Search Documents

By Carla Lupi, Mauro Pasquali

"Photographic technology is based on light sensitivity of silver halides that, because of silver properties, are capable of forming photographic images. Photographic laboratories and hospital departments because of digital photographic systems less use this technology today. Nevertheless recovery of silver is still advantageous because environmental problems related to Ag ions danger to biological system. Many processes have been studied to treat silver containing photographic bath: cementation, chemical precipitation and electrowinning. In this work, after preliminary voltammetric tests, a batch electrometallurgical process has been studied to completely deplete the silver containing photographic fixing baths. The effect, of silver concentration in the electrolyte, varying over the range 0,2-1 g/L, bath stirring and current density ranging from 10 to 500 A/m2 on process yield and deposit quality, has been investigated. Introduction Photographic wastes, electronic scrap and spent catalysts constitute the main sources of materials for silver recycling. Among those silver secondary sources, the photographic discharged material could be still important and useful, even if photographic laboratories and hospital departments, because of digital photographic systems, less use photographic technology. Several processes have been developped in order to recover silver used in the field of photography from both photographic solutions and scrap film paper[1-5]. Fixing solutions are very complex baths but, because of silver position in the electromotive series, electrolysis could represent an advantageous method for silver recovery. Electrolysis produces high purity silver without generating new pollutants, while the fixer can be reused: obviously it is necessary to purge off a portion of this solution in order to avoid the excessive build up of other deleterious compounds into solution. A tested recovery method was constituted by the dissolution of silver from X-ray films with concentrated nitric acid. Internal electrolysis and external electrolysis methods were carried out using a steel electrode as cathode and a copper electrode as anode [6]. Silver recovery from photographic chemical solutions has been also performed in a special cell [7]: the solution is supplied to the bottom of a non-agitated cell having a vertically elongated form and including a central anode enclosed by a cathode. An other study discloses the use of an electrolytic cell comprising at least one anodic compartment and one cathodic compartment: the solution is treated in the cathodic compartment and then recycled in the anodic one [8]. A more recent work proposes the use of zirconium cathode for the recovery of silver from photographic fixing solution [9]: studies carried out by cyclic voltammetry showed that about 98% of total Ag can be recovered with an electrical efficiency close to 92%."

Jan 1, 2008

By Maria Salazar-Villalpando, Todd H. Gardner

"Efficient utilization of CO2 can help to decrease global warming. Methane reforming using carbon dioxide has been of interest for many years, but recently that interest has experienced a rapid increase for both environmental and commercial reasons. The use of CO2 provides a source of clean oxygen, which eliminates the need for costly oxygen separation plants. The product of dry reforming is useful syn-gas, which can be used to generate electrical power in a SOFC or in the production of synthetic fuels (hydrocarbons and alcohols). Hexaaluminate catalysts prepared at NETL may represent a product that can be utilized for the conversion of CO2 to syn-gas. In this work, transition metals dispersed in barium hexaaluminate have shown to be promising new catalysts for dry methane reforming. In this investigation, a series of BaNixAl12-yO19-d catalysts with varying Ni content were prepared by co-precipitation followed by calcination at 1400°C. CO2 reduction by dry methane reforming was carried out to determine catalyst performance as a function of temperature and carbon formation was also quantified after the reforming tests. Results of catalysts characterization, dispersion and surface area, were correlated to catalytic performance.IntroductionEfficient utilization of CO2 can help to decrease global warming. Methane reforming using carbon dioxide has been of interest for many years, but recently that interest has experienced a rapid increase for both environmental and commercial reasons. The use of CO2 provides a source of clean oxygen, which eliminates the need for costly oxygen separation plants. The product of dry reforming is useful syn-gas, which can be used to generate electrical power in a SOFC or in the production of synthetic fuels (hydrocarbons and alcohols). The dry reforming reaction has been known for a long time. Recent publications have reported studies over several catalysts. For example, the CO2 reforming of CH4 over mesoporous nanocrystalline zirconium powders (ZrO2–3%M2Ox; M: Ce, La and K) at 700ºC have shown methane conversion up to 60% (1). Similarly, the effect of Ni content (1–12 wt%) on the surface and catalytic behavior of bimetallic PtNi catalysts supported on ZSM-5 for reforming of methane with CO2 has been studied and report shows a maximum conversion of 16% and catalyst deactivation was observed during the first hour of time on stream (2). In another report, (3) Ni/a-Al2O3 catalyst was tested for syn-gas generation at 750ºC. The maximum methane conversion was 25%."

