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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 Ehsan Vahidi, Fereshteh Rashchi, Ataollah Babakhani, Alireza Zakeri

"The synergistic effect of Cyanex 302 on solvent extraction of nickel and cadmium from sulfate solution with D2EHPA diluted in kerosene was investigated with the aim of increasing separation efficiency. Experiments were carried out within a pH range of 0.1-5.0 using sole D2EHPA and D2EHPA-Cyanex 302 mixtures in different ratios. Increasing Cyanex 302 to D2EHPA ratios in the organic phase caused a left shifting of the extraction isotherm of cadmium and a right shifting of the extraction isotherm of nickel. As a result, optimum separation was found with a Cyanex 302 to D2EHPA ratio of 0.1M:0.5M. In the present system, effect of a modifying reagent such as TBP was studied. The influence of various diluents including kerosene and carbon tetrachloride was also investigated.IntroductionBatteries are popular sources of portable energy. Ni-Cd batteries are manufactured in two main groups of small domestic cells and large industrial batteries with 80% being in domestic use. Ni-Cd cells have various uses, for example in cordless electric utensils, cordless telephones, airplane engine starters, and communicational distribution systems [1].Depleted Ni-Cd batteries are classified as hazardous waste since nickel and cadmium are heavy metals and suspected carcinogens. Given the risk associated with uncontrolled disposal, directions for issuing legislation on disposal and recycling of used batteries have been made in industrialized countries [2]. Recycling of Ni-Cd batteries is important from both economic and environmental points of view. Different methods have been used for recycling these wastes through pyrometallurgy [3], biotechnology [4,5], and hydrometallurgy [1,2].Due to the advantages of hydrometallurgical processes, several studies have been implemented on leaching and solvent extraction (SX) of the used Ni-Cd batteries. Leaching of batteries is usually done in sulfate or chloride media; while solvent extraction has been used in different extractants: two-stage solvent extraction by D2EHPA and Cyanex 272 [6]. Solvent extraction of Cd from leach solutions has been studied using various extractants; Cyanex 301 [1], D2EHPA [7], Cyanex 302 [8], Cyanex 923 [9], Cyanex 272, Tops 99, PC88A [10]. Application of phosphorus based extractants for the solvent extraction studies of Ni such as TOPS 99 [11], D2EHPA [12], Cyanex 272 [2], has been investigated. Separation of Cd(ll), Ni(II), and Co(ll) from chloride leach liquor of spent batteries [13], were explored in the earlier studies. Cd extraction with D2EHPA involves co-extraction of both Ni and Co [14], which causes issues in the separation process efficiency."

Jan 1, 2012

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 M. Omneya El-Hussaini, M. Galal Abdel Wahab, A. Mohamed Mahdy, M. Fathi El Shahat

"Um-Gheig Pb-Zn representative sample was collected from the main adite of Um-Gheig mine along Red Sea coast in Egypt. Its chemical analysis shows that, it contains 16% Zn, 2.3% Pb, 0.1% Cd and 0.1% B as elements of interest. After H2SO4 agitation leaching, the chemical composition of Um- Gheig Pb-Zn deposit ore residue assayed 2.26% Pb, 1.5% Zn, 0.085 % B and 0.01% Cd. This residue was leached with 20% HCl at S/L ratio 1/3 for 2 hours at 80o C. The chloride leach liquor was found to contain 18 g/l Pb, 13 g/l Zn, 0.1 g/l Cd and 0.75 g/l B with the corresponding leaching efficiencies 79%, 86%, 100% and 88% respectively. Lead was precipitated from the chloride leach liquor using concentrated H2SO4 to obtain PbSO4 with precipitation efficiency 96%. While boron was extracted by the selective resin Amberlite IRA743 with loading efficiency of 80%. On the other hand, Zn and Cd were precipitated using Na2S solution with 86.7% and 100% recovery efficiencies respectively.IntroductionLead-zinc ores occur in Egypt in a few localities distributed along the Red Sea coast between El Qusier and Ras Banas.. The reserve of the ore deposits has been estimated by Soviet and German Experts to be about 900,000 Ton, [1]. Onal et al., [2] recovered Pb from Pb–Zn sample containing 10.17 % Pb and 10.98 % Zn from Aladag in Turkey. El-Sherif, [3] used concentrated HCl to leach lead-zinc ore sample of Um-Sammuki area in Egypt. As had been published by Marchioretto et al. [4], the precipitation of heavy metals with lime, sulfide and caustic soda are the most commonly used economical methods for metal removal. Lead was completely removed from the anaerobically digested sludge by precipitation with NaOH and Na2S at waste water treatment plants. Mahdy et al., [5] had successfully extracted boron from the bittern solution of Qaron Lake by ion exchange resin (Amberlite IRA 743). The extraction of boron was mainly depending upon the pH value. They extracted 80% of boron at pH 5.5, while at pH 3.9 about 74% boron was extracted. Kabay et al. [6] used the column-mode to remove 1g/l of boron from geothermal waste water of the Kizildere-Geothermal Power Station by using Diaion CRB 02 Nglucamine- type chelating resins. In this regard, the removal of lead, cadmium and boron allow the residue to be reclassified as non hazardous material."

