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By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By I. Iwasaki, K. A. Smith, X. Cheng

The reaction mechanism for the cathodic decomposition of pyrrhotite in deoxygenated solutions at natural, near neutral pH levels was studied using potential and cyclic voltammetric measurements. Reaction products on the pyrrhotite surfaces were examined by Auger Electron Spectroscopy (AES), by X-ray photoelectron spectroscopy (XPS) and by analyzing the voltammograms for the electron balance of the reactions. Surface properties of the pyrrhotite/solution interface were characterized using an ac impedance technique. The parameters of an equivalent circuit were determined by the nonlinear least-squares fit (NLLSF) technique. The effect of cathodic polarization on floatability was investigated by performing microflotation tests. Possible implications to the flotation separation of chalcopyrite-pyrrhotite ores are discussed.

Jan 1, 1995

By X. Cheng

The mechanism of cathodic decomposition of pyrrhotite was studied in deoxygenated solutions at natural, near neutral pH using potential and cyclic voltammetric measurements. Reaction products on pyrrhotite surfaces were examined by AES and XPS, and by analyzing the voltammograms for the electron balance of the reactions. Surface properties of the pyrrhotite/solution interface were characterized using ac impedance technique. The parameters of an equivalent circuit were determined by the nonlinear least squares fit (NLLSF) technique. The effect of cathodic polarization on floatability was investigated by micro-flotation tests. Possible implications to the flotation separation of chalcopyrite-pyrrhotite ores are discussed.

Jan 1, 1993

By Y. C. Guan

The dissolution behavior of silver and copper form their elemental states and Ag/Cu alloys in ammoniacal solutions has been studied using rotating disc electrodes. The variables studied included concentration of ammonia, oxygen partial pressure and rotating speed of the disc. The results have been interpreted in terms of the mixed potential theory. The effect of local current resistance on the overall current has also been examined as a part of the governing theory of the dissolution. It was observed that the dissolution potential and the rate of dissolution were very much affected by the composition of the alloys.

Jan 1, 1995

The dissolution behavior of gold and copper from their elemental states and from Au/Cu alloys in cyanide solutions has been investigated using a rotating disc electrode. The anodic and cathodic reactions were studied separately and the resulting polarization curves were combined to examine the overall dissolution reactions. The dissolution rate of pure gold in the aerated cyanide solutions was inhibited by the anodic passivation on the gold surface, while the dissolution rate of pure copper was found to be mass-transfer-controlled. On the other hand, the dissolution of gold and copper from the alloys was partially controlled by electrochemical reaction and largely by mass transfer.

Jan 1, 1994

By William E. Foreman

The results of the electrokinetic study of the activation of quartz by divalent cations showed that the charge reversal was related to the point at which the cation hydrolyzed. The reversal was not due to the presence of solid hydroxide at the surface of the quartz but due to the charged ions in the solutions. The charge reversal for beryllium at a log molar concentration of 1x10-4 was observed at pH 5 and 9. The quartz was positively charged between a pH reading of 5 to 10. Magnesium at the same log molar concentration did not show a charge reversal from pH 2 to 12. The probable cause of the charge reversal was due to the ionized Be3 (OH)3+3 or Mg (OH)+ . Variations in the electrokinetics of quartz were minimized by heating the sample to 300° C.

Jan 1, 1968

By W. W. Wen

The objective of this investigation was to study the electrokinetic behavior of oxidized coals to indicate the feasibility of separating oxidized coals from ash materials and pyrite by an mine flotation process. The effects of soluble inorganic electrolyte products from coal oxidation were also examined. The electrokinetic behavior of coals of different rank and degree of oxidation were studied by an electrophoreses technique. Generally, increasing the oxidation increases the negative value of the zeta-potential and decreases the isoelectric point (IEP). Flotation results indicate that the flotation recovery increases with decreasing pH values, and that with ferrous sulfate at pH 6.5 the flotation recovery is optimum while the pyrite was depressed. Comparing the flotation results with the electrokinetic results verified that in the presence of ferrous sulfate, the maximum hydrophobicity of oxidized coal with dodecylamine and frother is near its IEP which is around pH 6.5 to 7.0.

