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By K. K. Kelley

Despite the wide interest in titanium and its compounds, no heat and free-energy-of-formation values for titanates (that is, compounds formed from titania and other metal oxides) have been available heretofore except for ilmenite (FeTi03). Such data are needed for understanding and developing processes for producing titania and titanium tetrachloride from ores (and possibly slags) and in connection with ceramic usage of titania. This paper reports experimental measurements of the heats of formation at ordinary temperature of 11 titanates-ilmenite, perovskite, barium metatinate, strontium metatitanate, barium-strontium metatitanate, barium orthotitanate, strontium orthotitanate, barium-strontium othotitanate, geikielite, magnesium-titanium spinel, and magnesium dititanate. The experimental method was solution calorimetry. The solution calorimeter was operated at 73.7°C. and used a strong hydrofluoric-hydrochloric acid mixture as the calorimetric fluid and reaction medium.

Jan 1, 1954

ORANGE FREE STATE BRANCH MINUTES OF THE COMMITTEE MEETING HELD IN THE WELKOM CLUB ON WEDNESDAY, 8th NOVEMBER, 1972 Present: C. J. Isaac (in the Chair), E. T. Wilson, J. M. Meyer, C. Mostert, P. L. Nathan, D. A. Smith, R. Sutherland. Apologies: G. Young. MINUTES OF THE PREVIOUS COMMITTEE MEETING The minutes of the Committee Meeting held on the 19th January, 1972 were taken as read and thei r adoption was proposed by Mr J. M. Meyer and seconded by Mr E. T. Wilson. There were no matters arising from these minutes.

By P. J. Miranda, C. G. Anderson, L. G. Twidwell

Titanium is a metal of increasing worldwide strategic importance. The Center for Advanced Mineral and Metallurgical Processing (CAMP) at Montana Tech of the University of Montana is currently directing two titanium research initiatives. The first program, Titanium Extraction Mining and Process Engineering Initiative (TEMPER), is focused on producing low cost titanium through the identification and development of new mining, beneficiation and extraction technologies which will significantly reduce the cost of titanium production. This will directly benefit worldwide commercial applications. Secondly, CAMP is evaluating new technologies for fabrication of titanium utilizing the Free Form Titanium Fabrication (FFTF) initiative. These technologies may drastically reduce the cost and time to manufacture titanium components. Because of the high strength to weight ratio of titanium coupled with its superior corrosion characteristics, these programs will be of vital importance to expanding the commercial and strategic applications of titanium. An overview of these two new titanium initiatives will be presented in this paper.

Jan 1, 2005

By M. Hertzberg

This Bureau of Mines report describes experimental and theoretical studies of diffusion flames in free convection. The cross-coupling between buoyancy-induced flows and the combustion process is explored as it relates to the size, structure, and radiative balance of flames. New data are presented for the size-dependent radiance oscillations of diffusion flames and for the angular distribution of the total radiant intensity from a small methanol pool flame. Both amplitude and frequency of the measured oscillations are compared with theoretical predictions that are based on a new view of the structure of diffusion flames. This new view, which is at variance with the traditional one, assumes uniform reaction in the diffusive mixing zone, and recognizes the significance of the role played by convective buoyancy and its duality in both aiding and impeding flame propagation. Buoyancy quenches propagation at low burning velocities, introducing a real discontinuity in the combustion rate. A "flammable volume" is thus defined as that bound between lean- and rich-limit contours. However, in the flow disturbances generated by combustion waves that consume that volume, buoyancy aids propagation by promoting the convective mixing of a new flammable volume. The measured radiance oscillations are manifestations of these propagation and remixing cycles.

