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By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By C. H. Mathewson

MicrOscopic metallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent rnicrostructural rnosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atoms or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientatjions and it is always possible to derive one from the other by some form of- rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

Jan 1, 1928

By James Gayley

The atmosphere, which plays such an important part in the manufacture of iron and steel, is the most variable element involved in its several processes; and particularly is this true of the blast-furnace process, which consumes air in large quantitiee. At no time since the blast-furnace became an important and widely used apparatus—even when it was operated in the most crude manner—have the variations in composition of the raw materials used been as frequent and as great as the variations in humidity of the atmosphere. Important improvements have been made in the blast-furnace and its accessories, such as the hot-blast stoves, the increase in size and change in the shape of the furnace, more efficient blowing-engines, the increased protection given to the bosh-walls, and the careful preparation of the raw material, all of which have exerted a pronounced influence on the furnace-operations from a metallurgical standpoint. But during the past eight years little advance has been made in this direction; the fuel-consumption has not diminished, nor has there been any material increase in production. Within that period, however, there has been witnessed the greatest development in appliances for the economical handling of material. So complete has been the work in this direction, that, except in isolated cases, in this country at least, a further extension does not hold out much promise of a satisfactory return on the investment required. It seemed that, with the exception of the gas-engine, we had about reached the limit, for like a strong wall, the atmosphere, with its humidity as variable to-day as when first blown into a primitive blast-furnace, appeared to stand as a barrier to

Jan 1, 1905

By C. O. Brawner

FACTORS THAT INFLUENCE STABILITY AND STABILIZATION METHOD The most effective stabilization method and design can only be developed if the cause(s) and mechanics of the slide are known. Therefore, it is important that the stability be evaluated by an engineer who has had extensive rock stability experience. The most important factors that influence stability are structural geology, ground water, blasting and the mining method or methods. Structural Geology - The majority of failures in rock slopes occur along discontinuities in the rock (joints, bedding planes, shear or fault zones, etc.). Therefore, on all surface mining projects, the development and maintenance of a comprehensive structural geologic mapping program should be a first priority program that is considered a part of the operations function. This program should include mapping all major features - faults, shear zones and through going joints. All structural features which could influence stability should be mapped and presented in a structural domain format for the entire mine (Canmet, 1977). Where planes, wedges or blocks will be undercut by the mining excavation, shear strength and strain to failure tests should be performed on the joints, fault gouge and gouge-rock contact surfaces. These tests must be performed on the samples in the direction of potential slide movement and must determine the range of peak and residual shear strength values. A preliminary assessment of friction angle can be obtained from measurements of failed surfaces in the field (Figure 1) or from core sliding tests (Barton, 1981). An assessment must be made of the past geologic history of

Jan 1, 1983

By W. H. Davitt

While it is true that taxes, especially income taxes, whether they be federal, state, or local, are not usually thought of as a "cost" of doing business, it is equally true that these tax costs do reduce the distributable profits just as much as the cost of power, supplies, or labor. Therefore, the consideration given to taxes is often as important as that given to other costs. Hopefully you will recognize that, within certain limits, taxes can be controlled to an economic advantage. The tax laws as now imposed are quite complex. Many of these laws and the regulations thereunder involve many factual determinations, technical considerations, and specialized valuations that can best be made by people trained in the specific area concerned. A substantial amount of a tax liability turns on the proper consideration given to issues involving facts and principles which are peculiarly engineering in nature. The importance of these "engineering" issues in tax administration has been significantly increased in recent years by our rapidly advancing technology, automation, stepped-up mineral and oil exploitation, new industries such as electronics and nuclear power, and the extension of percentage depletion to all minerals. These specialized requirements incorporated in the law are so technical that full consideration can not be given by people with a non-engineering background.

Jan 7, 1974

By Bradley Stoughton

[Secretary's Note.—TO avoid repetition of foot-notes, references to authorities are made in this paper by means of figures, referring to a numbered list in the appendix.—J. S. 1 Introduction. This paper gives the results: first,, of a research into the somewhat extensive literature of titanium; and second, of a series of original tests upon the effect of titanium on iron castr ings. New investigations have also been made upon the effect of titanium on steel, but I hope to treat this subject in an independent paper at some later date, and, therefore, will not discuss the experiments in detail here. The combined results of this study, which extended over a period of more than two years, can be briefly summarized as follows : 1. Steel or cast-iron, in which the titanium is properly proportioned, and which has been properly treated, is improved in strength, toughness, and durability against wear, such 'as, for example, the wear of railroad-rails, of steel and chilled-iron rolls, car-wheels, etc. 2. These improvemerits seem to be caused, not so much by the direct effect of titanium on the metal, as by its cleansing influence in removing harmful impurities, such as oxygen and oxides, nitrogen, occluded slags, and perhaps also sulphur. It appears also to reduce segregation, which would contribute to the same end. 3. In order that its effects may be fully realized, the treatment of steel or iron with titanium must be correctly performed. There are a few simple, but essential, details to be observed; if they are neglected, the best results cannot be expected. To illustrate by an example: A series of tests on cast-iron

