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By C. M. Ball

The very considerable progress made during the past three years in the crushing and concentration of ores, lends special interest at the present time to any means of a more efficient character than such as are already generally known and in use, for the rapid and regular reduction of large quantities of the harder and heavier grades of mineral-bearing rock. Such means are of exceptional importance in connection with the preparation of iron-ore for separation by the magnetic process, since in this operation the capability of dealing with large volumes of material and of securing by ready means of adjustment, a granulation of the material under treatment to any required mesh or fineness, is of the greatest possible value. With these, however, must be coupled the further considerations of the amount of power expended for the work done, and the wear and tear, represented in the cost for renewal of parts of the crushing machinery, per ton of material reduced to a given degree of fineness. In general terms it may be stated that the operation of a crushing train, capable of reducing an ore-rock of average density and hardness, from the condition of mine lumps to pass 1/16-inch screenopenings at the rate of 20 tons per hour, should not call for an expenditure of more than 125 horse-power, and that the wear and tear of the crushing machinery, all told, should not exceed 2 cents per ton. In the design of a crushing-train for an ore-dressing plant, there are, moreover, considerations of great importance which relate to the simplicity or complexity of construction and arrangement, the wear and tear of few or many elements, the easy ability or difficulty of maintaining the working adjustment of the various elements of the train, and the number of hands required for the operation of the system. With these points in view, it is thought that the Cummings ore-

Jan 1, 1893

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1941

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By Joseph Kuti

Longwall mining is the term used for the underground extraction of a wide and deep panel of coal. Such a panel may be blocked out by one or more entries on either side ("head" and "tail") of a longwall face. If all the entries are pre-driven, the panel extraction is termed longwall retreat mining. With one exception, all the longwall faces in the United States are of this type.1 Prior to the general decline in the rates of production with Continuous Miners, the development of the multiple entries generally kept ahead of the longwall extraction rate. This is no longer the case: longwall extraction rates far exceed the rate of development. In addition to this problem, in newly established mines, the development of a haulage and bleeder system based on multiple entries results in a lead-time of three years or more before longwall mining can be applied.

Jan 11, 1979

By B. Fernow

(Read at the Philadelphia Meeting, February, 1878.) THE question of preserving the forests in this country is an important one, not only to trades using wood but to the whole nation, and though agitated for many years has not received that general consideration which its broad bearing demands. Those who are interested in and working for reform in the treatment of American forests are looking to the government for help, suggesting the creation of a commission to study the conditions of forests at home and abroad, and hope that a sound system of managing the woodlands will be thereby inaugurated. This reform will cost time and money, all the more because the government can bring to bear upon private owners hardly any power but that of good example and encouragement. There is, however, another aspect of the question to which I wish to draw your attention, namely; the more economical use of the valuable material which our forests offer, a more careful and exhaustive utilization of its constituents in all cases where wood or its products are applied. The wasteful consumption of wood in the United States is in every way so enormous as to justify the statement that by merely adopting an economical husbandry in this particular the destruction of forests might be delayed for many years, while the neglect of this imperatively needed and immediately practicable reform deprives legislative remedies of much of their value. In this regard I wish to draw the attention of metallurgists, especially those who are interested in the manufacture of charcoal iron, to a more economical and profitable use of wood in iron manufacture. For thousands of years of human history wood was the main, nay, the only material used for fuel. Mineral coal came into use only in the fourteenth century, and it is only recently that it has largely displaced its less carbonaceous predecessor as fuel. The art of concentrating carbon in the form of charcoal for easier transportation and readier use in distant places was, according to Pliny, known to the ancients long before Christ, and was practiced in all countries, especially in connection with the iron- manufacture.

Jan 1, 1878

By D. A. Bailey, F. L. Kadey

During recent years, expanded perlite has found extensive use in a wide variety of commercial applications. Specifications for a range of uses call for aggregates having different physical properties and requiring various types of processing. The mitre scopic examination of expanded aggregates in specially prepared thin sections has yielded important information regarding internal structure and can be a useful aid in evaluation of the product. Perlite is an acid volcanic glass containing from 2 to 5 pct combined water. When crushed and rapidly raised to a temperature of 1500° to 2100°F, the volatilization of the combined water, coincident with softening of the siliceous glass, causes the particles to expand or pop. Expansion of perlite to densities as low as 1-1/2 lb per cu ft has been achieved, although the normal range is from about 2.5 to 10 lb per cu ft. Low-density materials of this nature have found application in cryogenic insula- tions, insulating tile and board, plaster and lightweight concrete, soil conditioners, filter aids after comminution, and a host of other uses. The expansion of perlite may be controlled by a number of variables. Some of these are ore milling, furnace design, expanding temperature, use of preheating techniques, screen size distribution, and feed rate of the crude. For the specific intended uses, the art of perlite expanding has developed to the point that much is known about the effect of these variables on the end product. The requirements, however, for an aggregate to be used in plaster are different from those for an expanded perlite to be used in lightweight concrete or for cryogenics. In the study of perlite, many practical questions remain unanswered. One of the most important is, "why do some perlites make hard aggregates while others cannot resist crushing or compaction?" The usual tests and methods for evaluation of nonmetallic substances have been tried and have contributed their share to our knowledge. But chemical analyses, compaction resistance tests, screen analysis, etc., will reveal only a limited amount of information. The answers to these complex questions may well be found in an examination of the intemal structure of the expanded particle. Such questions and the ex-