Jan 1, 2008

By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By Yotamu Hara, Animesh Jha

"High Curie temperature and large magnetic anisotropy make cobalt an important magnetic material for power engineering applications of magnets operating above ambient. It is also an essential constituent of modem lithium - cobalt oxide batteries, without which modem electronic gadgets will be functionless. Both these applications of cobalt save energy and reduce C02 emission. Ironically, however the production of cobalt from copper and nickel smelting in the world remains one of the least energy efficient process. The paper analyzes the energy balance, material and process chemistry of overall cobalt recovery and the waste generated, which entail the process limitations. We discuss a novel approach for the reduction of sulphide minerals with CaS04, permitting better separation of metals from slag and generating higher concentrations of S02. Such an approach may seem to be an alternative energy efficient option for processing and further purification of cobalt in metallic form. The results are discussed in the context of process thermodynamics and reaction kinetics for Coalloy production.IntroductionCopper sulphides bearing minerals are predominantly associated with iron and cobalt sulphides minerals. Carrollite (CuC02S4) is a mineral that has both copper and cobalt sulphides [1,2], which may also contain FeS, by substituting either Cu2+ or Co2+ ions in mineral lattice. On smelting copper - cobalt - iron sulphide concentrates, some parts of the cobalt often partition to matte at preferentially low oxygen potential by forming eventually an alloy phase with copper, however a significant fraction is often lost into an oxide slag rich in iron and silica. The slag heaps accumulated in the Copperbelt region in Zambia from last 60 years of mineral processing and metal extraction is reported to be 0.3 to 2.6 wt% of cobalt element, which is high [3]. Cobalt is also available in smaller concentrations in the copper smelting and converter slag, as reported in the investigations on the recycling of such slag materials using leaching with ammonium salt [4], iron chloride [5], and sulphuric acid [6], and solvent extraction [7].The recovery of cobalt from slag, irrespective of the techniques researched so far, does not seem energy efficient because the molten slag at 1300°C is quenched by losing thermal and chemical energy. The quenched slag is again reheated to above room temperature for leaching and above liquidus for carbothermic reduction of residual cobalt oxide. For example, in Mintek DC arc smelting [3], 80% of cobalt and 95% nickel are recovered by expending 600 kW per tonne. Assuming that the mineral carrollite is the starting phase, the univariant calculations for the Co-Ca-Si-S-0, Fe-Ca-Si-S-0, and Co-C-Si-S-0 systems are shown in Figure la, lb, and le, respectively at 1573 K."

