many operations in the United States and South America contain chalcocite (79.9% Cu) as a major component, yet the grades of these concentrates rarely exceed 25 to 28% Cu. Mineralogical studies made by E.P. Cadwell indicated that the low grades were caused by dilution by pyrite rimmed with secondary chalcocite. Laboratory and plant tests proved that concentrates could be significantly upgraded by using a simple, low cost cyanide leaching technique to dissolve the rims and reject the pyrite. The many advantages of this new procedure are cited and the process steps and a typical flowsheet are described.

Jan 1, 1984

By K. S. Choi, B. S. Shin

The adsorption characteristics of sodium silicate on scheelite, calcite, and fluorite minerals were investigated. Adsorption equilibrium took about 60 minutes. Adsorption data show that the masimum amounts of adsorption of sodium silicate occurs at about pH 9.8. The adsorptivity was in the order of calcite > fluorite > scheelite. The amount of adsorption of sodium silicate increased with the increase in temperature of sodium silicate solutions. The amount of adsorption of sodium silicate decreases in the low concentration range of ferrous sulfate, while in the high concentration range of ferrous sulfate, the adsorption of sodium silicate increases.

Jan 1, 1986

By Andy B. Wallace

Veins in the Pyramid district of northwestern Nevada occur along steep fractures in Oligocene and Miocene quartz latite tuffs. The vein mineralization is zoned from a central enargite-pyrite zone outward through a complex polymetallic pyrite-tetrahedrite-sphalerite-galena-chalcopyrite-bornite-chalcocite zone, and finally to an outer zone of pyrite and galena. Wall rock alteration includes advanced argillic and sericitic envelopes along veins superimposed on district-wide propylitization. The ore distribution and alteration patterns were probably produced by an increase in pH, a decrease in sulfur fugacity, along with cooling of the migrating hydrothermal fluid.

Jan 1, 1981

WALTER P. JENNEY, Rapid City, S. Dak.: This paper is the first publication, I believe, of the fact that traces, up to two or three ounces to the ton, of tellurium have been found in the gold ores of the Black Hills occurring in the Potsdam formation. There are two great classes of ore-deposits in the Black Hills. First, the gold-ores in the Archæan, of which the great Homestake lode, extending from Lead City to Central, in the northwest section of the Hills, may be taken as a type; second, the refractory gold-ores found in the Potsdam sandstone over a

Jan 1, 1897

By E. T. Cox

The peninsula of Florida is remarkable for the uniform character and simplicity of its geological structure. Major Henry Whiting, of the U. S. Army, was one of the first to give an account of the physical features and rocks of Florida, in an article published in 1839, in the American Journal of Science (vol. xxxv., p. 47). He says: " The rocks found in situ are all calcareous, though siliceous boulders are occasionally seen, and nodules of hornstone are here and there mingled with the limestone, which elicit sparks and are sometimes used by the Indians for flints."

Jan 1, 1896

By AIME AIME

ADDRESSING the Ohio Section at a recent meeting in Columbus, Ohio, R. C. Allen, executive vice-president for Oglebay, Norton & Co., Cleveland, spoke on "The Iron-Ore Industry of the Lake Superior Region in Prosperity and Depression." The speaker considered this region in connection with the problem of national security. This is the age of minerals; progress depends on them; and next to agriculture, the mineral industry is of prime importance. The United States has no shortage of minerals rather an over-supply; but many mines have been and are being exhausted. The shifting of the sources of supplies of minerals so important as copper, petroleum, and iron to other countries would create internal strains and affect international relations. There will be no early decline of ore mining in the Lake Superior region unless it is forced by unwise public policies. Iron ore is industrial strength and self-sufficiency. A study of economic geography is important for statesmen and mining men, because the minerals essential for peace and war are haphazardly or irregularly distributed throughout the world. Of these minerals, 75 per cent are owned by 10 per cent of the population, mainly peoples of Anglo-Saxon origin.