Jan 1, 1962

By B. R. Eichbaum, J. E. Murphy, J. A. Eisele

The US Bureau of Mines demonstrated ferric chloride leaching of galena concentrate on a continuous bench scale basis. Leaching was performed at 95°C (200°F) and with a contact time of 15 minutes. The ferric chloride leaching solution was continuously fed to a leaching tank at a constant rate for periods up to 45 hours. In each test, a constant redox potential was maintained in the slurry exiting the leaching tank by controlling the concentrate feed rate. In the 45 hour test, lead extraction exceeded 99.5%, and the lead chloride produced was 99.97% pure.

Jan 1, 1986

By C. D. Rubert, W. J. Parton

Large quantities of fine anthracite with associated impurities are discharged with the waste water from the coal-cleaning plants in the Pennsylvania anthracite region. Furthermore, for many years this fine material has accumulated and formed silt banks. The difficulty of removing the impurities from the fine material and the lack of adequate markets are responsible for the waste of this material. In view of a larger demand for fine coal, mainly for pulverized fuel, the Lehigh Navigation Coal Co. Inc. decided to investigate the froth flotation process for recovery of fine coal from these waste solids. A test plant was constructed and operated for six months during 1942 in order to determine the practicability of recover ing coal from the waste water of a a plant (breaker) by froth cleaning and to obtain operating data for designing a commercial plant if the results were favorable. Preliminary Investigation Before the pilot plant was constructed information was obtained by field and small-scale laboratory tests to serve as a guide in the design and operation of the pilot plant. Size and ash analyses of a representative sample of the material discharged in the wash water from a cleaning plant are given in Table. The refuse content increases progressively as the size of the particles decreases The larger particles (+35 m.) are low in ash content and could be marketed without cleaning. Since these solids are discharged from the breakers with 90 to 95 per cent water by weight, the first step in the recovery of the coal was that of reducing the quantity of water so that water in excess will not have to be handled. Furthermore, it was found that the removal of most of the minus 200 mesh high-ash material was desirable to permit the most efficient flotation of the cod. Classification tests were run and showed that a hydroseparator overflow rate of 12 ft. per hour* was sufficient to elimi-,late much of the minus 200-mesh material while allowing the coarser material to settle and be thickened,

Jan 1, 1944

By C. D. Rubert, W. J. Parton

Large quantities of fine anthracite with associated impurities are discharged with the waste water from the coal-cleaning plants in the Pennsylvania anthracite region. Furthermore, for many years this fine material has accumulated and formed silt banks. The difficulty of removing the impurities from the fine material and the lack of adequate markets are responsible for the waste of this material. In view of a larger demand for fine coal, mainly for pulverized fuel, the Lehigh Navigation Coal Co. Inc. decided to investigate the froth flotation process for recovery of fine coal from these waste solids. A test plant was constructed and operated for six months during 1942 in order to determine the practicability of recover ing coal from the waste water of a a plant (breaker) by froth cleaning and to obtain operating data for designing a commercial plant if the results were favorable. Preliminary Investigation Before the pilot plant was constructed information was obtained by field and small-scale laboratory tests to serve as a guide in the design and operation of the pilot plant. Size and ash analyses of a representative sample of the material discharged in the wash water from a cleaning plant are given in Table. The refuse content increases progressively as the size of the particles decreases The larger particles (+35 m.) are low in ash content and could be marketed without cleaning. Since these solids are discharged from the breakers with 90 to 95 per cent water by weight, the first step in the recovery of the coal was that of reducing the quantity of water so that water in excess will not have to be handled. Furthermore, it was found that the removal of most of the minus 200 mesh high-ash material was desirable to permit the most efficient flotation of the cod. Classification tests were run and showed that a hydroseparator overflow rate of 12 ft. per hour* was sufficient to elimi-,late much of the minus 200-mesh material while allowing the coarser material to settle and be thickened,

Jan 1, 1944

By Charles Morgan

AN increased demand for brown iron ore in the Birmingham district during the past 18 months has caused renewed activity both in prospecting and mining these ores. In recent years the production in Alabama has ranged from 41,559 tons in 1932 to 639,351 tons in 1928. During the last 9 years about 83 per cent of the total brown ore produced in the United States has come from Alabama (Tables 1 and 2).