Jan 1, 2012

By Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

By Mohamad Omarei, S. M. Sadrameli

"The aim of this research work was to produce biodiesel (fatty acid methyl esters, FAME) from canola oil using KOH loaded on y-Al203 support as a heterogeneous catalyst. Different parameters such as effects of the molar ratio of methanol to oil, catalyst amount and reaction time on the yield were investigated. Scanning electron microscope (SEM) and X-ray diffraction (XRD) were used for characterization of the catalysts. A biodiesel yield of 86.67% was obtained under catalyst preparation and transesterification conditions of calcinations temperature of 773 K, 4 h of reaction time at 338 K, and using 3.5 wt% catalysts and molar ratio of methanol/oil of 15:1. The leaching of potassium species in the spent catalyst was observed.1. IntroductionBiodiesel is an eco-friendly and alternative energy source for diesel engines that can be synthesized by transesterfication of vegetable oil or animal fat with alcohols [1 ]. There are four principal approaches to the synthesis of biodiesel involving the transesterification of the triglycerides of the plant oils and animal fats: base catalysis [2], acid catalysis [3-5], employing supercritical alcohol conditions [6] and enzyme catalysis [7]. The commonly used homogeneous catalysts are NaOH, KOH and their alkoxides. Homogeneous alkali-catalyzed transesterification is much faster than acidcatalyzed transesterfication [8]. However, a large amount of water is required to transfer the catalysts from the organic phase to a water phase after the reaction. Therefore, it is considerably more costly to separate the catalyst from the produced solution [9]. These disadvantages could be removed by use of a heterogeneous catalyst [10]. The use of heterogeneous catalysts eliminates the neutralization step, hence it results much easier to separate from liquid products. Also, they can be designed to give a higher activity and selectivity and to have longer catalyst lifetimes [11]. A large number of different heterogeneous catalysts have been synthesized for biodiesel production. For example, calcined Mg-Al hydrotalcites [12], zeolite and metal catalysts [13], metal oxides such as calcium oxide (CaO) [14], magnesium oxide (MgO) [15], zirconium oxide (Zr02) [16], and supported catalysts [17] have been investigated as heterogeneous catalysts. CaO and MgO are most frequently used heterogeneous catalysts for biodiesel production [18]. In this present work, we aimed at developing an efficient catalyst for transesterification of canola oil. We have prepared KOH/ Al203 by impregnation and applied to determine the optimum conditions for biodiesel production. Three different variables including reaction time , alcohol to oil molar ratio and catalyst loading with may influence the quality of the produced biodiesel were optimized. Moreover, SEM (scan electron microscope), XRD (X-ray diffraction) and XRF were used for characterization of the catalysts."

Jan 1, 2012

By Matthew Tunnicliffe, Akram Alfantazi, Paul Nesbitt, Farzad Mohammadi

"Lead and its alloys are proper candidates for anodes in electrowinning processes mainly because they are insoluble in the leach solutions and relatively cheap. However, the annual cost of corrosion problems associated with these anodes is millions of dollars. In this study lead-silver and lead-calcium anodes were tested under typical nickel electrowinning conditions and the effect of chloride on the corrosion performance of the anode materials was investigated. Corrosion rates of the anodes were calculated using the discharge plateau (reduction of lead dioxide to lead sulfate) after galvanostatic experiments. It was found that lead calcium anodes have the highest corrosion rate both in the presence and absence of chloride. Surface morphology of the electrodes was studied using SEM and the corrosion products were characterized using XRD.IntroductionLead (Pb) is usually the preferred material for commercial anodes since it is insoluble in the leach solution and the costs are manageable. One advantage of using an insoluble material as an anode is the higher purity of the cathodic deposits and better quality of the end product. During nickel electrowinning, metallic nickel is deposited on the cathode while oxygen evolution reaction (OER) takes place on the anode. In practice, relatively high potentials are necessary for the reaction to proceed at the desired rate because of the high overpotential of OER on lead. Lead anodes get oxidized in typical electrowinning conditions and usually have two to three years of lifetime. Although the price of each anode is insignificant, the overall cost of corrosion of these anodes is considerable, which is due to the large number of anodes used in a plant, typically two to three thousand. Therefore, corrosion is a significant problem associated with lead anodes in commercial nickel electrowinning plants and industries show interest in addressing this problem. Corrosion of lead electrodes in acidic environments has been previously the subject of many research studies [I-7]. It has been reported that, during the anodic polarization of lead, several phases may be present on the surface, depending on the potential range that is being studied [8]. Lander showed that lead is oxidized at potentials higher than 0.252 YsHE with tetragonal lead monoxide being the main reaction product [9]. At 0.666 YsHE lead can transform to lead dioxide; however, it is not stable and transforms to lead sulfate and lead oxide. At potentials higher than 1.684 YsHE, lead dioxide is eventually a stable phase and forms a protective layer on the surface [I 0, 11]. Under conditions of a typical nickel electrowinning plant, usually a 200 A/m2 current density is passed through the electrodes."