Jan 1, 2008

By Erich Hovestädt, Hans-Jürgen Odenthal, Christian Wuppermann, Herbert Pfeifer, Antje Rückert

"During the argon oxygen decarburization (AOD) process high-chromium steel melts are decarburized by oxygen and inert gas injection through sidewall nozzles and a top-lance. Due to the large amount of the injected processing gas, low frequency oscillations of the vessel can be observed. It is suspected that these oscillations can influence the converter's structure. The exchange of forces between fluid and the surrounding vessel is the focus of this study. An oscillation model was developed and tested, one objective being to limit the computational effort which is necessary for fully coupled and time resolved CFD and FEM simulations. Experimental results obtained from water-model studies as well as from on-sight measurements are available and were used in order to validate the numerical results. The authors' intention is a contribution towards a more in depth understanding of the factors influencing vessel vibration during the AOD process.IntroductionDuring the last four decades the AOD process has been established as a reliable and efficient refining process in stainless steel making. The injection of process gases (O2, N2, Ar) through sidewall nozzles shows advantages in mixing effectiveness compared to other injection geometries e.g. bottom blowing [1]. Stainless steel grades contain usually more than 10% chromium. With decreasing carbon content during the decarburization periods the tendency of chromium oxidation increases according to the varying chemical equilibrium which depends on the partial pressure of carbon-monoxide (CO) in the gas phase. That's why oxygen is gradually replaced by inert gases, usually argon or nitrogen, in order to lower the CO partial pressure and thus to minimize chromium oxidation. Despite the high injection velocity of approximately Ma = 1, the kinetic energy of the gas jets is consumed within a short distance from the nozzle exits due to the large density ratio between gas and melt of approximately 1:8000. With increasing distance to the nozzle exit, the initial horizontal velocity of the gas jet decreases and due to buoyancy force motion of the detached bubbles turns into a vertical direction. Subsequently a gas plume develops with its typical conical shape described by various authors [1-4]. Due to the drag force between gas bubbles and melt also the liquid phase is forced into a vertical motion. Near the free surface and the wall regions the melt flow is deflected in different directions. Subsequently, the typical flow pattern in the AOD vessel arises, as sketched in Figure 1 and described in literature [5-9]."

Jan 1, 2012

By Jinqian Zhao, Jiarong Li, Shizhong Liu

"Creep cavitation of in single crystal (SX) superalloy was investigated. The constant load creep tests, in single crystal superalloys DD6, were conducted at the conditions of 800°C/700MPa, 850°C/550MPa and 900°C/450MPa, respectively. It was found that there were square facets on the stress fracture surface, and microscopic cavities in the ruptured specimens in the vicinity of the fracture surface. Both the square facets on the fracture surface and microscopic cavities in the section of the ruptured specimens show the morphology of the same thing at the different views, namely creep cavities, which are take the form of flatten cuboid. In fact, creep cavities are the longitudinally tensiled creep cracks slowly growing during the stress tensiling. The factors of creep cracks nucleation and growth conditions include: (a) enough high temperature to activate diffusion (b) casting pores as nucleation origination (c) high strains and strain rates. Eventually, the instantaneous fracture mechanism of creep specimen is cleavage fracture.IntroductionFor the materials used in elevated temperature service, creep behavior has to be accounted for. It is well recognized that creep rupture in polycrystalline materials at high temperature occurs principally by the nucleation and growth of microscopic cavities at grain boundaries, followed by microscopic cavities linkage to form micro- and eventually macro-intergranular cracks[l,2]. Without the usual grain boundaries, SX superalloys have superior capabilities at high temperatures to polycrystalline superalloys, and have become an established feature of gas turbine technology where they are commonly employed in the manufacture of high performance blades[3]. A considerable amount of work has been done over the past tens of years, and many models for nucleation and growth of creep cavities have been proposed, however, those are mainly for polycrystalline materials.In order to improve creep resistance that single crystal superalloys, in which grain boundaries are removed, have been developed. Because there don't exist grain boundaries in SX superalloy, the mechanism of nucleation and growth of creep cavities must be different from that in polycrystalline materials.Understanding the formation and characteristics of creep cavitation is crucial to model the lives of single crystal superalloys.M. Marchionni and L.G. Zhao et al. found that there were square facets on the stress fracture surface [4,5]. Roger C. Reed pointed out creep cavities lie in the necked region[6]. In this paper, the effects on the formation of creep cavities are discussed, as well as the morphology of creep cavities and fracture mechanism of SX superalloys."

Jan 1, 2013

By Jian Li, S. Penttilä, P. Liu, W. Zheng, C. Bibby

"The materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. The current Canadian pressure-tube supercritical water (SCW) concept design requires core outlet temperature of 650 °C at 25 MPa with peak cladding temperature reaching as high as 850 °C. Aside from oilier challenges, there is currently very limited data on candidate stainless steels' corrosion resistance under this operating condition. Austenite stainless steels that include 316L, 304H, AL6XN and 3 l0S that cover a wide range of Cr contents are promising candidates for either direct in core applications or as base coating materials. However, their corrosion resistance has not been tested systematically under this stringent condition. In this study, these types of stainless steels are tested, and their corrosion resistances are compared.IntroductionThe Canadian pressure-tube supercritical water (SCW) concept will operate at a core outlet temperature of 650 °C at a pressure of 25 MPa, with potential peak cladding temperature reaching as high as 850 °C. High-temperature corrosion resistance is one of the key design requirements for fuel cladding components. As summarized by Allen [1 ], most testing to date has been carried out at temperatures below 730 °C. To date, SCW corrosion data above 600 °C is very limited. Even at relatively low temperature exposure to SCW (e.g. 500 °C), F/M steels develop a thick oxide layer rapidly, while some austenitic stainless steels develop thinner surface oxide. Ni based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of intermetallic precipitates [2-5]. Dissolution of major alloying components from all of these alloys could also pose significant problems for downstream piping [6]. Kaneda et al. [7] suggested some modified stainless steels provide better SCW general corrosion resistance, with no sign of SCC under the slow-strain rate test.Cho [8] suggested that as the Cr content increase, general corrosion resistance improved at 510 °C and 25 MPa. However, similar to Cho's work, most of the SCW corrosion resistance assessments were based on weight change measurement. This can be unreliable due to potential exfoliation of thick oxide film. Besides, there have been no systematic SCW corrosion resistance tests for candidate stainless steels under higher temperatures. SCW corrosion rate increase dramatically for alloys tested at 600 °C [1]. It is also important to understand the role of major alloying elements under this stringent operating condition, not only for fuel cladding components' materials selection, but also for coating materials development."