Jan 1, 1937

By Edward P. Chapman

IN the Leadville district toward the close of the "intermediate mesothermal period" of mineralization, there occurred a stage of ore deposition marked by a rather complex mineral association. As bismuth minerals formed in many places during this period, it is here called the "bismuth stage" for convenience of description. The minerals so far identified with this stage, listed roughly in the order of prominence, are: chalcopyrite; several varieties of galena, differing slightly from one another in their small contents of silver, bismuth and tellurium; altaite; hessite; galenobismutite; alaskaite; aikinite; ,gold; tennantite; argentite; and perhaps sphalerite and arsenopyrite. With the exception of gold, the age relations of these minerals are difficult to determine. As shown in their descriptions, they all appear contemporaneous and hypogene. Gold may be in part contemporaneous, but most of it is distinctly later. Where minerals of this stage occur so that they can be mined alone, as at the Tucson mine, they constitute high-grade ore. Elsewhere their presence in small amounts has served to increase greatly the value of what otherwise would be low- grade pyritic or zinc-lead sulphide ore. The distribution of the bismuth ores corresponds closely to the distribution of gold ores, though not so general. It seems probable that most of the gold in the district was deposited during the "bismuth stage." These ores occur relatively near the supposed centers of mineralization in Breece and Printer Boy Hills or deep down along the Tucson-Maid fault, which is one of the well recognized channels of mineralization in the Iron Hill and Graham Park areas. Consideration of the high-grade nature of this mineralization and the fact that it appears to be found relatively close to the source of mineralization suggests that prospecting along some of the known channels, even deeper than they have yet been prospected, may offer hope of commercial success.

Jan 1, 1939

By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others.

Jan 3, 1951

By R. W. Diamond

Three mills are now operated by the Consolidated Mining & Smelting Co. of Canada, Ltd.: (1) The Sullivan Concentrator, Chapman Camp, B. C. (near Kimberley, B. C.), (2) the St. Eugene Concentrator, Moyie, B. C., and (3) the Tadanac (Customs) Concentrator, Trail, B. C. Differential flotation is the only concentration method employed in all three plants. Tables are used for pilot work only. Values in all ores treated are as minerals of some or all of the metals —lead, zinc, gold or silver. Occasional customs ores contain small amounts of copper. Sulfide iron content of ores treated varies from a low figure in some ores to 38 per cent. iron in Sullivan ore. Gangue minerals vary considerably. A few customs ores are somewhat oxidized and as a result present difficulties. Flotation equipment and control are similar in the three mills, and the flow sheets at the St. Eugene and Tadanac mills, while much simpler, are modeled after that of the Sullivan Concentrator. In this paper I will not detail treatment nor equipment in any of our plants but will describe special features in, or in connection with, all of them. I will then deal with flotation reagents, describing our use of each of them, particularly where differing from general practice. I will conclude with comments on special subjects related to differential flotation.

Jan 1, 1928

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949

By O. P. Chisholm

The most noticeable change in lead smelting over the past few years has been the increase in the smelting rate of lead blast furnaces. For several years a great deal of attention has been paid to the preparation of the blast-furnace sinter charge but more recently the plan has been to incorporate- almost the entire makeup of the blast-furnace charge, excepting coke and scrap iron, at the sintering machines. Formerly, sintering machines were used primarily for removing, sulphur and for agglomerating finely divided material both sulphide and oxide in character. Limestone flux usually was so proportioned that a relatively large amount was added to the furnace charge direct. This procedure was also followed with oxidized ores, which were purposely crushed coarse' so that they would be adaptable for direct smelting on the furnace charge. In later years it has been the tendency in western smelters to include practically all of the limestone and oxidized ores in the sinter charge. This has been somewhat more costly because fine crushing is required for sintering purposes and because these oxidized materials were given additional processing through the sinter plant. The addition of such oxidized materials to the usual charge to be sintered, brought about, in certain instances, a deficiency in heat ordinarily supplied by the sulphide constituents of the charge. This heat deficiency has been remedied by the addition of carbonaceous fuel, in the form of finely crushed coke breeze, or in a few instances by the addition of zinc retort-plant residues. The enhanced gold price has stimulated the mining of crude siliceous ores throughout the Western States and in the smelting of such ores more limestone is required for fluxing. Shipments of gold-bearing pyritic concentrates to Western smelters have increased, and the combination of increased silica, limestone and pyrite has increased the percentage of slag, which, in itself, is an aid in .securing smoother and more rapid smelting in the blast furnace. By the addition of these substances, the percentage of zinc in the slag has been appreciably lowered. at many plants, with resultant benefit to smelting speed at the blast furnace. This increase in slag formation with lowered zinc content has caused also perceptible lessening of the amount of lead on the charge and this has benefited the blast-furnace smelting. Although a satisfactory sinter is fundamental in increased rate of bullion production per furnace, there has been a trend over the list four or five years to decrease the percentage of coke and increase the percentage of scrap iron and limestone on the blast-furnace charge. As a result of these changes in practice certain blast furnaces, without any mechanical change, have doubled or tripled their tonnages. For furnaces whore the volume of air is recorded, records show decidedly larger air volumes with a comparatively small increase in air, pressure, or, none at all.

Jan 1, 1941

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969