Jan 1, 2012

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 Suleyman Tekeli, Serdar Salman, Bulent Aktas

"The effect of La2O3 content up to 15 wt% on phase stability, sintering and microstructure of cubic zirconia (8YSZ) was investigated. XRD results showed that the specimens containing up to 15 wt% La2O3 were composed of only cubic structure. Also, the specimens doped up to 5 wt% La2O3 revealed no La2O3 peaks, indicating that La2O3 was completely solubilized in the cubic structure. However, when> 5 wt% La2O3 was added, the peak of La2Zr2O7 compound emerged, showing that the overdoped La2O3 was not solubilized in the 8YSZ matrix. The lattice parameter of the 8YSZ slightly decreased with the increasing La2O3 content up to 1 wt% but further increase in the La203 amount resulted in an increased lattice parameter. The comparison of grain size of the 8YSZ specimens with various La2O3 content showed that grain size slightly increased with the increasing La2O3 content up to 1 wt% but further increase in the La2O3 amount resulted in a decreased grain size.IntroductionAt atmospheric pressures, three polymorphic forms of Zr02 are stable at different temperatures i.e. monoclinic, tetragonal and cubic. A high-pressure orthorhombic form of Zr02 has also been reported[l]. The successful production of pure Zr02 bodies is not possible all the time due to the large volume expansion associated with the martensitic tetragonal-monoclinic transformation. This fact restricts the applications of zirconia, in spite of its excellent mechanical and thermal properties. However, the stabilization of the high temperature polymorphs at room temperature as stable phases is made possible by addition of suitable dopants. Fully stabilized cubic Zr02 and partially stabilized tetragonal Zr02 show interesting properties and are widely used as ionic conductors, coatings and gas sensors in solid oxide fuel cells and structural applications[2]. Most frequently used dopants include Y203, CaO, MgO and Ce02, although other oxides, such as those of rare earth elements, can also act as stabilizers of the high temperature structures. The incorporation of aliovalent cations to the lattice, forming substitutional solid solutions, allows to control the concentration of anionic vacancies in the structure. This aspect is particularly important in designing ionic conductors[3], and is also determinant in the stabilization process[ 4]. The process of stabilization with larger ionic radii dopants is rationalized by the crystal chemistry model[ 5], that describes the dopant cations as typical stabilizer when they have larger ionic size, lower charged state and higher ionicity than Zr4+ The ionic radius of Zr4+ is 0.84 Å and that for La3+ is 1.016 Å [6]."