Jan 1, 2013

By Jie Li, Liangxing Jiang, Yexiang Liu, Junfeng Gui, Bo Hong, Xiaocong Zhong, Yanqing Lai, Xiaoying Yu

"Pb-based alloys with Pr and Ag were prepared in vacuum electromagnetic induction furnace. The tensile strength, corrosion rate and anodic potential in sulfate solution were measured, and the experimental data were analyzed according to the metallographic phases of alloys, the micromorphology and composition of their oxide films. The results show that, with the addition of Pr, the ultimate tensile strength and corrosion rate of pure lead were increased, and the anodic potential decreased. The extra addition of Ag can improve the properties of alloy further. Comparing with Pb-Ag0.8 alloy which is widely used in zinc electrowinning industry, the ultimate tensile strength of Pb-Ag0.6-Pr2.0 alloy was increased by 31.75%, the anodic potential under 50mA/cm2 was decreased by 30m V.IntroductionIn zinc electrowinning industry, the Pb-Ag (0.5-1.0 wt.%, 0.8wt.% normally) anode is widely used as an insoluble anode['l. It can meet the basic requirements, but still has several problems such as high oxygen evolution over-potential (about 860mV), unsatisfactory corrosion resistance, lead contamination of the cathode product and high consumption of Ag etc.In order to reduce the energy consumption, enhance the corrosion resistance, improve the product quality and reduce the consumption of Ag (or even dispense with it), much research has been done, mainly focusing on Pb-based alloy anodes and Ti-based coated anodes. Detailed investigations have already been carried out on binary alloys (Pb-Ca and Pb-Co), ternary alloys (Pb-Ag-Ca, Pb-Ag-Ti, Pb-Ag-Sn, Pb-Sr-Sn, and Pb-Ca-Sn) and quaternary alloys (Pb-Ca-Sr-Ag, Pb-Ca-Ce-Ag, and Pb-Ag-Sn-Co)[Z-4l, Although these anodes can effectively reduce the consumption of Ag, only the Pb-Co and Pb-Ag-Sn-Co anodes perform well with regard to reducing the anodic potential. However, their complicated manufacturing conditions restrict further commercial use.Besides its application in nonferrous metal electro-winning industry, Pb-based alloy is also used as grid alloy for lead-acid battery, serving as active materials supporter and current collector. In order to enhance the corrosion resistance and deep-cycling performance, reduce the impedance of the corrosion film, the addition of appropriate rare earth elements into anodic grid alloys has become a research focus. Studies proved that RE can enhance the mechanical strength of grids, inhibit the formation of anodic Pb(II) film on the surface of grids and then reduce the impedance of the film[ 10-12l."

Jan 1, 2013

By Gaifeng Xue, Lei Zhang, Xia Liu, Lina Wang, Pu Liu, Benquan Fu

"Experiments were conducted to investigate the behavior of the integrated process with a three-dimensional electrode reactor combined with Fenton process for coking wastewater treatment. Effects of initial pH value, reaction time, H20 2 dosage, Fe2+ dosage on Total organic carbon (f OC) removal rate were investigated. The kinetics of degradation of TOC from coking wastewater by three-dimensional fluid bed electrode reactor combined with Fenton process was also studied. Experimental results shows that three-dimensional fluid bed electrode reactor combined with Fenton process had better synergic effect, average 17.4% TOC removal rate was improved within an hour. It was found that TOC degradation in coking wastewater followed a pseudo-first-order reaction kinetic model. The optimum degradation efficiencies of TOC were up to 60% as pH3.4, 3.5 mM ofFe2+ andl.2-1.8ml/L H20 2 in 90min reaction period. Furthermore, the integrated process showed a rapid reaction performance at a low temperature within a short reaction time and remained high efficiencies for TOC removal. Overall, the integrated process was proved feasible for coking wastewater treatment in practical applications.IntroductionCoking wastewater is generated from coal coking, coal gas purification, and by-product recovery processes of coking, which is composed of phenolic compounds, heterocyclic compounds, polycyclic aromatic hydrocarbons, ammonia, cyanide, polycyclic nitrogen-containing aromatics, acyclic compounds, etc. Most of these constituents are refractory, poor biodegradability, toxic and carcinogenic['-31. Currently, coking wastewater is usually treated by different forms of A/O biological nitrogen removal process as the primary treatment process, but the aforementioned processes are not efficient enough to meet the requirements from the National Discharge Standard in China (GB13456-1992). According to the continuous requirement on improving environmental protection for coking industry (revised 2008), increasing wastewater utilization ratio and reducing discharge of effluent in the coke industry has to be implemented for cleaner production and sustainable development. Therefore, advanced technologies need to be developed to treat coking wastewater and reutilize the product as industrial cooling water, which would be one of the best choices to achieve zero discharge of wastewater and reduce water consumption per ton of steel [4-51 . In this study, three-dimensional fluidized bed electrode reactor combined with Fenton process was adopted to advanced treatment of coking wastewater, and the effects of operating conditions, including H2O 2 dosage, Fe2+ dosage, initial pH, and reaction time on TOC removal rate, were investigated. Meantime, study of kinetics of reaction was estimated."