Jan 1, 1934

By F. Louis Grammer

THE difference between blast-furnace gas and ordinary producer-gas is chiefly that blast-furnace gas is richer in CO, and poorer in hydrocarbons and hydrogen, as is shown in Table I. TABLE I.-Volume-Composition of Producer-Gas and Blast-Furnace Gas.. Producer-Gas. Blast-Furnace Gas. Per Cent. Per Cent. (Volume.) (Volume.) CO . 22 to 33 25.5 00., . 6 to 3 13.0 H . . 13 to 7 1.5 CH, 3 to 1.5 0.0 N . 54 to 60 60.0 If natural gas, water-gas, or by-product coke-oven gas be available, blast-furnace gas can be made to resemble very closely in calorific value the average producer-gas by merely mixing in one of these products, which are richer in hydro-carbons and, hydrogen. Blast-furnace gas, however, possesses a virtue which is sometimes absent in producer-gas, especially with coals very high in sulphur-namely, that blast-furnace gas is relatively free from sulphur. In some regions the sulphur in coal is an acute problem, and it is highly desirable to find uses for the products which are specially high in sulphur-content. An advantage would be gained if coal was coked before charging into the gas-producers, but this adds to the expense. Sulphur may be partly eliminated from coal by washing it, the success depending upon the form in which the sulphur occurs, and upon the efficiency of the washer, but it cannot always be removed to the extent desired at most American plants. It is not practicable to remove all the sulphur from producer-gas by washing it, though Mr. Reinhardt, of Germany,

Sep 1, 1908

By W. J. Taylor

The discussion on my paper entitled "Experiments with a Straight or No-bosh Furnace," read at the Philadelphia Meeting, September, 1884 (Transactions, vol. xiii., p. 489), suggests the propriety of slipplementing it with another, giving my views as to the cause of the failure, which was so decided as to create surprise among furnace men. As then stated, the Chester (8. J.) furnace, which had been 60 feet high, and 13 feet in diameter at the bosh, was altered to an 8-foot bosh, with a 7-foot hearth, 7-foot stock-line, and 4-foot bell,

Jan 1, 1886

By Thomas M. Drown

IN a communication to this Institute at the Baltimore meeting, February, 1879,* on the "Determination of Silicon in Pig Iron and Steel," the method recommended was the treatment of the metal with nitric acid until action had ceased, and then evaporating with sulphuric acid until the nitric acid was nearly or quite driven off After filtration of the siliceous and carbonaceous residue, and washing with hot water and hydrochloric acid, a silica was obtained, on ignition, which was quite pure. Since this paper was read before the Institute, we have had large experience with the method, and * Transactions, vol. vii, p. 346.

Jan 1, 1880

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear to divide into two or more branches within a short distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down com¬mences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat-marsh moving on in that direction, the other side may be rising,

Jan 1, 1873

By HOMER L. WILLIAMS

WHILE some of the mining companies have been pumping a small amount of water for some time, it is only in recent years that large quantities of water have been encountered in the Tonopah district. The water appears to be in different zones or belts so that the draining of one property does not necessarily affect the one adjoining. Consequently, each company has its own pumping plant and its own conditions. The companies panes handling the largest amount of water are the Tonopah Extension Mining Co., Halifax Tonopah Mining Co., West Tonopah Consolidated Mining Co., and Great Western Consolidated Mining Co. The Halifax shaft is on the eastern end of the district and the other three properties on the western. The ore-bearing formation occurs at greater depth on -the eastern and western ends, hence the water problem in these properties.

Jan 1, 1921

By Philip D. Wilson

IT has been my privilege to read the article prepared by R. S. Dean entitled "Production of Alumina from Low-Grade Domestic Materials" which appears on another page of this issue. Dr. Dean should be congratulated on the preparation of such an erudite and scholarly dissertation on bauxite and on the work which the Bureau of Mines has been doing in connection with the development of processes to use low-grade domestic materials.