Jan 1, 1978

By N Gruber

In the continuous casting of ultralow carbon (ULC) steels, free carbon is used to control the melting behaviour of mould powders. If the carbon is not completely removed during melting, it is enriched at the top of the slag pool. Liquid steel may come into contact with this layer because of the turbulence of the molten metal, resulting in its recarburisation, which negatively affects the desired product quality. Thus, a reduction in carbon input is desirable. For this purpose, SiC and/or Si3N4 with and without antioxidants were selected as melt-control additives to replace carbon in the mould powders. Thermodynamic calculations were performed to quantify their effect on the melting behaviour based on the chemical composition of a flux already applied to ULC steels. To experimentally assess the liquefaction behaviour, laboratory mould powders were prepared and annealed in steel crucibles closed with a lid. Crucibles were inserted into a furnace that was already preheated to selected temperatures between 900–1200°C for 10 mins and quenched to room temperature. Subsequently, the samples were mineralogically investigated. The results confirmed those obtained from the thermodynamic calculations. Si3N4, and SiC in particular, are suitable raw materials for delaying the solid-solid reactions of raw material components during melting. Owing to their stability at high temperatures, the necessary SiO2 content to form a liquid phase is not available, resulting in lower amounts of the liquid phase. The addition of antioxidants to delay the oxidation of SiC further reduces this positive effect. Attempts to decrease the SiC content without negatively affecting the melting behaviour resulted in a reduction in the CO2 emission by at least 27 g CO2/kg of mould powder when compared to the carbon-containing standard mould powder. These investigations revealed differences in the melting behaviours of granules and loose powders, which are related to their respective production processes.

Jun 19, 2024

By O. C. Baptist

The gravitational pressure gradient (GPG) in porous sandstone containing free gas was determined to define the proper GPG to use when calculating the rate of downdip flow of oil in the Sub-Scalez No, 1 sand, Elk Hills field, Naval Petroleum Reserve 1. The GPG was determined at several gas saturations using long, artificially consolidated sandstone models that were mounted vertically in some tests and horizontally, with rotation, in others. Also determined by laboratory and field tests were relative permeabilities, capillary pressure relations; critical gas saturation, water sensitivity, and depletion drive performance. The critical gas saturation in the models having an absolute permeability of 1 to 2 darcys was about 2 percent of pore volume. The GPG with the critcal gas saturation was that due to the weight of the gas-saturated oil. The GPG in the upper part of the models was reduced as gas saturation increased to a value considerably larger than the critical. The exact gas saturation at which the GPG became less than that due to the weight of the oil could not be determined but was estimated to be of the order of 10 percent of pore volume. Tests indicate that the rate of oil production is not permanently reduced by exposure of the sand to fresh water but that the rate of injection of fresh water will be considerably less than that to brine, Methods for determining the factors mentioned above are discussed.

Jan 1, 1967

By Alexander J. Verstraeten

Work started on the building of the Amsterdam Concert Hall in 1880 by driving over 2000 wooden piles of 13 m on which foundation-beams out of wood and brickwork were made. During construction the design was changed. This was due to the latest German developments, requiring double walls instead of single, so that the space in between could be used for ventilation and heating. Therefore the pile load, originally designed at approximately 100 kN, increased even to 170 kN for some piles, causing settlements and unacceptable cracks in the brickwork. Settlements of up to 18 cm were measured. In 1985/1986 around 400 vibration-free Tubex-displacement-piles were installed under the Concert Hall, with a shaft of 0355 mm, a pile shoe of 0560 mm and a pile length of approximately 18 m. After these Tubex piles had been installed they took over the complete weight of the whole building, thus eliminating further settlements and damage. 95% of all the construction activities took place while the concerts went on. The chosen solution also made it possible to create a new basement under the Concert Hall as an extension for dressing-rooms etc.

Jan 1, 1987

By Nar S. Dala1, Xianglin Shi, Val Vallyathan

"Electron spin resonance (ESRJ and cytotoxicity measurements were made on newly fractured silica to examine specifically the role of the fracture-induced, silicon-based radicals (Si· and SiO·) and silica-generated hydroxyl (·OH) radicals in the mechanism of the cell membrane damage by silica. The concentration of the Si· and SiO · radicals was controlled through decay processes, thermal annealing, and boiling, while that of the ·OH radicals was varied by using catalase, superoxide dismutase, KMnO, Na;iSeO:y ascorbic acid, and metal ions, and monitored via ESR spectroscopy. The dust's cytotoxicity potential was evaluated by measuring the silica-induced hemolysis and also by determining lipid peroxidation (using linoleic acid). From the comparison of hemolysis and ESR results it is deduced that the radicals play little or no role in the silica-induced hemolysis. However, the lipid peroxidation data indicate that the radicals might be involved in the initiation of an oxidative chain reaction leading to the macrophage membrane damage through lipid peroxidation. INTRODUCTIONThe biochemical mechanism of quartz-related pneumoconiosis is still not fully understood. It is believed, nevertheless, that one event of primary importance is the perturbation of cell membranes by the dust particles (Allison et al., 1966; Allison and Harrow, 1971; Bateman et al., 1982; Parazzi et al., 1968; Reiser and Last, 1979; Shi et al., 1989; Summerton et al., 1977). The ensuing cell: membrane damage unleashes certain lytic enzymes resulting in additional cell injury and eventual fibrosis (Nolan et al., 1981; Summerton et al., 1977). Thus considerable effort is currently being made toward the understanding of the processes by which quartz particles disrupt the membrane of a red blood cell (RBC) or a pulmonary alveolar macrophage (PAM). A simple but important method of evaluating the membrane damage potential of a dust is the hemolysis test (Harington et al., 1971). Even though this test is used routinely for screening dusts for their cytotoxicity potential, the biochemical mechanisms underlying the cell lysis by many dusts, including quartz, is still controversial (Kilroe-Smith, 1974; Singh and Rahman, 1987), and this provided us the impetus for the present undertaking."