Jan 1, 2013

By Xuewei Lv, Maojun Zhou, Xiaobo Huang, Rende Zhang

"The characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. In this study, an evaluation of the roughness of the iron ore particles, with the measurements of size distribution and the measurements of specific surface area with the liquid nitrogen absorption, was developed. The main theory of this method is the fact that the roughness of the particle influences the specific surface area apparently. The specific surface area of the particles can be measured with the laser diffraction method and the liquid nitrogen absorption method. The influence of the surface roughness of the particle can be measured with the nitrogen absorption and cannot be measured with the laser diffraction. Therefore, the roughness can be got by comparing the specific surface area with two measurement methods.IntroductionThe characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. There are three main methods for measuring the size distribution of mineral particles: sieving, laser diffraction, and sedimentationl). Many techniques involve sedimentation such as the Horiba2, 3) and the Cyclo-sizer1). In the mineral industry, size distribution is usually determined by sieving because it can be carried out accurately for all particle sizes larger than 45 . The preferred method to obtain the size distribution of finer particles is laser diffractometry. The technique has several advantages: it produces measurements in a few minutes with considerably less labor compared with the cyclo-sizer and for a range of sizes considerably wider in comparison with the sedigraph4). The equivalent-sphere size distribution reported by laser diffractometry is valid for metallurgical calculations and can be routinely used in mineral processing plants. The surface area of the particles can be measured by the BET method of nitrogen adsorption, or it can be calculated from the size distribution. However, the latter calculation requires the size distribution to be accurately known across the whole size range, and assumptions have to be made about the shapes and surface roughness of the particles and presence or absence of pores (see below). The BET method is based on the physical adsorption of gas over the whole exposed surface area and measures the surface area stemming from the roughness and open pores on the surface of the particle5). The calculation of the surface area from the size distribution is usually based on the assumption that all the particles are smooth spheres, without considering the shape and/or roughness of the particles. Determining the surface roughness of the particle with these methods, is the objective of this study."

Jan 1, 2012

By Y. Moriya, Y. Sadayoshi, Y. Nonogaki, Y. Takeda

"Preparation and growth processes of CaF2 on Si(111) and of . InxGa1-x,As islands on CaF2 by molecular beam epitaxy (MBE) are described. It was found that first of all the Si(111) surface treatment process to obtain the 7x7 reconstructed structure was necessary to ensure the cleanness of the surface and to grow a flat and high quality CaF2 on it. Growth of InxGa11-x,As islands on CaF2 was tried by droplet heteroepitaxy using the same MBE reactor. In,GaxGa1-xAs islands were successfully grown epitaxially, and the size and density of the islands dependent on the In composition were investigated.IntroductionThough semiconductor/semiconductor heterostructures are widely used for many device applications, small band off-sets of the conduction bands and the valence bands restrict the utilization of the intra-subband transitions to far-infrared regions. With InAs as the quantum well and fluorides as the barrier layers, we can design three-electronic-level systems in the infrared region, which is the low loss transmission window of the silica optical fibers. To realize those structures, we have grown InxGa1-xAs islands on CaF2 thin films that were epitaxially formed on Si(111) substrates by molecular beam epitaxy. By the droplet heteroepitaxy that we invented, the InxGa1-xAs islands with height of -10 nm have been obtained successfully. Optimum processing to obtain atomically smooth surfaces of Si and CaF2 and high quality InxGa1-xAs islands is reported.ExperimentsMBEMachineCaF2 was grown on Si(111) and InxGa1-xAs islands were grown on CaF2 successively by MBE. The MBE machine consisted of a growth (or reactor) chamber and a loading chamber. The reactor chamber was equipped with Ga, In, As and Er metal source cells and CaF2 and BaF2 source cells. Cell materials were P-BN for Ga, In and As metals, and were graphite for CaF 2, BaF 2 and Er to avoid reaction with BN cells. The electron gun and screen were attached to the reactor to observe the RHEED pattern during the substrate surface treatment and the growth of CaF2 and InxGa1-xAs islands. The substrate manipulator was designed to heat up the Si substrate up to 1,200°C for the surface cleaning. The QMS was also equipped to analyze the residual gas species in the reactor chamber. The base pressure of the reactor chamber was 2-5x10-11 Torr, being pumped by ion pump and the liquid nitrogen shroud"