Jan 1, 1943

By Charles G. Yale

(San Francisco Meeting, October, 1911.) A FEW years ago somebody connected with one of those self-constituted bodies of unofficial character, like a Chamber of Commerce, Board of Trade, or State Development Board, started a catch-phrase referring to California as " The Land of Sunshine, Fruit, and Flowers," and the railroad magazines and folders keep it steadily in use, working day and night. Yet it altogether ignores the substance which brought the State into the Union, which peopled it, and which made it famous through-out the world. You ladies and gentlemen who have come from what we here call "the East," have in your own States, no matter which one, sunshine, fruit, and flowers. But your Eastern States, having these things as we do, have not the gold that we do. Therefore, the old designation of "The Golden State," applied to California, should be revived, as being the most distinctive term. It is worthy of remembrance, too, that during the dark days of the civil war this State handed over $172,000,000 in yellow gold, and saved the credit of the nation. Gold-mining has been carried on in California since " The days of old, The days of gold, The days of 49," and it still continues. Since that historic year, and up to the end of 1910, the State has produced, in gold alone, $1,530,214,468. Since 1792 the entire United States production of gold has been $8,261,573,500, so that the single State of California has, in that period, produced within $201,144,564 of one-half of all the gold from Alaska, Arizona, Colorado, Idaho, Montana, Nevada, New Mexico, Oregon, South Dakota, Utah, Washington, and the Southern and scattering States. In other words, all the other 25 gold-producing States of the United States combined

Mar 1, 1912

By Evan Just

Attempting to analyze a 25-year forecast after less than a third of the time has elapsed may seem premature. The President's Materials Policy Com- mission's report necessarily painted with a broad brush and made no claim for pinpoint accuracy in its predictions. More importantly for present purposes, it made no attempt to predict the detailed courses of production and consumption during the period forecasted. Several statistical highs and lows may very well lie between now and 1957, so comparing recent figures with points taken from the report on a straight-line basis would be illogical. Moreover, the report assumed that the general trend of consumption-domestic and foreign-would be upward. Contrarily, domestic figures were lower in 1957 than in 1950. Therefore, to project curves from 1950 through 1957 leads to conclusions that are probably false. Many in the industry would feel more uncertain about forecasting 1975 domestic conditions now than they would have been in 1950, even though nearly a third of the 25 years has elapsed. In making comparisons, several statistical problems are encountered. The Paley report figures for 1950 were estimated in several cases and corrected figures vary as much as 10 pct. For example, the report placed 1950 lead consumption at 800,000 tons, whereas actual consumption was 885,000 tons. Obviously, in comparing more recent figures with the report's projections, adjustments must be made for positions taken in error from the start. Over the long pull, such discrepancies will probably be insignificant, but they must be noted in comparing short-term changes.

Jan 10, 1959

The term metamorphism as commonly used means any change in a rock in either form or composition, from whatever cause. By metasomatism, according to Lindgren, is meant a metamorphism that involves a change in the chemical composition of a rock by the addition or subtraction of substance. Certain types of metamorphism are due to the action of mineralizing solutions, and are closely connected with ore deposition; they form, therefore, valuable guides in the exploration for ore- deposits. Other types of metamorphism are due to regional processes, and are not connected with ore deposition. By dynamo-regional metamorphism is meant a primary alteration of rocks over large areas under conditions of pressure, flowage, and heat. This process produces schists and gneisses from either sediments or igneous rocks. It is thought that there is little migration of minerals or of elements in dynamo-regional metamorphism, and that the changes are due chiefly to recrystallization and rearrangement of original minerals in bands with their major axes oriented normal to the direction of greatest pressure. Under these conditions limestones are commonly altered to marble, and sandstones to quartzite, basic igneous rocks to greenstone or serpentine, while rocks of normal or acid com- position commonly yield the usual types of schist or gneiss. Dynamo-regional metamorphism, extending over large areas, has no connection with mineralizing processes, and is, therefore, no guide to ore deposits; while this process has certain features, such as characteristic mineral associations, in common with contact metamorphism, the results of the two processes may usually be distinguished without difficulty.