Jan 1, 2012

By M. A. Rabah, F. E. Farghaly, M. A. Motaleb

"Wastewater from industrial galvanization industry was reclaimed under current flow stream conditions. Results showed that the raw water contains 0.7 % by weight total suspended solids (TSS) causing turbidity amounting to 30. Measurements of Zeta potential as a function of pH revealed that solid separation takes place at pH 9. Addition of H2O2 to the polmer solution helps to oxdize ions of iron and zinc metals toinsoluble ferric oxide and zinc hydroxide to a higher state of oxidation. Addition of 5 mg/L of cationic magna flocculants polymeric solution helps the rapid separation of the turbidity. Separation of floccules so formed takes place by filtration. Addition of peroxide ions to the turbid wastewater confirms the physical stability of the flocs so formed. Impurity flocculation takes place in few seconds. Maximum temperature for safe solid removal was <30°C. The treated water was pure and safe for recycling or use in domestic purposes.IntroductionStocks and et. al. [1] show that the galvanizing process introduces spent pickling acid waste production, but its major constituent, could be used. Survey of the operational procedures adopted and the acid wastes produced by UK Galvanizers are reported. Various methods to recovery spent acid of suitable composition and to eliminate zinc contamination was considered. Application of the Kleingarn acid management system reduces waste volume, saves hydrochloric acid (HCl) and increases component throughput whilst, in conjunction with zinc elimination, could allow recycling of the majority of galvanizer’s acid wastes.Dahab [2]; Kerney [3] reported recycling of galvanizing products, including pickleliquor. Kerney suggested a mobile treatment plant for recycling pickling acids. Dahab found that pollution reduction could be achieved by relatively simple operational changes to the process that gave fairly short payback times.Rozenblat and et. al.[4] studied the extraction of zinc (II), iron(III) and iron(II) with Tributyl phosphate (TBP) from hydrochloric acid solutions containing high zinc(II) concentration. Two technological approaches for the separation are considered. Firstly, the selective extraction of iron(III) (iron(II) is oxidized to iron(III)) over zinc(II) with TBP deficiency. Secondly, iron(III) reduction to iron(II) followed by zinc(II) selective extraction with an excess of TBP. Prior stripping, the organic phase was washed with small amounts of water. Scrubbing of TBP solutions containing iron(III) contaminated with zinc(II) gives always a mixture of zinc(II) and iron(III) which must be recycled to the extraction step in continuous process. The following technological concept is proposed: reduction of iron(III) to iron(II), extraction of zinc(II) with 5-10 volume excess of TBP, washing of TBP phase contaminated with iron(II) with small volumes of water and recycling of the scrubbings and stripping of zinc with water."

Jan 1, 2008

By Kumar P. Dharmasena, Haydn N. G. Wadley, Bill W. Choi

"Non-contact eddy current sensing methods have been developed and applied to Cd0.955Zn0.045Te crystal growth to obtain a better understanding of the melt, solid nucleation, and the growth process. The application of this sensor approach relies on a large difference in liquid and solid electrical conductivities near the melting point and requires knowledge of the relationships between the electrical conductivity, melt composition, and temperature. Using a multifrequency encircling eddy current sensor, the electrical conductivities of three different Cd1-xZnxTe (x=0.00, 0.045, and 0.08) alloys were measured as a function of temperature in a laboratory-scale vertical Bridgman furnace. The measured solid and liquid electrical conductivities were then used in electromagnetic finite element models to analyze the multifrequency responses of eddy current sensor designs during the simulated growth of a crystal. These eddy current sensors were fabricated and installed in a vertical Bridgman furnace and used to monitor many Cd0.955Zn0.045 Te growth runs. One sensor was placed in the vicinity of the ampoule tip to detect undercooling/spontaneous nucleation and two other sensors (""absolute"" and ""differential"" designs) placed to monitor the movement/curvature of the liquid-solid interface during crystal growth. The sensor data was used to characterize the initial melt state, detect the onset of nucle-ation, determine the growth velocity, and identify the shape of the interface.IntroductionSingle crystal CdTe and its solid solution Cd1-xZnxTe alloys (0.03<x<0.05) are used as infrared transparent substrates for infrared focal plane array (IRFPA) detectors [1-6] and as solid state y- ray detectors [7-9j. Cd1-xZnxTe substrates are normally ""mined"" from large polycrystalline boules grown by the unseeded directional solidification of Cd1-xZnxTe melts using either a vertical or horizontal Bridgman process [10-14]. The vertical Bridgman method is particularly popular for growing CdTe and its related compounds. In this process, a Cd1-xZnxTe ingot is produced by first melting a charge in the hot zone of the furnace and then vertically translating the furnace (with its associated axial temperature profile) relative to the stationary crucible to cause directional solidification. In spite of many experimental efforts to investigate the relationships between material purity, stoichiometry, the controllable growth parameters (furnace temperature profiles, ampoule geometries/materials, furnace translation rates and starting position) and the resulting material characteristics (grain structure, dislocation densities, IR transmission, macro-segregation etc.), the yield of Cd1-xZnxTe of a quality suitable for large area (e.g. 4 cm x 6 cm) substrates remains low (<10%). Since much of this poor yield is directly associated with the crystal growth process (e.g. melt stoichiometry, solidification velocity, interface shape, temperature gradients, cooling rate, etc.) intensive efforts are under way to improve this technology."