Jan 1, 2000

By Nagahiro Saito, Takashi Nishimura, Takamichi Ichikawa, Akio Fuwa

"Yttria-stabilized zircohia (YSZ) has high potential to be used as solid-oxide fuel cell (SOFC) electrolyte. However, the high efficiency of SOFC has not been yet achieved due to the high internal resistance of bulk electrolyte. The resistance becomes lower with the decrease in the electrolyte thickness. Thus, the decrease in electrolyte thickness leads to lower internal resistance. . The aim of this study is as follows: (a) to prepare the thin films of YSZ by inductively-coupled RF plasma-enhanced metal organic chemical vapor deposition (PEMOCVD) process using Zr(t-OC4H9)4,Y(DPMh and oxygeil, and (b) to reveal the relationship between the structural characterizations and the process parameters.1. IntroductionYttia-stabilized zirconia (YSZ) has, been widely used as not only heat-resistant materials but also the components in automotive oxygen sensors, electrolytes of solid-oxide fuel cell (SOFC)(1)(2) and the buffer layers for the high-temperature superconductor because of its low thermal conductivity, good mechanical properties and high ionic conductivity. However, it is said that the internal resistance of the bulk electrolyte is too high to be appropriate as a solid electrolyte for high-efficient SOFC. The authors believe that the thin YSZ electrolyte can give a high performance to characteristics SOFC, since the internal resistance becomes lower with the decrease of electrolyte thickness. Thus the process technology to prepare YSZ thin films is desirable and must be established.In recent years, the YSZ thin films have been reported by chemical vapor deposition (CVD), thermal CVD using metal chlorides (MC) of ZrCl4 and YC(3)(4), thermal CVD using metal organic compounds (MO)(5)(10) Zr(t-OC4H9)4 and Y(C11H19O2)(11) and plasma-enhanced (PE) CVD using MO. Here, these methods are called MCCVD, MOCVD and PEMOCVD. MCCVD has two disadvantages; a large quantity of chlorinated impurities in deposited films and high processing temperature (> 1273K). This high processing temperature leads to damage of substrates in particular, so the application of this technology is limited. On the other hands, the processing temperature by MOCVD becomes and is lower. Unfortunately, the accurate vapor pressures of these metal organic compounds have not been, known so: that it is difficult to control the composition and the film thickness by MOCVD method well. Moreover, the large amount of carbonic compounds in the films prepared by MOCVD method is produced. However, plasma-effect has been reported to decrease large amount of the carbonic impurities by PEMOCVD. However, PEMOCVD has many reaction parameters in plasma processing; the geometry of experimental apparatus, radio frequency, electronic power input and so on. Thus, the general understanding about the relationship among reaction parameters, the composition and crystal structure of thin deposit film by this method has not yet been established."

Jan 1, 2000

By Chikabumi Yamauchi, Mitsuru Tanahashi, Tsuyoshi Taniguchi, Nobuo Furuta, Toshiharu Fujisawa

"It is essential to clarify the equilibrium relations among nonmetallic inclusions of the Mn0-SiO2-CrOx system and molten stainless steel in order to control non-metallic inclusions formed by the deoxidation of stainless steel with silicon. In the present study, the phase equilibria of the MnO-SiO2-CrOx system were measured by conducting the following experiments under controlled oxygen partial pressure, Po2, at 1873 K:1) Phase equilibria of the MnO-Cr20 3 binary system were measured for Po2 = 2 x 10-6 ~2 x 102 Pa.2) Phase equilibria of the MnO-SiO2-CrOx ternary system were measured for Po2 = 2 X 10-6 Pa.Based on the results, the phase diagram of this ternary system was established under the condition of the Si-deoxidation process of stainless steel (Po2 = 2 x 10-6 Pa and T = 1873 K).IntroductionAt the deoxidation stage in steelmaking process, generally multiple deoxidizers participate in deoxidation reactions, and the composition of deoxidation products ""non-metallic inclusions"" greatly varies depending on deoxidizing efoments and their contents. In order to control non-metallic inclusions formed by the refining process of steel, it is essential to clarify the equilibrium relations among non-metallic inclusions and molten steel.Especially, during the refining process of stainless steel, nonmetallic inclusions in molten steel seem to- change as follows. After the oxidation refining, Mn-chromite is formed in molten steel as non-metallic inclusion. By the deoxidation with silicon addition (mainly less than 1 mass%), Mn-chromite inclusions are changed their compositions to Mn-silicate. Segawa et al.[l] have reported the effect of amount of silicon addition on composition and mass ratio· of non-metallic inclusions during the Sideoxidation process of 18Cr-8Ni stainless steel at 1873 K, as shown in Figuri; L At higher silicon content than 0.5 mass%, only Mn-silicate was identified as non-metallic inclusion. On the other hand, at lower silicon content, both of Mn-chromite (MnO Cr2O 3) and Mn-silicate were identified. However, the thermodynamic and the kinetic analyses of the above-mentioned Sicdeoxidation process have not been made due to lack in the thermodynamic data for the non-metallic inclusions· of the MnO-SiO2-CrOx system, such as the phase diagrams, the activities of the components, and the free energy of intermediate compounds. In relation to the phase diagram of this system, those of the MnO-SiO2 [2] and the SiO2-Cr2O 3 [3] binary systems have been only reported"