Jan 1, 1932

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1) dump leaching, where the ore is moved from its original location to be leached at another site; and 2) In-situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains. Whichever leaching method is used, it is almost always necessary to break up the ore before leaching. In this paper a study is reported which indicates that rock broken by an explosion-in particular, an underground nuclear explosion-is significantly more amenable to leaching then is rock broken by other methods. These results suggest that the leaching speed and efficiency could be increased by nuclear fracturing of the ore. Not only would the leach time be shortened, but the resulting increase in strength or richness of the solutions would decrease plant installation expense as well as reduce pumping and processing costs. A considerable fund of experience has been accumulated in the course of several hundred experimental underground nuclear explosions, so that the gross results of any given nuclear explosion can now be predicted with a fair degree of confidence.' From this knowledge it seems clear that, under the proper conditions, large ore bodies can be fractured much more economically-macroscopically speaking-by nuclear explosions than by other methods. The present study concentrates on smaller scale effects that is, the cracks in the chunks of rock broken by the explosion-and shows that here too, in the microscopic domain, there are important advantages to nuclear fracturing. The intense shock produced by the very fast acting, high-brisance nuclear explosive fractures the rock in a way that should significantly improve its leachability. Experimental Procedure This study compared rocks broken by nuclear explosives with rocks produced by conventional mining, quarrying, or core drilling. The test samples, granite chunks 6 to 8 in. on a side, plus core sections, came from the area of the Hardhat*2 nuclear explosion and were taken both before and after the explosion. For comparison, several samples of quarried granite were obtained from a local gravestone monument company. The general procedure was to soak the test samples in leaching solution and then determine the extent of penetration. A standard commercial copper leaching solution was used (10 gpl Cu, 10 gpl H2SO4, 5 gpl ferric Fe, 15 gpl total Fe, pH about 1.5), to which a water-soluble penetrant dye, Zyglo 1-c, had been added. Details of the procedure were as follows: 1) Sample leached in solution containing Zyglo penetrant dye. 2) Washed with water. 3) Air-dried. 4) Cut with granite wire saw. 5) One face polished with granite monument polish. 6) Sent directly to be photographed, or heated at 110°C for 2 hr and then sent to be photographed. 7) Photographed under ultraviolet light to show crack patterns. Results After 10 days of leaching at 70-75°F, the samples were removed from the solution, washed, dried, and cut in half with a granite wire saw to study the penetration of the leach solution. Since the Zyglo dye in the leach is visible under ultraviolet light, the degree of penetration of the leach (and hence the cracks in the samples) can be studied on photographs of the crosscut samples made under ultraviolet light. The photos in [Fig. 1] show how the leach solution penetrated various representative samples. Of the 71 rock samples examined, fractures were most frequent and prominent in samples from the rubble produced by the nuclear explosion [(Fig. 1D)]. Fracturing was less apparent in shaft-mined rock [(Fig. 1B)], still less evident in drift-mined rock [(Fig. 1C)], and practically nonexistent in cored or quarried specimens [(Fig. 1A)]. The samples in [Fig. lA-C] were from the same general area as the nuclear explosion, but they were obtained before the explosion. Results of the crack studies are summarized in [Table 1]. The Zyglo-treated leach solution penetrated the test samples at the rate of about 1/2 mm during the first hour, 1 mm by the end of 4 hr, 2 to 3 mm in 12 hr, and 4 to 6 mm in 10 days, showing a progressively slower rate with time.

Jan 1, 1972

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By Charles Camsell

MORE than one-third of all Canada is embraced in the federal domain known as the Northwest Territories. Its most northern point, Cape Columbia, on Ellesmere Island, is only 500 mi. from the Pole. It includes parts of the main physiographic divisions of the North American continent. In the West there is a strip of 30.000 sq. mi. lying in the Cordilleran region, where peaks in the Mackenzie Mountains rise as high as 8500 ft. East of this strip and extending roughly to a line through Great Bear and Great Slave lakes to the Arctic coast is a section of the interior plains. This section, known as the Mackenzie Lowlands, contains the great artery, the most striking feature of the Northwest Territories-the Mackenzie and Slave river waterway impressive in its width, almost two miles in places, and in it's navigability for 1357 miles without obstruction to the sea. Adjoining the Mackenzie Lowlands on the East is the greater portion of the mainland of the Territories, which, as well as a large share of the island area, is in the Canadian Shield.