Jan 1, 1913

By L. C. Kern

This paper presents information on the use of a new propping agent (malleable aluminum particles) which has been used successfully for producing high-conductivity fractures. The conductivity of a packed fracture depends on the width of the fracture as well as the permeability of the propping material. It is significant that the flow capacity of a propped crack is often increased many fold by propping the crack with a sparse distribution of particles. However, the flow capacity of a sparsely propped crack can be limited by two phenomena: (I) crushing of the propping particles, and (2) embedment of the propping particles in the formation walls. Malleable aluminum particles exhibit interesting properties which tend to overcome these limitations. As high loads are applied to the particles they will deform slightly, rather than shattering. The deformation results in a greater bearing area against the formation wall. This reduces the stress on the particle and reduces particle penetration into the formation. The behavior of aluminum particles under load and the bearing capacities of serveral formation rocks have been measured in the laboratory. By properly using these data, as explained in this paper, the flow capacities of aluminum-propped cracks can be calculated for a variety of conditions. Aluminum particles have been used successfully in the field to prop fractures. Where high-conductivity fractures were needed, the aluminum-propped fractures have given greater well stimulation than could have been expected for conventional fracturing processes. INTRODUCTION The purpose of a hydraulic fracture treatment is to create a conductive channel from the wellbore out into the oil or gas formation. The word conductive is emphasized because we believe that the fracture conductivity (flow capacity) is one of the most important factors influencing fracturing results. Previous papers have pointed out the additional well stimulation that can sometimes be achieved by increasing fracture conductivity. Several years ago, we investigated in some detail the effect of fracture conductivity on productivity increases to be expeced from vertical fractures. Both electrical analog and theoretical studies of unsteady-state flow behavior were made. A discussion of the electrical analog equipment and some of the results of the study were given in a previous paper' by Dyes, Kemp and Caudle. Further details were given recently by McGuire and Sikora.5 Fig. 1 shows the remarkable influence of relative fracture flow capacity and length on well stimulation. Briefly, the study indicates the following. 1. High-permeability formations require high-conductivity cracks for best results. 2. The longer the crack, the higher the fracture conductivity required for best results. 3. If the conductivity of the crack is very large compared to the formation (i.e., flow is not being limited by crack conductivity), then the longer the fracture, the better will be the results. Judging from recently published articles,1,314 there is current interest in methods for obtaining high fracture conductivities. Hence, we would like to present in this paper a discussion of a new fracture propping process (use of aluminum particle) which we have used successfully to obtain highly conductive fractures. There are several factors which influence the conductivity of a propped crack. Conventional fracturing techniques frequently result in a crack completely packed with fracturing sand. For such conditions, the crack conductivity is the product of the width of the packed fracture and the permeability of the propping material. It is significant that a large increase in conductivity sometimes can be obtained by propping with particles which are distributed sparsely (less than a

By L. T. Leyson, U. C. Tainton

Some time ago, at ameeting of the Institute Prof. J. W. Richards1 said, "I take exception to the statement that all the factors in the production of electrolytic zinc were known long ago.... There is possible in my opinion an improvement of perhaps 50 per cent. in the new electrolytic processes." An examination of the literature of the subject will show the justness of Professor Richards' contention. The work of the earlier investigators was carried on in the shadow of difficulties that, today, are hardly more than memories. We seldom hear now of zinc sponge, that bête noir of the electrolytic-zinc pioneers. Zinc sponge was the name given to a peculiar, soft, black, non-adherent form of zinc deposit that was utterly useless for melting into ingot form. At the big plant at Cockle Creek, New South Wales, in 1897, Edgar Ashcroft2 said that the solution in the plant would suddenly, and without ascertainable cause, go' "bad" and begin to deposit spongy zinc. The most delicate, even spectroscopic, methods of analysis were unable to detect any difference between "good" solution and "bad" solution; either form might change to the other on being kept for a while. When it is added that an outbreak of this insidious disease (which appeared to be infectious, or at least contagious) could be dealt with only by discarding the solution and washing out all tanks and pipe lines, some idea may be gathered of the troubles of the zinc electrometallurgist in what may be spoken of as the "sponge age" of electrolytic zinc. Thanks to the efforts of a number of investigators, we are today able to diagnose with considerable certitude the nature of the malady that puzzled Ashcroft and his co-workers. The researches of Mylius and