Jan 1, 2000

By Xiaohui Li, Lianyun Liu, Hongmin Zhu, Chunfang Zi, Kai Huang, Hongjie Li

"The dissolution kinetics of steelmaking slag in pure water was studied, and the relative influential factors were investigated. The dissolution behavior of slag particles in water was well described by Noyes–Whitney equation, and for this kind of sparingly soluble rigid mineral this simple model was extensively applicable to describe their dissolution process. Experimental data were also obtained to confirm the significant promotion effect on the growth of some algae.1 . IntroductionIt has been found that the population of phytoplankton distributed in the ocean was significantly related to the concentration of some elements [1]. For example, silicon and iron were very low in the high-nitrate low-chlorophyll (HNLC) areas, which was the main factor limiting phytoplankton and other biomass growth in these open ocean surface water [7]. The silicon and iron-rich test also confirmed that the supply of these elements had the direct effect on the growth of phytoplankton processes at HNLC areas [2-8]. So in order to promote the growth of phytoplankton in these ocean areas, providing some of these elements into these ocean areas is a natural idea for choice. Steelmaking slag is a good resource for consideration because it usually contains silicon, iron, phosphorus and other elements that are necessary for the growth of phytoplankton [8-10].Haraguchi has proposed the following idea that [5-6], if steelmaking slag can be spread to the open ocean, the trace components like silicate, iron and phosphate as the indispensable nutrients for the growth of phytoplankton, will be leached into the sea water, not only promoting the growth of phytoplankton, but also making good use of these huge amount of steelmaking slag produced every year. Based on this idea, they have carried out studies in recent years and they found that silicon and iron in the slag could be extracted into seawater effectively and play a positive role in the growth process of many algae. About the dissolution of the steelmaking slag, the Japanese scholars' research work mainly focused on the thermodynamic analysis of its dissolution possibility, and in the process of dissolution they tried to adjust the pH value of the seawater by continuously adding hydrochloric acid, which was deviated from the natural conditions of dissolution, and so the laws drawn under these special conditions can not give the identical guide to the practical application. Therefore, it is quite necessary to investigate the dissolution behavior of the steelmaking slag in the seawater at the normal pH range without adjustment to simulate the dissolution possibility under the natural conditions. In the present study, the silicon extraction behavior from the steelmaking slag was investigated and the dissolution kinetics in this process was also discussed in detail. Further studies were also performed here to evaluate the promotion of steelmaking slag on the growth of algae."

Jan 1, 2011

By Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By P. K. Jimack, C. E. Goodyer, A. M. Mullis, P. C. Bollada

"We review the application of advanced numerical techniques such as adaptive mesh refmement, implicit time-stepping, multigrid solvers and massively parallel implementations as a route to obtaining solutions to the 3-dimensional phase-field problem with a domain size and interface resolution previously possible only in 2-dimensions. Using such techniques it is shown that such models are tractable even as the interface width approaches the solute capillary length.IntroductionMulti-scale modelling impinges upon many areas of science, engineering and technology where the interplay between processes occurring on disparate length and/or timescales can affect the properties of systems in a complex, and sometimes unforeseen, manner. One such is the processing of materials where interactions at the atomic scale, through the nano- and microstructural scale can have a profound affect on the macro-scale response of engineering components. Here we focus on one such problem, the crystallisation of alloy melts, to illustrate how a range of advanced numerical techniques make the modelling of such systems tractable.The modelling of solidification structures, in particular the growth of dendritic crystals, is a subject of intense and enduring interest within the scientific community, both because dendrites are a prime example of spontaneous pattern formation and they have a pervasive influence on the engineering properties of metals. For alloy systems, which form the vast majority of engineering materials, solidification involves the rejection of both solute and latent heat from the growing solid, forming a coupled diffusion problem in which both the chemical and thermal diffusion equations should be solved. The multi-scale nature of this problem arises from the disparity between the thermal and solutal diffusivities for most liquid metals, which are typically 10-5 m2 s-1 and 10-9 m2 s-1 respectively. The ratio of these two, referred to as the Lewis number (Le =Dia), is therefore typically of the order 10,000 and gives a measure of the multi-scale nature of the problem. In fact, in many cases the thermal diffusivity is so much larger than its solutal counterpart that thermal diffusion is considered instantaneous, wherein the system can be approximated as isothermal such that the multi-scale calculation does not need to be performed. This is certainly a reasonable approach in most conventional castings. However, there is a class of solidification problem in which this approach is far from satisfactory, namely Rapid Solidification (RS). The application of isothermal phase-field models in such situations are highly likely to produce spurious results or to fail totally, particularly for temperatures below To (the temperature at which the free energies of the solid and liquid phases are equal at the concentration of the bulk alloy), wherein partitionless solidification may occur."

