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By A. D. Neuman, C. C. Davis, M. R. Lopez, A. C. Martinez, T. A. Nothwang, F. G. Hampel, S. L. Voit

"One of the thrust areas for the Global Nuclear Energy Partnership (GNEP) program is the development of actinide bearing fuels for transmutation in a fast reactor. Mixed Oxide (MOX) fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition from which minor actinides can be incorporated for use as a transmutation fuel. The current study involves characterization of precursor powders and pellets destined for the Advanced Test Reactor in Idaho. These pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of minor actinide mixed oxide (MAMOX) with oxygen to metal ratios (O/M) of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders were characterized using a field emission gun scanning electron microscope (FEG-SEM) to determine particle morphology, size, and size distribution. An electron probe microanalyzer (EPMA) was used to characterize element distributions in the pellets.IntroductionThe fundamental purpose of GNEP is to enable a fuel recycling partnership between member nations. The customer nations utilize the fuel for electricity generation provided by and subsequently recycled by the supplier nation. The supplier nation recycles the actinide constituents, mainly uranium and plutonium, in advanced nuclear power reactors, and thus reducing waste volumes [1, 2]. Nuclear materials are strictly controlled through the International Atomic Energy Agency. One of the thrust areas supported by the GNEP program is the development of actinide bearing fuels for transmutation in a fast reactor under the U.S. Advanced Fuel Cycle Initiative (AFCI) in order to transmute long-lived transuranic actinide isotopes into shorter-lived fission products [3].MOX fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition into which minor actinides can be incorporated for use as a transmutation fuel [4]. Irradiation performance data on oxide fuels with high concentrations of minor actinides is limited, which has prompted this study. This paper discusses the characterization results of precursor powders and pellets prepared for the Advanced Test Reactor in Idaho to determine the effects of including minor actinides in the fuel, and addresses two fuel test matrices proposed by Hilton et al. [3]. The pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of MA-MOX with O/M of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders, uranium oxide (depleted, DUO2 and highly enriched, HEUO2), neptunium oxide, NpO2, americium oxide, AmO2, and plutonium oxide, PuO2, were characterized using a FEG-SEM for particle morphology, size, and size distribution. The morphology of the actinide powders was studied in the areas of flowability and porosity in order to predict manufacturability. The MOX pellets were characterized using an EPMA in order to determine impurity levels and locations."

Jan 1, 2008

By Lanre Oshinowo

Computational Fluid Dynamics (CFD) is used in conjunction with process modelling at HATCH to achieve a superior level of confidence in the process design of hydrometallurgical process plants. The use of these tools to evaluate designs through virtual prototyping reduces the risks associated with making design decisions. This paper highlights the development of a co-simulation strategy at Hatch for the seamless integration of process modeling software addressing different scales (process time and space): flowsheet level models and .equipment level models. With co-simulation, the process design engineers can improve design accuracy, troubleshoot and optimize performance and influence decisions impacting equipment operation by representing specific unit operations in the flowsheet model software with detailed CFD models. Specifically, this paper will focus on the co-simulation of a Ni/Co high-pressure acid leach (HPAL) process including heaters/heat exchangers and flash system, autoclave and quench/scrubber system. The knowledge developed can be transferable to other processes.

Jan 1, 2004

By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By J. F. Elliott

The thermodynamic behavior of sulfur and oxygen in copper matte has been measured by equilibration of the melt 00 a gas consisting of CO, SO2 and Ar. The oxygen potential ranges from 10-9 to 10-7 and that for sulfur from 10-4 to 10-2 atm. The work is a continuation of the earlier study by Luraschi and Elliott in our laboratory. A model has been developed that permits extra-polation of the results to ascertain compositions of the matte that are saturated with various oxides of iron.

Jan 1, 1983

By Zheng Wei, Jian Cheni, Zhenliang Weng, Wei Liang, Hongbo Zhu, Jinhui Peng, Linqing Dai, Qianxu Ye

"By testing the dielectric constant and the dielectric loss factor of concentrated Dahongshan, mill scale, anthracite and light-burned dolomite in different frequency and temperature, and by studying the temperature-rising characteristics of the materials in the microwave field of 2.45GHz in frequency, the research in the paper shows that to reach at 1250°C under the same condition -2KW the microwave power and 30g the mass --the time concentrated Dahongshan takes is 330s, whereas the millscale is 855s and the anthracite is 820s. About the last one, the higher the temperature is, the stronger the absorptivity is. After the temperature has rose to 400°C, the anthracite's absorptivity increases dramatically. The result of the research would serve as the foundation of the further study on making direct reduced iron by microwave heating.1. IntroductionUnder the microwave fields, materials' dissipation of dielectric bodies would generate thermal effect. Therefore, the dielectric constant and the dielectric loss factor are closely related to materials' ability of absorbing microwave energy-the larger the dielectric constant and the dielectric loss factor are, the stronger the material's ability of absorbing microwave energy is, and the better the thermal effect would be[1-2]. In order to research how to make reduced iron from iron ore fines by microwave heating deeply and systematically, the test of raw materials' dielectric constants and dielectric loss factors are of the essence. What's more, because a mineral' conductivity is influenced by its components and crystal structure[3], it is necessary to study different materials' different temperature-rising characteristics; hence such studies would provide theoretical foundation of further research."