Jan 1, 1990

By C. Ortuglio

The effect of cracking by increasing the free space above the charge on the composition and yields of the volatile products from carbonization of Pittsburgh-bed coal and one industrially used blend from Eastern United States and one from Western United States was investigated with the BM-AGA carbonization apparatus. Increasing the free space above the charge from 1 inch to 3 inches, to 6 inches, and to 9 inches resulted in lower tar yields and increased gas and light oil yields. Anthracene and naphthalene yields were increased; quinoline and benzene insoluble fractions of both the tar and pitch increased considerably with increased free space, although the carbon content of the tars and pitches increased only slightly. Increased cracking, occasioned by the increase in free space, resulted in a decrease in the yields of tar acids, tar bases, neutral oils, olefins, aromatics, and paraffins and naphthenes. Gas composition was relatively constant; hydrogen and methane tended to increase and ethane decrease. Results of the investigation are being used to design a unit to upgrade the volatile products of carbonization by cracking the hot products as they leave the carbonization chamber.

Jan 1, 1970

By Martin Froehling, Curtis Mohns, Rahim Rajwani, Michael Fullam

"The Kemess mining and milling complex is operated by Northgate Minerals Corporation and is located in the mountains of north-central British Columbia, 430 kilometers northwest of Prince George. The complex consists of the Kemess South open pit mine and a 52,000 tonnes per day mill. Hypogene, supergene and leach cap ores are processed using conventional crushing, grinding, and flotation techniques to produce gold-copper concentrates with minor by-product silver value.The rougher flotation concentrate is re-ground in closed circuit before being cleaned to final concentrate grade. Historically, gold losses in the cleaner tailings were primarily associated with pyrite, with only minor amounts of free gold. More recently, with the processing of high pyrite ores, the major losses were found to be free gold less than 10 microns in size. The fine grind required for the high pyrite ores resulted in over-grinding of the free gold particles in the regrind circuit, contributing to poor flotation characteristics. It was thought that if this free gold could be recovered by gravity at coarser size in the regrind circulating load, the free gold losses in the cleaner tailings could be reduced.Preliminary test work carried out by Knelson Gravity Solutions indicated the potential for free gold recovery in the regrind circuit. A Knelson XD-30 Concentrator was installed with variable speed capability, and a series of optimization tests were carried out. In addition, cleaner tailings were characterized with gravity operating and with gravity not operating to determine the overall gold recovery benefit. The single Knelson XD-30 installation recovers ~10% of the total gold in the regrind circuit and increases overall recovery by 3% when high pyrite ores are processed."

Jan 1, 2007

By Harold R. Larson, John F. Elliott

The standard free energies of formation of several nzetallic sulfides have been measured by a reversible electromotive-force cell employing stabilized zir-conia as the electrolyte. The oxygen potential at the cathode was fixed by the use of pure oxygen gas at 1 atm. It was established at the anode by bringing to equilibrium the reaction between the sulfide and oxide species present. Thus, Gf: for the sulfide could be obtained from the cell potential and the standard free energies of formation of the oxides participating in the reaction. The results in calories per cam rnole for the temperature range 850" to 1100°C are: Use of the reversible electromotive-force cell having an oxide-ion electrolyte to obtain the standard free energies of formation of some of the more stable metallic sulfides offers a convenient experimental method that is very productive. It also avoids some of the problems inherent in the experimental methods' for such studies which rely on precise determination of gas compositions, particularly if these compositions lie near the limits of our capabilities for accurate chemical analyses. The reaction equilibrium between the lowest sulfide of a metal, SO2 at a fixed pressure, and an oxide of the metal has a characteristic oxygen potential. For example: and for metals whose lowest sulfide is much more stable than the oxides of the metal, the equivalent reaction might be:

Jan 1, 1968

By Richard A. Thomas, Connor B. Brown, Thomas H. Dubaniewicz, Teresa Barone

Electric vehicles powered by lithium-ion (Li-ion) batteries are being developed by mining vehicle manufacturers as a replacement for diesel-powered vehicles. Explosion-proof (XP) enclosures are frequently employed to enclose electrical ignition sources in gaseous underground mines to prevent the spread of an internal methane-air explosion to a nearby explosive atmosphere. Due to thermal runaway (TR), Li-ion batteries have the potential to cause pressurized explosions in an enclosed structure. Past research has shown the potential for well-confined Li-ion cell TR to drive pressures beyond the conventional pressure specification for XP enclosures. Researchers at the National Institute for Occupational Safety and Health (NIOSH) used an Accelerating Rate Calorimeter (ARC) to induce thermal runaway of Lithium Titanate or Lithium Titanium Oxide (LTO) type 18650 cells enclosed within containers with various volumes and found an inverse power relationship between the TR pressure and available free space. The results were similar in magnitude to that of lithium iron phosphate (LFP) cells, which were used in prior testing. Temperatures, gas amounts, and TR pressure-rise rates were also recorded. The data indicate that with enough free space, the pressures can be lowered below the conventional pressure specification for XP enclosures.

Feb 1, 2024

By Bruno Lebon, Koulis Pericleous, Georgi Djambazov, Mayur Patel

"High speed compressible jets are used in a number of steel-making applications. In the case of the BOF, a compressible oxygen jet reacts with a carbon-rich iron bath to reduce carbon levels and produce steel. The intensity of the process is governed by the speed of the jet and by the size and shape of the depression created in the metal and slag by the force of the jet, i.e. by the corresponding free surface. This is a difficult CFD problem, since there are compressible and incompressible regions in the flow domain, which need to be handled differently in a finite-volume (FV) pressure-correction scheme. Also, standard turbulence models do not account for compressibility, or the large difference in density between the cold oxygen jet and the hot reacting surroundings. Corrections are introduced to the k-E model to remedy this deficiency and the results are validated against experimental data. The compressible/incompressible boundary is handled through a transition region, based on Mach number.IntroductionThe deformation of a free surface by a compressible high speed jet is of paramount engineering interest, particularly for understanding the physical processes within a Basic Oxygen Furnace (BOF). In a BOF, a supersonic oxygen jet impinges on a molten iron surface, thereby creating a cavity. Oxygen penetrates the bath and removes carbon, resulting in low carbon steel [1].The challenges in modelling such a process lie in coupling a solution domain with distinct compressible and incompressible regions and in dealing with large density differences between the modelled gas and liquid. The modelling of compressibility within the jet is crucial, since the correct velocity profile in the jet is required to determine the cavity depth with accuracy."

Jan 1, 2012

By M. M. Coleman

An investigation of the behaviour of sphalerite, chalcopyrite, galena and pyrite during flotation was conducted on selected circuits in the Brunswick Mining and Smelting Corporation Ltd. concentrator in Bathurst, NB. Samples were collected from 59 locations and analyzed for Zn, Pb, Cu, Ag, Fe, As, Sb, Sn, Bi and S. Metal balances were computed using the CAMP Material Balance Program (MATBAL 5) and the metal recoveries for each cell and circuit were calculated. An automated image analyzer interfaced with an electron microprobe was programmed to measure the size of sphalerite, chalcopyrite, galena and pyrite grains in each sample. The percentage of each mineral occurring as free grains and the relative amount of each mineral present in binary and ternary particles was calculated. The recoveries and losses of Pb, Zn and Cu are compared with the amount of liberated and unliberated galena, sphalerite and chalcopyrite present in the concentrates and tailings.