Jan 1, 2013

By Thomas Schuman, Jaan Kers, Lucas N. W. Damoah, Xiangjun Zuo, Lifeng Zhang

"Rapid technological innovation has propelled the use of electronic equipment leading to the generation of more and more waste electrical and electronic equipments (WEEE). Printed wiring board (PWB) is a component made of one or more layers of insulating material with electrical conductors. To investigate an environmentally friendly process to recycle PWBs, PWB samples with and without additives were pyrolyzed. Liquid, gas and solid products were achieved with different conversion fraction. Analysis of the exhaust gases from the experiments using GC-MS and MS showed that without CaCO3 additives poisonous gases such as C6H6 and HBr were produced which were adequately controlled if CaCO3 was added.IntroductionPyrolysis is one of the best methods for treating complex mixtures of waste polymers and to recover the material and energy content. The process consists of thermal decomposition at moderate temperatures in total absence or small amount of oxygen in which the structures of polymers break down into smaller intermediate products "". The decomposition temperature of a substance is the temperature at which the substance breaks up into smaller substances or into its constituent atoms 2). Thermal treatment of PWBs were reported using DC Arc Plasma furnace 3), and fixed bed reactor 4). One drawback in dealing with thermal treatment of PWB scraps is the likely production of super-toxic halogenated dibenzodioxins and dibenzofurans from the bromine containing structures. Pyrolysis of organic materials contained in waste PWBs leads to the formation of gases, oils, and chars which can be used as chemical feedstock or fuels ""'. Dehalogenation of the pyrolysis product of electronic scraps is essential to make it commercially acceptable. It would be obviously the most advantageous solution as pyrolysis and dehalogenation are carried out simultaneously. Reported pyrolysis investigations are at experimental stage and have been carried out in vacuum, molten salt, fluidized bed, rotary kiln, entrained, stationary, and moving bed reactors 7). Comparing to the incineration and combustion of PWBs, the pyrolysis process has several characteristics: 8'"">) 1). Converting the organic solid substance into fuel gas, fuel oil and carbon-black as storage energy; 2) Emitting toxic substances such as sulfur, bromine and heavy metals in wastes; and 3) Keeping metals from being oxidized. Although many researches into the pyrolysis of PWB wastes have been reported, most of the works have been carried out using analytical pyrolysis techniques or very small batch reactors ""~'5). Also, most of the works for the pyrolysis of PWBs haves concentrated on the composition of the organic products, particularly the brominated organics. The current study is to investigate the pyrolysis of PWB powders in a small TG-DTA scale and a 50-gram tube furnace scale."

Jan 1, 2011

By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Vladimir Lobanov, Vladimir Skorohodov, Andrew Evdokimov, Ural State Technical University 19, Boris Radionov

"The bulk of raw materials in metallurgy of secondary platinum metals are the wastes such as multilayered ceramic-metal systems, e.g. the spent catalysts of the chemical and petrochemical industry, automobile catalysts, etc. Due high chemical resistance of a ceramic basis the extraction of platinum metals by leaching even at very fine crushing is poor. The study of sorption leaching of platinum and a palladium from the spent automobile catalysts are carried out. The average content of PGM is 0.5%. A few methods of raw materials sampling were compared: 1) direct hydrometallurgical leaching of platinum metals from the fine-grained catalyst and atomic absorption analysis of the obtained solutions; 2) fusion to a metal or sulphidic collector of precious metals with the alloy analysis by direct spectrometry; 3) fusion with dissolution of a precious metals collector and atomic absorption analysis of PGM in solutions. Leaching allows detecting out no more than 90% of a palladium and 80% of platinum. Fusion to a collector gives the best results at the chemical ending. Researches on sorption leaching are executed. Under optimum conditions the extraction of platinum metals to concentrates is comparable with similar indicators of collector fusion.The large part of raw materials in metallurgy of secondary platinum metals are the multilayered or tridimensional ceramic-metal systems, in particular the spent catalysts of the chemical and petrochemical industry, automobile catalysts, ceramic-metal condensers, etc. The content of the sum of PGMs can be from hundreds grams per ton to several percent. For processing of such materials the hydrometallurgical methods of platinum metals leaching by various reagents are used commonly. High chemical resistance of the ceramic basis covering the metal particles causes low recovery even at very fine grinding. Other fundamentally different method of catalysts opening includes dissolution of the ceramic basis in the solutions of hydrofluoric acid and the subsequent recovery of platinum metals from insoluble residue. Application of this method is associated to use of corrosive medias and appropriate equipment. Fusion of the specified materials with collecting of PGM by copper, nickel or lead at the specialized enterprises provides higher extraction in semiproduct. At the same time, complexity and duration of the subsequent extraction of platinum metals concentrates causes high total cost per unit. Thereby this method is economically acceptable only for rather poor raw materials (no more than 0,1%). Undoubtedly, that the raw materials with the high content of PGM are reasonable to process by individual technology. In the present work the processing of some kinds of ceramic-metal raw materials, particularly automobile catalysts (neutralizers) with various collectors at the conditions of a target fusion are investigated."