Jan 1, 1937

By D. Kunstelj, M. Stubicar, A. Tonejc, A. Bonefacic

A. Bonefafcic, D. Kunsfeli, M. Stubicar, and A. Tonejc The present communication is concerned with the variation of the texture in aluminum wires with die angle and temperature, at constant speed of extrusion. Experiments were carried out concurrently on refined samples, with a stated purity of 99.997 pct pure A1 and commercial samples of 99.5 pct Al. Ingots of refined aluminum samples were machined to 30-mm-diam by 150-mm-long billets. These billets were transformed to 5-mm-diam wires by drawing. The final form, suitable for examination, was obtained by extrusion through conical-face dies with a 1-mm hole diam and extrusion ratio 5:l in diam. The initial form of the commercial aluminum samples was drawn wire 5 mm in diam. These samples showed a poorly defined texture with (111) as a major and (001) as a minor component. A similar defined texture appeared in the refined aluminum samples after drawing to 5 mm diam. Conical-face dies with different angles (defined by the axis and the generating line of the cone) were used in our experiments. The values of the angles were 27, 35, 45, 57, 63, and 90 deg. The extrusion container was fitted with a heating element and controller permitting temperatures up to 600°C to be maintained within i5"C. Extrusion was performed at 250°, 300°, 350°, 400°, and 500°C at constant speed (approximately 1 mm per sec) and constant die reduction. The extrusion product was a wire 1 mm in diam and approximately 20 cm long. In order to remove the surface layer with the "conical" texture and to reduce the absorption by the X-ray examination of the samples, the extruded wire was etched to 0.22 mm in diam. Experiments were performed in the middle sections of the 20-cm-long wires. In addition to the die of l-mm hole diam, dies with a 1.5-, 0.7-, 0.6-, 0.5-, and 0.4-mm hole diam and 63-deg die angle were constructed. In our experiments we did not find in these ranges any important difference concerning the texture of the extruded wires and we continued our work solely on the 1.0-mm die. The diffracted X-rays (Cu K radiation) were recorded photographically. Diffracted intensities were measured on the (111) reflection with a microphotometer. The relative amounts of texture components were determined from the areas under the diffracted maxima. We found the texture of extruded aluminum wires to be strongly influenced not only by the temperature of extrusion and the purity of the sample but also by the form of the die. It is generally admitted that cold-drawn aluminum wires have mainly a (111) texture with a small amount of (001) component, Table I of Ref. 1. In our experiments with wires extruded in conditions represented by Fig. 1, in some cases a single (001) texture was obtained. If these wires were drawn repeatedly at room temperature, X-ray measurements revealed a duplex (001)-(111) fiber texture. Further drawings increased the (111) and decreased the (001) texture component. In Fig. 1 the percentage of material oriented with (001) parallel to the extrusion direction is represented as a function of the temperature and the die angle (a), for commercial and refined aluminum samples, respectively. From these diagrams we may draw the following conclusions. The slope of the die (a) influenced more strongly the texture at the lower rather than the higher temperatures. Again, a stronger influence was found in the case of the commercial in comparison with refined aluminum samples. In the case of the commercial aluminum samples the amount of material with (001) texture increases with increasing wire temperature in an approximately linear manner. This effect is less pronounced in the pure aluminum samples, with the exception of the die with a = 45 deg. In this case the (001) texture decreases with increasing temperature, as shown in Fig. 1. Component (001) is more pronounced in higher-purity aluminum samples. Our experiments led to the conclusion that both (001) and (111) components are essentially stable in extruded aluminum wires. As we obtained a single (001) texture starting with a sample of drawn wire in which the (001) component was very weak, our experiments revealed that the (001) component is not a remnant of the initial texture; this is in disagreement with the findings of Vandermeer and McHargue.1 We gratefully acknowledge discussions with Professor M. Paic. 1 R. A. Vandermeer and C. J. McHargue: Trans. 7MS-AME, 1964, vol. 230, p. 667.