Jan 1, 1997

By Samuel Senanu, Benjamin Agyei-Tuffour, Lifeng Zhang, Eivind Øvrelid, Adegboyega Nathaniel Femi

"The solar grade silicon ingot produced from directional solidification process usually pushes the impurities to the top and finally cut off and discarded, which leads to material loss. The hard inclusions lead to wire breakages during the cutting of the ingot in wafers. The main kinds of inclusions found in solar grade silicon have been investigated using vacuum filtration: needle-like Si3N4 and lumpy SiC inclusions. Clusters of SiC inclusions and Si3N4 are also found. Surface observations of the scraps before polishing reveals that Si3N4 inclusions are usually bigger and in some cases can be about a few millimeters. SiC inclusions are usually smaller, ~200µm but can be ~500µm in some cases. Inclusions observed after filtration are mainly SiC with diameters ~10µm. Through the vacuum filtration, 99% inclusions can be removed 99%. The possible mechanisms of filtration are cake filtration for the larger sized Si3N4 and SiC inclusions and deep-bed filtration the SiC inclusions. For the directional solidified silicon ingot, an approximate distance of ~10mm gave an encouraging cutoff thickness. The inclusions sizes were below 10µm. Introduction The search for an alternative source of energy to fossil fuel has led to a dramatic increase in the demand for solar energy due to its high dependability (abundant in nature) and environmental friendliness 1). During the last 5 to 10 years, the annual worldwide production of solar cell by the photovoltaic industry has increased to an annual rate of 30 to 40 percent 2). A necessary condition for the maintenance and even an increase of this growth rate is a decrease in the cost of feedstock for the solar cell production 1). The total international production in 1997 was 130 MW worth more than $500 million. In 2004 the consolidated world total production of PV cells increased to 1146 MW or around. $7 billion (Figure 1) 3). Silicon is currently the most dominant semiconductor material used in the PV industry. As shown in Figure 2 3), solar cells consist of two types of material, often the p-type and n-type silicon. Light of certain wavelengths are able to ionize the atoms in the silicon (causing atoms to either gain or lose electrons) and the internal field produced by the junction separates some of the positive charges (“holes”) from the negative charges (electrons) within the photovoltaic device. The holes are swept into the positive or p-layer and the electrons are swept into the negative or n-layer. Although these opposite charges are attracted to each other, most of them can only recombine by passing through an external circuit outside the material because of the internal potential energy barrier. Therefore if a circuit is made, power can be produced from the cells under light because the free electrons pass through the load to recombine with the positive holes."