Jan 1, 2012

By Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

By Alejandro R. Alonso, Lizet Alvarado, Gretchen T. Lapidus

"Cobalt and lithium recovery from spent Li-ion secondary batteries has been increasingly studied in recent years due to the high value of both metals and the low proven reserves for lithium. The standard method employed until now has been the deactivation and crushing of the batteries, followed by leaching of the L1C0O2 spinel from the battery cathode using acid solutions, such as 1.5 to 2.0 M HC1 or H2SO4, in a temperature range from 120°C to 250°C. Once leached, the cobalt is separated by electrodeposition and the lithium by precipitation, using large amounts of carbonate to bring the solution to alkaline pH values. In the present work, citric-thiosulfate solutions are used for the spinel leach at room temperature, favoring a reductive environment at room temperature, which stabilizes the cobalt(II) as cobalt citrate and lithium(I) at pH 5, and recovers approximately 99% of both metals.IntroductionThe Li-ion batteries industry has become an important economic sector in recent years. This type of battery is the most promising system for energy storage, because of its high efficiency in charge-discharge cycles, and its adaptability to many configurations. The demand will probably increase because of the need for mobile energy sources in many types of devices ranging from cell phones, tablets, and laptops to medical, navigation and sophisticated communication equipment and even in automobiles.One major problem related to the use of these batteries is the method employed for recycling the components, mostly cobalt and lithium. Currently, there are two processes employed on an industrial scale: the Sony/Sumimoto process, used since 1990 [1] and the Toxco Process [2]. In the first case, incineration is used to open the batteries and at same time volatilize the organic solvents. After that, the metals (copper, iron and aluminum) are physically separated. The cobalt and lithium are recovered as oxides and then thermally treated in order to recycle them for new batteries manufacture."

Jan 1, 2012

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By Maurizio Marezio Bertini

Ammonia - ammonium sulfate solutions were sparged in a glass reactor with a SO2/O2 gas mixture (2% SO2 and 98% O2) to leach copper from pure chalcopyrite and chalcopyrite concentrate. The SO2/O2 mixture produces higher and faster extractions than O2 by itself. The effect of temperature, particle size and free ammonia concentration was investigated. The fastest and highest recoveries were obtained at 80 oC from a chalcopyrite concentrate with a d80equal to 13 m, with about 83 gpl free ammonia, an average pH equal to 8.75 and a stirring speed of 500 rpm. The extraction process was controlled by diffusion through a product layer, according to the shrinking core model, with an activation energy of 41 kJ/mole.

Jan 1, 2003

By Adam J. Gesing

Eddy current separators are increasingly used by the auto shredder operators to produce higher grade of nonferrous metal concentrate for recycling. While this increases the unit price of the concentrate, metal losses through inefficient metal recovery quickly offset the price differential. We show how to optimize the eddy current separation system at the shredder to maximize mate- rial throughput, nonferrous metal recovery and grade of the nonferrous metal concentrate.

Jan 1, 1998

By V. Yahorava

Mintek has developed a non-destructive Resin-in-Leach method for the recovery of Rare Earth Elements (REE) from phosphogypsum (PG) waste dumps. However, PG from different sources was found to be highly variable in terms of REE recovery and physical properties. Development of a pre-treatment process was initiated to improve the robustness of the current REE recovery process in order to render it effective for any type of PG. Extensive research into the mineralogy of REE associations with PG revealed that the majority of REE are trapped inside phosphogypsum clusters which inhibits their recovery. Hydrothermal treatment of PG-containing slurry was found to result in re-crystallisation of gypsum with the release of REE phases encapsulated in it. This process was tested on various PG samples and subsequent REE recoveries improved from 5 to 80%. This approach carries a large potential for unlocking value associated with gypsum dumps worldwide.