Jan 1, 1969

By G. Derge, Ling Yang, G. M. Pound

The specific conductance and its temperature dependence were measured over the entire composition range of the molten Cu2S-CuCI system. At a typical temperature of 1200°C, 10 rnol pet of the ionically conducting CuCl reduced the specific conductance from about 77 ohm-lcm-l for pure Cu2S to about 32 ohm -1cm -1, and 50 mol pet CuCl reduced the conductance to that for pure CuCI—about 5 ohm 1cm1. The nature of electrical conduction in molten Cu2S, FeS, CuCI, and mixtures was studied by measuring the current efficiency of electrolysis at about 1100°C. The Cu2S, FeS, and mattes were found to conduct exclusively by electrons, but addition of 1 5 wt pet CUS to Cu2S produces a small amount of electrolysis. Addition of CuCl to Cu2S suppresses electronic conduction, and ionic conduction reaches almost 100 pet at a CuCl concentration of about 50 mol pet. These facts are interpreted in terms of electron energy level diagrams by analogy to the situation in solids. RESULTS of electrical conductivity studies on molten Cu-FeS mattes as a function of composition and temperature have been reported.' The specific conductances ranged from about 100 ohm-' cm-' for pure Cu2S to 1500 ohm-' cm-1 for pure FeS. This is in sharp contrast with the low specific conductance of molten ionic salts for which the transfer of electricity is by migration of ions in the field. In general, these ionically conducting molten salts, such as NaC1, KC1, CuC1, etc., have a specific conductance of the order of magnitude of 5 ohm-' cm-'. It was concluded on the basis of this evidence that molten FeS and Cu,S exhibit electronic conduction. Pure molten FeS has a small negative temperature coefficient of specific conductance, resembling metallic conduction, while pure molten Cu2S has a small positive temperature coefficient, resembling semi-conduction. The molten Cu2S-FeS mattes follow a roughly additive rule of mixtures, both with respect to specific conductance and temperature coefficient. Savelsberg2 has studied the electrolysis of molten Cu2S and Cu2S + FeS. He concluded that while molten Cu2S is an electronic conductor, there is some ionic conduction in molten Cu2S + FeS3 owing to the formation of the molecular compound 2Cu2S.FeS and its dissociation into Cu1 and FeS2-1 ions. The present work does not verify his results. Chipman, Inouye, and Tomlinson" have studied the specific conductance of molten FeO and report a high specific conductance, about 200 ohm-1 cm-1 of the same order of magnitude as that found for molten mattes, and a positive temperature coefficient. They interpret these results in terms of p-type semiconduction in the ionic liquid by analogy to the situation in solid FeO.1 imnad and Derne' detected appreciable ionization in molten FeO by means of electrolytic cell efficiency measurements. In order to verify the conclusion that electrical conduction in molten Cu2S and mattes is electronic, and to gain further insight into the structure of molten sulfides, the following investigations were carried out in the present work: 1) The specific conductance, s of the molten system Cu2S-CuC1 was measured as a function of temperature over the entire composition range. As discussed later, molten CuCl is an ionic substance. It was thought that if molten Cu2S were simply ionic in nature, addition of small amounts of CuCl might not have a catastrophic effect in lowering the high conductance of the Cu2S. On the other hand, if much electronic conduction occurs, addition of the ionic CuCl should have a large effect in destroying the electronic conduction. 2) The electrolytic cell efficiency of the following molten systems was measured at about 1100°C in specially designed cells: Cu3; Cu2S + FeS, 50:50 by wt; FeS; Cu2S + CuS, 15 wt pet; Cu2S + CuC1, 5.9 to 46.4 mol pet; and CuC1. This gives a direct measure of the fraction of current carried by ions in these melts. Further, the cell efficiency, extrapolated to zero ionic current, is given by cell efficiency = (s leasile + s elexstronic). [1] s lucile for molten CulS would be expected to be no greater than that for molten CuC1, whose s lonle is about 5 ohm-' cm-1, as will be seen in the following. u,.,,.,.,.......for molten Cu,S is of the order of 100 ohm-' cm-'.' Thus, a large increase in cell efficiency from 0 to values of 10 to 100 pet upon addition of CuCl to Cu2S would indicate destruction of the electronic conductance. Conductance Measurements Experimental Procedure—The apparatus and experimental method were the same as those described in detail in connection with the study of electrical conduction in molten Cu,S-FeS mattes.' A four terminal conductivity cell and an ac poten-

Jan 1, 1957