Jan 1, 1924

By J. Gurland

THE microstructure of sintered carbides consists of particles of metal carbides, such as WC and TiC, embedded in a metallic binder which is usually a cobalt—or nickel-rich solid solution. One of the important factors influencing the strength of the alloys is the degree of dispersion of the carbide particles in the binder matrix. While it is generally accepted

Jan 1, 1960

By P. F. MINISTER

AT Lime Spur, Mont., the East Butte Copper Mining Co. has been quarrying limestone for twenty years. The quarry is beside the Northern Pacific R. R. in the Jefferson River canyon, 4 ½ miles east of Cardwell, at Lime Spur, Montana. HISTORY This quarry was opened early in 1900 by Dan Morrison of Whitehall, the discoverer of the Morrison cave, to supply a demand for smelter flux. Limestone was sold to the Pittsmont smelter of The East Butte Copper Mining Co. and to the Butte Reduction Works. As no particular effort was made at the quarry to select the rock that delivered to the smelters was unduly high in magnesia and impurities. The East Butte com¬pany, therefore. Bought the quarry. in 1909 and confined operations to the high-grade beds in order to supply rock of the desired purity for its own smelter and the Butte Reduction Works until the latter shut down. It also developed a market for some of its rock with the sugar factories. The latter market increased until in later years all rock, larger than 4 in. in size over a bar grizzly, was being shipped to the sugar factories, and the rock smaller than 4 in. was being used as a flux in the blast furnaces at the Pittsmont smelter. In 1924, the East Butte concluded a contract with the Anaconda company for the treatment of its ores, and the Pittsmont -smelter -was shut down: which made the minus 4-in. rock a useless by-product. Since there was not enough revenue in the sugar rock alone and also because of limited waste room it became necessary, if Lime Spur was to continue to operate, to increase- the proportion of plus 4-in. rock and to develop a market for the minus 4-in.

Jan 1, 1930

By L. S. Darken, H. A. Wriedt

THE constitution diagram of the iron-copper system derived by Daniloff' exhibits, at the iron-rich end, phase fields similar to those of the iron-carbon diagram. At 1484° 1094°, and 850°C there are, respectively, a 6-y-L peritectic, a y-E-Lperitectic, and a a-y-E eutectoid. The phase designated E is copper-rich, containing 4 pct Fe or less according to the temperature. The composition of copper-saturated ferrite (a-solid solution) has been determined previously only twice as a function of temperature. By electrical conductivity measurements, Buchholtz and Köster2 found 3.4 pct Cu in ferrite at a eutectoid temperature of 810°C. They represented the composition of saturated ferrite by the equation, log (%Cu) = 4.32-4125 (1/T) Gregg and Daniloff3 reported that Köster later modified his opinion, raising the indicated eutectoid temperature to 833 °C and the copper content of eutectoid ferrite to 3.7 pct. The literature contains several indications4-7 that the work of Köster and his co-workers is not reliable. Norton,8 using an X-ray method, found that 1.4 pct Cu dissolved in ferrite at the approximate eutectoid temperature of 850°C and that the solubility decreased to about 0.3 pct at 700°C. Below 700°C his experimental data show almost no change in solubility. These findings, although inconsistent with the work of Ruer and Goerens4 and of Smith and Palmer,7 have been used generally since their publication. In investigations involving the observation of arrests in temperature during continuous heating or cooling the precise location of the eutectoid temperature has been obscured by a large hysteresis. The more reliable work 579 where the results are not effected by this hysteresis indicates a eutectoid temperature between 840° and 850°C. The foregoing discrepancies, along with a few observations in this Laboratory relating to the precipitation of copper from ferrite, prompted us to rein-vestigate the lower temperature portion of the Fe-Cu system. In this investigation the solubility of copper in ferrite was obtained by the chemical analysis of high-purity iron equilibrated with copper-silver alloys. This method eliminated the necessity for retaining by a quench the physical state of the specimen existing at the equilibration temperature. EXPERIMENTAL The reaction of the iron with the copper alloy was