By Jiang Diao, Yong Qiao, Xuan Liu, Tao Zhang, Bing Xie

The equilibrium experiments between the FeO-SiO2-MnO-TiO2-V2O3-Cr2O3-MgO slag system and solid pure iron were performed to investigate the vanadium and chromium distribution ratio under Ar atmosphere. The influence of w(FeO), w(V2O3) and w(Cr2O3) in slag on vanadium and chromium distribution ratios were studied at 1653 K. The experimental results were compared with calculated distribution ratios based on molecule and ions coexistence theory. Both of them showed that higher FeO content in slag would improve the distribution ratios of V and Cr between slag and hot metal. The distribution ratio of Cr or V increased with the increase of Cr2O3 or V2O3 content, respectively. To optimize the oxidation of V and Cr from hot metal, a high oxidizing slag and suitable content of Cr2O3 and V2O3 in the slag were recommended. The results provided reference for the further study on the extraction of V and Cr in VTi magnetite.

Jan 1, 2016

By John P. Hager

One possible approach for the recovery of mercury from acid plant blow-down sludge in smelters is the use of a vacuum retort reactor for the vaporization of the mercury with subsequent collection of metallic mercury in an attached condenser. An experimental study was undertaken to investigate the vaporization of mercury when present as a compound in the Hg-S-O and Hg-Se systems. A transpiration reactor was modified to operate under reduced pressure and with a continuous flow of inert sweep gas. A water-cooled cold finger was inserted into the exit end of the reactor to provide for the rapid quenching of the exit gases and the collection of the mercury. Rates of vaporization were measured at several temperatures for each compound and were generally found to be constant at a given temperature and reactor pressure. The results were used to determine the minimum operating temperature for 100% vaporization of the compound in 60 minutes. For Hg2SO4, HgSO4, and HgSO/2HgO the required temperatures. for a reactor pressure of 50 Torr. were determined to be 634°, 622°. and 603°C. respectively. For HgO, HgSe, and HgS the required temperatures were 557°. 451°. And 382°C. respectively. For HgS the rate of vaporization was also measured at a reactor pressure of 1 00 Torr. The rate of vaporization was found to be slower resulting in an increased vaporization temperature of 423°C. It was also determined that the mercury vapor present in the exit gas stream can back-react with the other gas species to a significant extent and can result in very little condensed metallic mercury. For the vaporization of both HgS and HgSe. the mercury vapor was found to have back-reacted to the extent that virtually none of the vaporized mercury was collected in metallic form. For the vaporization of Hg2S04? HgS04, and HgSO4*2HgO the amount of metallic mercury recovered varied from approximately 50% for HgS04*2HgO to approximately 10% for Hg2S04 and HgS04. Only for HgO was the recovered mercury in primarily elemental form. The application of the results to the operation of a vacuum retort and condenser system is discussed.

Jan 1, 2001

By B. Manana

In heap leaching, the oxidative dissolution of value minerals encapsulated deep within large particles cannot be fully understood on the basis of the bulk solution conditions relative to variable solution conditions near the mineral surface. In the present study, the diffusion of the oxidising species through inner particle pores is simulated in a model apparatus that separates an inert platinum electrode under controlled reduction potential from the bulk solution through narrow pores of varying length. The Cu-NH3 system was selected as a model system and Cu(II)/Cu (I) as the redox couple of interest. Platinum probes inserted in the pores allowed the measurement of varying redox potentials along the pore length. Results showed that in a 10 mm pore, there exists a narrow (0.5 mm) zone near the reduction surface that is depleted of the oxidant and in which its supply is strongly diffusion limited, even if it is in abundance in the bulk solution. The consistent presence of this narrow diffusion region across all experimental results indicated that the transportation of the reduced species away from the reaction surface had the most significant influence on the potential variations within the pore. This was further supported by the minimal effect of varying concentrations of both Cu(II) and dissolved oxygen on the solution potential within this region.

By Cao rong-jiang, Tang Xin-he

"In ordinary manufacture process of tungsten powder, a preferable intermediate product used is ammonium paratungstate (APT). The particle size of tungten powder made from it through W2OO58 is larger than 1. 0 um. In order to obtain ultrafine tungsten powder with narrow size distribution, a new type of tungstate, hydraziniull tungstate, was studied. Its formula is 5(N2H5)2O·12 WO.s , with tetragonal crystal structure of a=5.821 , c=18. 468. Three methods for preparing hydrazinium tungstate (ART) were set up and ART can be produced by current industrial APT process with little modification of operation and without any change of equipment.Under certain PH and operation condition of the solution from which ART was produced, an autoreduction of tungsten occured, which produced a lower valency tungstate with blue color when ART was heated at different temperatures, in N atmosphere, tungsten bronze, tetragonal W0290 and W02.7E could be obtained respectively. They all have the superiorities, in the production of tungsten powder, of superfine size and narrow size distribution [average size of 0.5um or even smaller.The rate of autoreduction of ART is very fast at elevated temperature. The reduction reaction, which gaves tetragonal WO290, could be handled smoothly without explosion. To research their behaviors at autoreduction temperatures and the products of autoreduction will be new advances of tungsten chemistry and may also serve tungsten industry with new processes and materials."