Jan 1, 2008

By Min Chen, Zhen Tian, Hongxu Cui

"The effects of adjusting technology on the phosphorous enrichment in converter slag were investigated. The results showed that the grain size of 2CaO·SiO2 with high phosphorus containing content increased slightly with the decreasing of cooling rate, and the proper cooling rate was confirmed to be about l.0°C.min-1. Moreover, the morphology of the phosphorus-rich phase of 2CaO·SiO2-3CaO·P2O 5 was changed from granular for the higher basicity of converter slag to the coexistence of granular shape and rod-like for the lower basicity of adjusted slag. With the addition of adjusting agent such as SiO2 to lower the basicity of converter slag, the phosphorus in converter slag could be transferred into 2CaO·Si02 phase effectively, and P2O 5 content in high phosphorus containing phase reached to above 30%.IntroductionThe yield of converter slag is very large in China, but most of the slag is stacked usually after the separation of iron, which not only takes up a lot of land, but also affects the ecological environment seriously. Therefore, improving the comprehensive utilization and value-added products of converter slag is of great significance to recycle the steelmaking slag[l-3]. On the other hand, the refining of hot metal with high phosphorous content is an unavoidable problem with the decreasing of high grade iron ore, and as a result, more amounts of high phosphorus containing steelmaking slag are produced. However, the current recycle of converter slag is more focused on the emission reduction and reuse of steelmaking slag inside the iron and steelmaking process without considering the recycle of phosphorous resources[4-6]. At the same time, the development and utilization of phosphate ore as a strategic resource is drawing more and more attention, but the phosphate ore in China is mostly low grade and significant amounts of tailings are produced which is harmful to the environment. Therefore, it is important to separate phosphorous resources in steelmaking slag which can be used as phosphate ore for fertilizer material[7-9].Literature studies showed that most of the phosphorus in steelmaking slag existing as 2CaO·SiO2-3CaO·P2O 5 solid solution phase in 2CaO·SiO2 particle. The P2O 5 content in the phosphorus containing phase is very low due to the fact that the basicity of converter slag is usually high and the precipitated amounts of 2CaO·SiO2 particles during cooling are very large, resulting in the fact that the P2O 5 contents in 2CaO·SiO2-3CaO·P2O 5 solid solution phase are much lower which is impossible to be used as phosphorous resources instead of phosphate ore. Thus, the enrichment of phosphorus in steelmaking slag is need[ 10-14]."

Jan 1, 2011

By Zhendong Tao, Wei Huang, Zhongxi Yang, Hang Guo, Haoran Geng, Jingxiang Yao

"CaSO3.0.5H2O typed Flue Gas Desulfurization (FGD) gypsum is a by-product formed in flue gas desulfuration by double-cycle fluid bed method, its composition is different remarkably from that of gypsum yield by normal desulfuration methods, and few studies using it as cement retarder have been carried out. In this paper, the experimental study using CaSO3•0.5H2O typed FGD gypsum as cement retarder was carried out. The experimental results indicate that, when FGD gypsum is added solely into cement, the retarding action is not satisfactory because of its slow dissolution rate; The composite retarder composed of FGD gypsum and natural gypsum can regulate efficiently setting time of cement over a wide range of addition and rate of both each other, and the mechanical property of cement can be improved significantly.Fire-power plants have discharged a lot of harmful gases such as SO2 etc., which has resulted in serious pollution on the environment. To reduce harmful gas containing sulfur in the flue gas, various flue gas desulfuration (FGD) techniques have been developed. At present, the FGD method used widely is to add desulfuration agents such as limestone powder or other calcareous-contained materials during the coal burning or in the flue gas so that the components containing sulfur react with them to form solid sulfate or sulfite and to be separated from the flue gas by collectors. CaSO3•0.5H2O and CaSO4•2H2O typed FGDgypsum can be obtained respectively by dry and wet FGD process[1,2]. As a by-product of fire-power plant, features of of FGD gypsum and its applications have been paid great attention. Pavel Tesa'rek et al [3] presented in full the characters and properties of FGD gypsum; Zofia Konik et al[4] prepared expansive additive used to cemnent industry by using FGD gypsum and aluminate clinker; A. K. Alva et al [5] investigated the effects of FGD gypsum and fly ash on soil properties and found the growth of seedlings of either rootstock improved significantly in soils amended with FGD gypsum and fly ash. FGD gypsum also can be used in gypsum binders, plasters and plasterboard manufacture [2.6]. C. S. Poon et al [7] investigated the effects of FGD sludge on the pozzolanic reaction of reject-fly-ash-blended cement pastes. Many studies using CaSO4•2H2O typed FGD gypsum as cement retarder has been reported[2,8-12]. Howevere, few studies using FGDG as retarder were reported so far. In present study, the chemical compositon, phase composition, structure and features of CaSO3•0.5H2O typed FGD gypsum have been analyzed, and its application characters used as cement retarder have been investigated experimentally."