Jan 1, 1976

By W. W. Wen, S. C. Sun

The objective of this investigation was to study the electrokinetic behavior of oxidized coals to indicate the feasibility of separating oxidized coals from ash materials and pyrite by an amine flotation process. The effects of soluble inorganic electrolyte products from coal oxidation were also examined. The electro-kinetic behavior of coals of different rank and degree of oxidation were studied by an electro-phoreses technique. Generally, increasing the oxidation increases the negative value of the zeta-potential and decreases the isoelectric point (IEP). Flotation results indicate that the flotation recovery increases with decreasing pH values, and that with ferrous sulfate at pH 6.5 the flotation recovery is optimum while the pyrite is depressed. Comparing the flotation results with the electokinetic results verified that in the presence of ferrous sulfate, the maximum hydro-phobicity of oxidized coal with dodecylamine and frother is near its IEP, which is around pH 6.5 to 7.0.

Jan 1, 1978

By G. Marchand, R. H. Hay, E. C. Pearson

"AbstractA polishing .technique is described together with two anodic etching methods for aluminum and its alloys. Some of the optical and structural characteristics of the film formed by •these etching methods are discussed and it is shown to what degree these properties of the film are related to the crystallographic orientation of the metallic substrate. Applications to the study of recrystallization and twinning phenomena and to the study of plastic deformation, banding, and texture estimation are discussed. Micrographs are shown .to illustrate the manner in which the technique is particularly well suited to the study of such phenomena.IntroductionThe physical metallurgist is constantly faced with the problem of polishing and etching of metallic sections. Mechanical polishing is tedious, time consuming, and not applicable whenever a surface entirely free from plastic deformation is required. Etchants are generally required to reveal the grain structure in order to determine its size, shape, and regularity, or to bring up constituents. In the case of aluminum, the .most common etchant to reveal grains is a mixture of three acids: HC1, HN03, and HF. This etchant is fairly satisfactory on certain alloys and for certain metallurgical conditions but in general fails to give a good definition of the grain on castings, on highly alloyed products, and whenever the grain is smaller than 100 microns in diameter. Besides size and shape, a grain, or crystal, has an orientation and may be endowed with several types of imperfections."

Jan 1, 1952

By W. G. Pfann

THE problem of forming points on wires that were from 0.002 in. to 0.010 in. in diam arose in the recent appearance of silicon and germanium point contact rectifiers as elements in microwave radar.1 In these devices a pointed tungsten wire makes a delicate contact with the surface of a semiconductor. Because the quality of such rectifiers is largely determined by the nature of this contact, considerable attention has been given to the formation of the metal point. Reproducibility of contour and freedom from burrs and even microscopic irregularities are considered essential. The operations involved must be simple and rapid enough for mass production. Previously tungsten wires had been provided with conical points by a grinding method which involved rotating a wire about its axis and causing it to bear at an oblique angle against a spinning abrasive disc. This was later complemented with an electrolytic polishing treatment which removed irregularities from the ground point and also rounded it off at the tip-a desirable feature. Finally, these operations were supplanted by the electrolytic pointing method described here. MECHANISM OF POINT FORMATION The wires to be pointed are partially immersed- in an electrolyte in a .vertical position whereupon they are provided with smooth rounded points entirely by electrochemical action. The process is independent of the depths to which the wires penetrate the electrolyte because the points are formed at the surface level. It may be used to point a single wire or many of them simultaneously and is applicable to wires of different diameters within a limited range. Solution of the immersed portion of a tungsten wire is accomplished by making it the positive electrode in an electrolytic cell, as shown in Fig I. While the wire is maintained at constant voltage the current through the cell falls continuously, principally because of the decrease in wetted area which results from solution of the tungsten. This increase in resistance occurs in a reproducible manner and is used as a control in the process. As the immersed portion of the wire dissolves, it remains cylindrical in shape except for the short section which is wetted by the meniscus. Here the rate of solution is lower and decreases as the top of the meniscus is approached. The result is the formation of a tapered section inside the meniscus. As solution continues, the cylindrical section either dissolves entirely or drops off just before complete solution, leaving only the taper which is now sharply pointed. Further action causes this point to become rounded and then quite blunt, until finally the end of the wire is almost plane. Fig 2 shows the stages in this development. Contour PF is most representative of those used in point contact rectifiers. Thus a variety of point