Jan 1, 1961

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By R. P. McLaughlin

In most branches of the mining industry it is a well-recognized fact that care must be taken to protect the mineral deposit from undue physical injury. It is comparatively easy to grasp this idea when the mineral is a solid and the lives of workmen depend directly upon the care with which it is removed from its natural position, but when the product is a liquid drawn up from pools several thousand feet beneath the surface of the ground through openings only a few inches in diameter, it requires some imagination to picture underground conditions and the changes which must often occur. The development of the petroleum deposits of California has been attended by numerous accidents, the results of which are readily noticed at the top of the wells and in the profit and loss accounts of the operators. Determination of the cause of these accidents has been the subject of considerable study, which naturally has fallen upon men familiar with technical methods. The greatest damage to the oil deposits of California has resulted from water finding its way into the oil-bearing sands, and it is the purpose of this paper to set forth briefly this phase of the oil industry. Much of the material here presented has previously appeared in publications issued by the California State Mining Bureau, which, under the direction of State Mineralogist Fletcher McN. Hamilton, has investigated the subject and taken steps toward improvement of conditions. The writer, having been in charge of this branch of the Bureau work, has gained considerable knowledge of existing conditions. Generally speaking, the oil-bearing formations of California are soft, unconsolidated sand beds, separated by clay strata, which are also soft. Some of the sand beds carry water instead of oil. All of the beds are more or less separated, probably being of lenticular shape. Very few of the beds in the oil fields lie flat or undisturbed over any great area. Folding and tilting are common, and faulting also occurs in some of the fields. The accumulation of oil is not confined to any single structural feature, such as the anticline, but occurs in many other structural features. Water-bearing strata occur in practically every oil field in the State. Complete data are not at hand for a comparison of the damage

Jan 1, 1916

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By Frank W. Osterwald

Violent, spontaneous destruction of coal faces and ribs during, what are commonly called, bumps endangers and at times destroys life and property in mines of the Book Cliffs coalfield, Carbon County, Utah. Because these mines supply much of the coking coal for the West Coast steel industries, mining is necessary, although costs are high and operating conditions are very difficult at times. As operations continue, mining will go to greater depths, and the difficulties will increase. Whether or not mining can be continued successfully depends in part on whether or not incidence of bumps can be controlled successfully. For this reason, the U.S. Geological Survey, at the request of and in cooperation with the U.S. Bureau of Mines, undertook a study of the Sunnyside No. 1 mine to determine what geologic factors were related to the incidence of bumps. This report presents the preliminary results of that study and indicates that some observable geologic features in the mine may be related directly or indirectly to bumps, and that other features may be used to infer stress distribution around workings that will aid in design of roof support measures. Coal is mined in the Sunnyside No. 1 mine from depths as great as 2500 ft by room-and-pillar methods. The surface topography is rugged with many steep cliffs and deep canyons, hence the load on the coal varies greatly within short distances. Much of the Sunnyside coal is under high stress, and while being mined, it shatters continuously' and falls from the face. Continuous shattering (bumping) makes mining easy, but if the shattering is interrupted, greater stress is built up and violent bumps may result when the coal is mined.

Jan 4, 1962

By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

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.1,4 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 crystalline 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 Sanford Belden

My topic, Recent Developments in the Design of Electric Mine Locomotives and Mining Machinery, does not require me to go into a general review of electricity as applied to the mining industry. Interesting as that subject always is, what I might say in regard to it, by way of introduction, would be unnecessary use of your time, since such facts are familiar to all. First, we will consider the recent development of the electric mine locomotive. We may well pause for a moment to reflect upon its importance to the coal-mining industry of to-day. With the dawn of the electrical age its advent was inevitable. Our practical interest is aroused not so much by the first crude effort as by the great efficiency attained during the 30 or more years since the electric locomotive made its first appearance. To judge accurately what it means to coal mining, and through coal mining to the industrial field at large, we would have to know how many of these locomotives are in use throughout the country and their aggregate daily performance, and then compare the results with what could be expected with other forms of power. Such data are lacking, but it requires no statistician to make it evident that the electric mining machine is a tremendous factor in modern progress, and that without it the work of the world could never have reached its present magnitude. Not only has the electric mine locomotive served its own special branch of usefulness, but incidentally it has solved in the main the whole problem of electric transportation. It is but a step from the triumph of a 25-ton locomotive leading a long train of loaded coal cars from a mine to the electrification of common carriers. We may or may not be near any great change in this respect. Economical reasons may hold it back for an indefinite period. But the fact remains that in the development of our mine locomotives we have met this larger emergency, in mechanical type and efficiency, whenever it may come.

Jan 6, 1914

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.14 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.' 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 crystalline 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, 1943

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.14 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.' 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 crystalline 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, 1943