Jan 1, 1988

By L. J. Friedman

Smelter operating and environmental requirements demand high on-stream time (high reliability) from the primary smelter sulfur retention device - the sulfuric ?acid plant. The key to reliable smelter sulfuric acid plant operation is the gas cooling and cleaning system. Problems in the gas cleaning system cause corrosion, plugging, equipment failure, etc - plant down time, in the contact section of the plant. The last fifteen years have seen major changes in gas cleaning system design _to the current standard of brick lined venturi scrubber, packed gas cooling tower with plate type liquor coolers and lead or plastic tube precipitators, The current? design offers improved' impurity scrubbing along with increased reliability. in addition, a number of alternate gas cleaning systems have been offered Chemetica LAB System; Monsanto DuPont D:Jna-Wave Syatem1 Lurgi venturi scrubber with lead star gas cooler. This paper will review the design and operating advantages, disadvantages, and risk of the standard gas cleaning system and compare it to the alternate systems. _

Jan 1, 1992

By T. Asahina, M. Nakamura, M. Mabuchi, I. Shigematsu, M. Nakanishi, G. Yamauchi

"Commercial stainless steels (SUS304L and SUS430) were subjected to equal channel angular extrusion (ECAE) at room temperature to a total strain of 2.3 to 9.2. For each type of stainless steel, it was shown that the sample processed by ECAE showed higher room temperature strength than the as-quenched sample. This is probably due to the heavily worked structure. On the other hand, both strength and elongation of the ECAE processed SUS430 were increased by annealing at 773K. It is likely that higher strength is attributed to both the heavily worked structure and fine substructures. It is also likely that higher elongation is attributed to the fine substructures. It is concluded that ECAE is available for improving the room temperature strength of commercial stainless steels.INTRODUCTIONEqual channel angular extrusion ( ECAE ) is a technique that provides the repetitive deformation and allows to high intensity of deformation. With this procedure, a sample is pressed through a channel that has an equal cross section but bent at an angle of ?> [1-2]. Shear strain is introduced when a sample passes through the bending point of the channel. Repetitive processing is feasible because the cross-sectional dimension of a sample has no change during processing. To date, many reports have described that ECAE is available for the fabrication of fine-grained materials [3-14]. On the other hand, an ECAE processed sample can achieve high intensity of deformation through repetitive deformation. According to the equation given by Segal [ 2 ], a strain of about 1 is introduced in each pass through die if the angle ? is 90 deg.It is well known that high tensile strength can be achieved in metallic materials through work hardening [15]. It is also known that metallic materials with fine grain size show high strength [16]. Hence, it is expected that ECAE is available for strengthening method in metallic materials. In the present paper, we will report the mechanical properties of stainless steels processed by ECAE. As samples, SUS304L austenite stainless steel and SUS430 ferritic stainless steel were chosen. Each alloy has a single-phase structure (fee or bee) and shows no phase transformation, so that transformation strengthening cannot be applied. Hence, a heavy cold work such as ECAE may be effective for strengthening of this stainless steel. Annealing was conducted for the ECAE processed SUS430 to vary its microstructure. Then, the effect of annealing on the strength of the ECAE processed SUS430 was also investigated."

Jan 1, 2000

By Rikiya Kamezawa, Rudiono, Manabu Takeuchi

"Schottky type solar cells based on phthalocyanine (Pc) thin films were fabricated, and their photovoltaic performance was investigated in various ambient atmospheres. Most of cells prepared in this study showed a good rectification and photovoltaic effects in the visible wavelength region. The introduction ofN02 gas into the measuring chamber was confirmed to increase the current both in dark and under light illumination. However, chemical reaction between the Al electrode and N02 formed some oxide and deteriorated the Schottky barrier, resulting in an increase in cell resistivity. SF 6 gas also showed similar effects on the cell performance.IntroductionPhthalocyanine is one of the typical organic semiconductors, which shows high photoconductive sensitivity in the visible to infrared region. Today, several kinds of metal phthalocyanines are used in electrophotographic photoreceptors. In addition, application of phthalocyanines to solar cells have also been trying by many workers [1, 2]. Many efforts have been made for improving performance of phthalocyanine solar cells by modification of device structure [3, 4], doping by dye or pigment [5, 6] and incorporation of metal clusters [7]. It is known that electrical conductivity in phthalocyanine is increased by adsorption ofNO2 [8, 9]. We tried to improve photovoltaic performance ofphthalocyanine solar cell by adsorption ofNO2. This paper describes the influence of N02 adsorption on the photovoltaic behavior of phthalocyanine solar cells."

Jan 1, 2000