Jan 1, 1947

By Robert L. Chufo

This paper describes a general purpose imaging technology developed by the U.S. Bureau of Mines (USBM) that, when fully implemented, will solve the general problem of "seeing into the earth." A first generation radar coal thickness sensor, the RCTS-1, has been developed and field-tested in both underground and highwall mines. The noncontacting electromagnetic technique uses spatial modulation created by moving a simple sensor antenna in a direction along each axes to be measured while the complex reflection coefficient is measured at multiple frequencies over a two-to-one bandwidth. The antenna motion imparts spatial modulation to the data that enables signal processing to solve the problems of media, target and antenna dispersion. Knowledge of the dielectric constant of the media is not necessary because the electrical properties of the media are determined automatically along with the distance to the target and thickness of each layer of the target. The sensor was developed as a navigation guidance sensor to accurately detect the coal/noncoal interface required for the USBM computer-assisted mining machine program. Other mining applications include the location of rock fractures, water-filled voids, and abandoned gas wells. These hazards can be detected in advance of the mining operation. This initiating technology is being expanded into a full threedimensional (3-D) imaging system that will have applications in both the underground and surface environment.

By David L. Moffatt, Leon Peters

A unique electromagnetic pulse sounding system for the detection and identification of geological and man-made anomalies which represent hazards in hard rock rapid tunneling operations is described. The main features of the system including a periodic video-type pulse interrogating signal and a probe structure that permits operational modes which either "see" or are "blind" to homogeneous-type targets are reviewed. The results of experimental pulse measurements on targets buried in the overburden and in a limestone medium are presented. Since the electrical properties of limestone are not radically different from those of a hard rock medium, conclusions based on these data should be valid for a hard rock media also.

Jan 1, 1997

By Robert L. Chufo

The U.S. Department of Energy Pittsburgh Research Center,1 has developed and field tested a spatial, spectral sensor for measuring the thickness of mineral deposits. Knowledge of the dielectric constant of the material is not necessary because the electrical properties of the media are determined automatically along with the thickness or distance measurement. The technology was developed to measure the thickness of coal remaining in the roof and floor of a mine or the thickness of a coal pillar remaining between two mining entries for the purpose of guiding a mining machine. However, field tests have shown the new technique is equally valuable for measuring the thickness of each layer in a multilayer manmade structure such as highway paving or building foundations and the thickness of geological deposits other than coal, such as, salt, granite and sandstone. The noncontacting electromagnetic technique uses spatial modulation created by moving a simple dipole sensor antenna in a direction along each axes to be measured while the complex reflection coefficient is measured at multiple frequencies over a two-to-one bandwidth. The antenna motion imparts spatial modulation to the data and enables frequency domain signal processing to solve the problem of media, target and antenna dispersion. The technique overcomes the problem of multipath reflections from nearby metal structures and avoids the use of radio frequency absorbing material. In its present form the system measures material thickness of zero to over 3 m to within ±2.5 cm accuracy. The system parameters are variable to suit the application but for most applications default values of 40 cm antenna motion with measurements made at 401 frequencies from 0.6 to 1.4 GHz at each of 32 antenna positions with a power level of 0 dBm or less are more than adequate to provide a satisfactory signal-to noise ratio. In the range of 0 to 10 m the system operates in the continuous wave mode and by simply turning off the transmitter for ranges beyond 10 m the problems of time domain processing are entirely avoided. The technique can be implemented with a vector network analyzer, a servo controlled L-band antenna positioner, an IEEE488 bus controller and a process computer. An electronics package designed and constructed to operate in the harsh mining environment and providing 1, 2 or 3 dimensional image presentation is being evaluated as a replacement for the network analyzer. Key words: Ground penetration radar, Spatial, Spectral