Jan 1, 2008

By Toshiyuki Hashida, Victor M. Lopez-Hirata

"Small-punch tests and determination of fracture toughness JIC were conducted at 4 and 77 K on new cryogenic JN1, JJ1 and JK2 austenitic stainless steels, after isothermal aging. Equivalent fracture strain ?qf determined by measuring the reduction of thickness in the small-punch test specimen. A linear dependence of JIC on ?qf was found in these new materials. Regression analysis of experimental data produced the following linear relation JIC = 1304.1 ?qf + 8.09 [kJm-2]. An analysis of present work relation was pursued on the basis of material properties and evaluation method of he. Results showed that the slope value has a strong dependence on material yield strength and JIC evaluation method. This linear relation is useful for the evaluation of fracture toughness JIC, measuring the equivalent fracture strain ?qf by means of small-punch test. Thus it can be useful for assessing the degradation of fracture toughness in small areas such as, the heat-affected zone in welded components.IntroductionCryogenic structural materials for superconducting magnets of fusion nuclear reactor are required to possess a good combination of strength and toughness. The mechanical properties are required beyond the capability of conventional austenitic stainless steels [1]. New cryogenic JN1, JJ1 and JK2 austenitic stainless steels were developed by the Japan Atomic Energy Research Institute (JAERI) [1]. The structure of superconducting magnets is constructed by welding of 200 = thick plates of these steels, which are solution treated at high temperatures and then water-quenched to avoid intergranular precipitation. However, the welding process involves heating and cooling [2], which cause microstructural changes in both base metal and weld. In this heterogeneous microstructure, it is important to estimate the fracture toughness of these materials at cryogenic temperatures. Therefore, it is necessary to evaluate the effect of aging process on the fracture toughness behavior of these new steels. To determine the cryogenic fracture toughness, the elastic-plastic JIC value has been co=only used [2]; however, the specimen size is much larger than heat-affected zones in welded components. Small-punch (SP) testing method, employing miniature specimens, has permitted to evaluate the fracture toughness behavior at different temperatures in different nuclear reactor materials [3,4]. Mao et al. [5,6] and Misawa et al. [7] found a linear relation between JIC value and equivalent fracture strain ?qf, determined by SP method in non-ferrous alloys and ferritic steels at room temperature and austenitic stainless steels at 4 and 77 K, respectively. So that, this kind of correlation would be very useful to assess the fracture toughness JICe values by means of SP test in small zones of welded components."

Jan 1, 2012

By Guanghua Wen, Jian Li, Mingmei Zhu, Fei Xiong, Shengjian Cao

"Small inclusions removal from molten steel in a continuous casting tundish by gas bubbles, which were generated in the turbulent flow region by introducing inert gas, was analyzed theoretically and the inclusion-bubble adhesion and flotation process was also observed by high-speed photo-graph in water model. Results showed that small inclusions in the range of 20-50µm removal from molten steel by bubbles flotation involves three stages: contact, adhesion and flotation. The inclusion-bubble adhesion processes include two ways: inclusions adhering to the upper part of the bubble and inclusions adhering to the lower part of the bubble. As the bubble floats up, the number of inclusions adhering to the bubble are increased. The proper size of bubbles, which could enhance small inclusions removal efficiency, should be controlled in the range of 1-2mm.IntroductionReducing inclusions content in molten steel is a very important way to improve quality of steel, and one of the main tasks in steel making process.A variety of methods have been used for inclusions removal in molten steel. At present, the main approaches to remove inclusions are gas stirring, slag cleaning, filtering, centrifugal separating, and by means of ultrasonic or electromagnetic field. Among these techniques, gas stirring is the most widely and effectively method for inclusions removal. Inclusions in molten steel will be aggregated and generated to form larger size inclusions, and subsequently floated to the surface of molten steel by buoyancy; meanwhile, some inclusions will be adhered to bubbles and floated together to metal-slag interface where inclusions are absorbed by the covering slag layer. Some research work showed that flow behaviors of small bubbles are different from that of big ones [1-2], and smaller bubbles are more efficiency for fine inclusions removal in molten steel.There are many methods to generate bubbles. During steelmaking process, highly turbulent flow in the ladle shroud can split introduced inert gas into small bubbles, which enhances the removal of fine inclusions from molten steel. Turbulent flow of molten steel injected into tundish from ladle shroud has a high speed and it is a strong turbulent area in continuous casting. The gas can be introduced into the shroud below the slide gate. The high turbulence flow would break up the gas into small gas bubbles. Fine inclusions will be easily adhered to small bubbles and subsequently floated to the surface of molten steel. Generation of small bubbles in ladle shroud have been studied in some literatures [3-4]. Some research have analyzed the fine inclusions removal with injecting gas from the ladle shroud by mathematical simulation, and the results show that the refining method can obviously improve the removal efficiency of fine inclusions in tundish [5-8]."

Jan 1, 2013