Jan 1, 1989

By S. S. Todd

[The purpose of this investigation was to obtain, heat-of-formation values a four Common titanates and, to conjunction with other requisite data, to derive free-energy-of-formation values In tem peratures in the range of 1,600°-1,800° K. T ht four titanites are tricalcium ?ditanite !['a¬spheremr?raritanar( rint-tir.rniurn rill( 1 This rc rr,rt sul,rlc?nu?nIs :r },r; vinu~ hul,lrc.irse,n3i n wlti h eht-rmnnIN-ti i n c {ar.a ai?rc? pu -,csseeri (or, 11 in(c-rnxiLIic co mrc+unrls conraininL~ rir:,niurrl. 'f Lac? !1~:)mc? c?xpcrirnc'ntnl n-ut rhod w,i. rna~loycul. lic?.ats of for rn:ltion of rlre comi?c,unr4~ it 29S.N. ut re mca,urc?,l by tioItl[ion e':iIorrr)utrv, using a ctrneaR }ryrlrc,fllanric-hY rir~chlorie- ,aci l mixttrrt .is rhr c-zle~rinrrrric- fluid and rc.actic~n rtu,liura}.]

Jan 1, 1956

By N. S. Dalal, X. Shi, V. Vallyathan

"Electron spin resonance (ESR) and cytotoxicity measurements were made on newly fractured silica to examine specifically the role of the fractured-induced, siliconbased radicals (Si· and SiO·), and silica-generated hydroxyl (·OH) radicals in the mechanism of the cell membrane damage by silica. The concentration of the Si· and SiO· radicals was controlled through decay processes, thermal annealing, and boiling, while that of the ·OH radicals was varied by using catalase, superoxide dismutase, KMnO4, Ha2seO3, ascorbic acid, and metal ions, and monitored via ESR spectroscopy. The dust's cytotozicity potential was evaluated by measuring the silica-induced hemolysis and also by determining lipid peroxidation (using linoleic acid). Prom the comparison of hemolysis and ESR results it is deduced that the radicals play little· or no role in the silica-induced hemolysis. However, the lipid peroxidation data indicate that the radicals might be involved in the initiation of an oxidative chain reaction leading to the macrophage membrane damage through lipid peroxidation. INTRODUCTIONThe biochemical mechanism of Quartz-related pneumoconiosis is still not fully understood. It is believed, nevertheless, that one event of primary importance is the perturbation of cell membranes by the dust particles (Allison et al., 1966; Allison and Harrow, 1971; Bateman et al., 1982; Parazzi, et al., 1968; Reiser and Last, 1979; Shi et al., 1989; Summerton et al., 1977). The ensuing cell-membrane damage unleashes certain lytic enzymes resulting in additional cell injury and eventual fibrosis (Nolan et al., 1981; Summerton et al., 1977). Thus considerable effort is currently being made towards the understanding of the processes by which quartz particles disrupt the membrane of a red blood cell (RBC) or a pulmonary alveolar macrophage (PAM). A simple but important method of evaluating the membrane damage potential of a dust is the hemolysis test (Harington et al., 1971). Even though this test is used routinely for screening dusts for their cytotoxicity potential, the biochemical mechanism underlying the cell lysis by many dusts, including quartz, is still controversial (Kilroe-Smith, 1974; Singh and Rahman, 1987), and this provided us the impetus for the present undertaking."

Jan 1, 1989

By D. M. Hausen

It has been demonstrated that microscopic techniques can be applied in a practical manner to the study of spodumene liberation in the processing of pegmatitic ores at the Kings Mountain spodumene plant, Kings Mountain, North Carolina. Spodumene and associated non-opaque gangue minerals are identified and quantified by microscopic point-counting of polished thin sections of heads, concentrates, middlings and tails fractions. Specially prepared polished thin sections? provide uniform thickness of particles for measurement of diagnostic optical properties and the alternate use of incident and transmitted light in distinguishing the various gangue and ore minerals. Spodumene is commonly associated and interlocked with quartz, albite, microcline and muscovite. Concentrate grade depends on the degree of spodumene liberation, which in turn depends on the crystal size and textural association of interlocked minerals. The liberation of spodumene can be measured as a function of screen size by means of microscopic point-count data. Microscopic data also provide useful metallurgical information about the nature of diluent minerals in spodumene concentrates, and the form of lithia losses in the tails. Lithium assays correlate closely with microscopic spodumene analyses in various flotation products from Foote Mineral's Kings Mountain plant, and confirm the applicability of quantitative optical microscopy to the study of liberation and recovery of spodumene from pegmatitic ores. A better understanding of recovery-grade relationships was developed as a result of quantitative microscopy studies.