By P. A. Davidson, D. J. Short

"In this paper we describe a 'non-contact' electromagnetic nozzle suitable for sprayforming and gas atomization processes. In such processes there is a need to control the flow rate and diameter of the liquid metal jet whilst minimising contamination of the stream. This can be achieved using an electromagnetic valve, which partially levitates the jet in freespace, using a segmented cylinder surrounded by an induction coil. This valve will significantly enhance the quality of the titanium alloys and nickel-based superalloys used in sprayforming and gas atomization. This paper describes the design and test of a laboratory prototype valve based on experiments performed with liquid tin.1. Introduction In many industries there is an increasing need for clean, high quality metals and alloys based on titanium and nickel. Two important processes are: 1) Spray deposition which allows the liquid metal to be converted to a near-net shape, thus alleviating the need for subsequent forging and extensive machining and; 2) Powder production of titanium by gas atomisation.In centrifugal spray deposition of titanium (see figure 1) the metal is induction melted in a cold crucible. The crucible consists of a number of water-cooled segments, which allows the high frequency magnetic field of the coil to pass through the crucible, and into the melt. The charge is melted by the induced eddy currents. Locally at the crucible walls the liquid metal solidifies, and is contained within a. 'skull' of its own solid, thus reducing contamination from the crucible wall. Once melted the metal is poured through an electrically heated graphite nozzle and into the spray forming chamber. The principal limitation of the process to-date, however, is that it currently uses a graphite and /or ceramic nozzle to direct the flow of liquid metal to the atomizing disk and as such there is considerable risk of nozzle erosion with inevitable effects in terms of contamination of the melt stream and variability in flow conditions. In this research programme we develop a. non-contact electromagnetic nozzle, which will totally eliminate refractories and/or ceramic materials from the melting and casting process. This will greatly enhance the technological capabilities of sprayforming and gas atomization processes."

Jan 1, 1999

By Ben Bowman

For certain ferroalloy furnaces, such as ferrochrome or ferromanganese, there is still doubt about the mechanisms operating under the electrode tips. In this paper a model is built that does not call upon an arc. The medium is best described as an electrically conducting slurry, a mixture of liquids, solids and gas. There are two sources of propulsion, the Lorentz force within the conducting part and buoyancy generated by CO bubbles, creating two opposed poloidal circulation loops, downward below the electrode axis and upward further out.

Jan 1, 2014

By R. A. Harrington

THE structure of anodic films formed on aluminum and other metals under varied conditions is not well known despite the wide use of such films both as protective coatings and as the dielectric medium in elec-trolytic condensers. The present work was undertaken as a survey of the possibilities of electron diffraction in the investigation of anodic films, especially in comparing the properties of anodic films formed under dif-ferent sets of conditions and subjected to various subsequent treatments. In addition, an effort has been made to compare surface films formed on aluminum by anodic treatment with surface films formed by heating, immersion in chemicals, etc, The electron diffraction method in many cases has been successfully applied to the study of thin surface films. Its principal advantage is that it can be used without removing the films from the base material upon which they have been formed. The low penetrating power of electrons, in the "reflection" diffraction method which has been used in this work, prevents the appearance of diffraction patterns from substances at depths greater than about 100 Angstrom units (10-6 cm.). Different investigations of the structure of anodic films have shown widely varying results, depending on the methods used in preparing the films. Apparently under some conditions these films are crystalline and under other conditions they are amorphous, and it has been difficult to say which type of structure will be found in any particular case. Schmid and Wassermann's' X-ray diffraction patterns of eloxal? films show two broad, diffuse bands, which these investigators attribute to finely divided cubic y-Al2O3-§ Burgers, Claassen, and Zernicke3 obtained sharp X-ray

Jan 1, 1940

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may' exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948