Jan 1, 1981

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By Michael L. Free, Zongliang Zhang, Joshua M. Werner

In the copper electrowinning process, short-circuiting between the anodes and the cathodes is a critical problem that changes the current allocation among local electrodes and reduces the current efficiency significantly. Possible reasons for the short-circuiting include the improper alignment of the electrode, bent electrode, and nodules on the cathode surface. In typical tankhouses, there is often a time between shorting and harvesting as well as between shorting and clearing. Therefore, it is inevitable to have short-circuiting affect the operation performance in practical electrowinning operations. However, one key piece of missing data is the actual measurements of the current efficiency as short-circuiting is approached and allowed to continue. Consequently, short-circuiting tests that allow tracking of electrowinning parameters before and after short-circuiting were performed in a laboratory scale Cu electrowinning cell. In the tests, the electrode spacing change, the mass of electrodeposited Cu, the deposition morphology, and the current allocation as well as the current efficiency before and after short-circuiting were studied. Results show that the short- circuiting affects the current allocation and the current efficiency significantly. Moreover, it changes the Cu deposition on the short-circuited cathode and therefore causes problems for Cu electrowinning. INTRODUCTION Electrowinning (EW) is commonly used for copper production around the world, with a rated production from 120,000 to 200,000 tons per year per operation (Wiechmann, Aqueveque, Henríquez, Muñoz, & Morales, 2014). In Cu electrowinning, Cu ions in the electrolyte are reduced on the cathode surface as metallic copper with a DC current, while on the anode, a counter anodic reaction occurs with oxygen gas generation (Werner, Zeng, Free, Zhang, & Cho, 2018; Zhang, Werner, & Free, 2018; Zhang, Werner, & Free, 2018). In copper electrowinning, an average current density of 200 to 400 A/m2 is applied to the electrowinning cell (Wiechmann et al., 2014). As the Cu deposits on the cathode, the distance between anode and cathode reduces and most of the time, short-circuiting forms between some anodes and cathodes in a large tankhouse containing thousands of electrodes, reducing the current efficiency and increasing the energy consumption significantly. The current efficiency in well-run copper EW operations is typically above 90 %. Most of the unused current is wasted through short circuits, stray currents, and by-byproduct formation (Davenport, King, Schlesinger, & Biswas, 2002; Wiechmann, Vidal, Pagliero, & Gonzalez, 2002; Wiechmann, Morales, & Aqueveque, 2010). Usually, in the tankhouse, the short-circuiting increases the current in the involved cathode by up to 1500 A (Wiechmann et al., 2010). Multiple reasons can cause the short-circuiting in the cell, and the most common reasons include the uneven current distribution among cathodes, tilted electrodes, bent electrodes, and nodules formed due to the large deposition roughness. Recognition of this challenge in the Cu electrowinning process has led researchers to perform many investigations on approaches to avoid and reduce the short-circuiting in the cell. A series of research investigations have been conducted to develop and improve a new type of intercell bar for Cu electrowinning (Wiechmann et al., 2002; Wiechmann, Morales, Aqueveque, & Burgos, 2007; Wiechmann, Morales, & Aqueveque, 2009; Wiechmann et al., 2010; Wiechmann et al., 2014). The associated test results show that this new design limits the occurrence and magnitude of short circuits and allows operation at higher current densities. Sandoval, Clayton, Dominguez, Unger, and Robinson (2010) stated several keys to control short circuits, such as maintaining the straightness of the cathode, removing “edge hair” from the cathode starter, and maintaining electrode alignment in the cell. Prengaman and Siegmund (1999) from RSR technologies developed a new Pb-Ca-Sn anode to prevent the anode deformation, thereby reducing the short-circuiting in the Cu electrowinning cell. Although the negative effects of short-circuiting on the Cu electrowinning have been recognized, and various investigations have been conducted to address this issue, the actual measurements of the electrowinning behavior and performance as short-circuiting is approached and allowed to continue are seldom reported. However, in typical tankhouses, there is a time between when shorting occurs and harvesting/clearing are performed. One key factor in determining the harvest time is the frequency of shorting. Consequently, we have performed short-circuiting tests that allow us to track electrowinning parameters before and after short-circuiting.

Jan 1, 2019

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960