Jan 1, 2008

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Nobuyuki Higashiyama, Ikuo Yonezu

"Hydrogen-absorbing alloys containing rare-earth elements are used in high capacity nickel-metal hydride secondary batteries,' hydrogen storage systems for portable fuel cells, and refrigeration systems. New hydrogen-absorbing alloys containing rare-earth elements have also been developed and introduced into these applications. High performance in nickel-metal hydride secondary batteries is strongly demanded because of the remarkable advancements in portable electric appliances. A large hydrogen absorption capacity, high electrochemical reactivity and superior corrosion resistance in an alkaline solution are required for hydrogen-absorbing alloys used in nickel-metal hydride batteries. The aim of this investigation is to improve the performance of conventional LaNi5 type hydrogen-absorbing alloys. For example, Mm(Ni-Co-Al-Mn)„ type hydrogen-absorbing alloys with various non-stoichiometric compositions were developed. In addition, a new process of rapid quenching process was applied for preparing these hydrogen-absorbing alloys in order to improve their performance.IntroductionRecently, the trend in electronic appliances toward portability has increased the demand for high capacity of secondary batteries as power sources. Since nickel-metal hydride batteries were first commercialized in 1990 in Japan, they have become increasingly popular as power sources for cellular phones, portable computers, electric shavers, and other, products.The performance of a nickel-metal hydride battery, such as its discharge capacity, high rate capability, and charge-discharge cycle life, strongly depends on the characteristics of the hydrogen-absorbing alloy negative electrode. Many types of hydrogen-absorbing alloys have been developed so far. For a hydrogen absorbing alloy to be used as the negative electrode material, (1) it must allow a large amount of hydrogen to be absorbed and desorbed in an alkaline solution, (2) its reaction rate should be high, and. (3) it must have long term durability under repeated charge-discharge cycling. However, LaNi5, a typical rare earth-nickel type alloy, shows significant capacity deterioration during repeated charge-discharge cycling. Therefore the first step in its development was to obtain sufficient corrosion resistance of the LaNi5 alloy for its use as an electrode material. A partial replacement of nickel with cobalt and a substitution of the lanthanum- content with misch metal (Mm), a mixture of rare earth elements such as lanthanum, cerium, praseodymium and neodymium, were very useful in improving the charge-discharge cycle life. However, the discharge capacity of the alloy was still not sufficient for a practical battery. A study of the effect of the partial substitution of aluminum and manganese showed that the best alloy composition was Mm(Ni-Co-Al-Mn)x, as follows.The stoichiometry x of Mm(Ni-Co-Al-Mn)x largely affects the discharge capacity and cycle life. Theose alloys with non-stoichiometric alloys with the compositions of [Mm(Ni-Co-AMn)x: 4.7<x<4.8] have a large capacity and a long cycle life. Nogami' et al. reported that 'a non-stoichiometric alloy with a Mm(Ni-Co-Al-Mn)x (x=4.76) composition showed approximately 10% higher discharge capacity than the stoichiometric alloy (x=5) [1] and greater influence of x on the electrochemical properties of multi-component AB„ type hydrogen-absorbing alloys for batteries."

Jan 1, 2000

By H. Y. Sohn, M. Y. Mohassab-Ahmed

"As part of research to develop a novel flash ironmaking process using reduction of iron ore concentrate by natural gas or hydrogen, sulfur and phosphorus distribution ratios between MgOsaturated slag and iron were determined in the temperature range 1550-1650°C under three different gas atmospheres: H2/H2O, H2/H2O/CO/CO2, and CO/CO2. The distribution coefficients of sulfur (Ls) were 4.0, 2.0, and 0.8, respectively, under these atmospheres. The distribution coefficients of phosphorus (Lp) were, respectively, 8, 17, and 20 under these atmospheres. In the flash process over -25 wt% P and S volatilize during ore concentrate downward flight in the reactor shaft in addition to avoiding coke. Therefore, iron produced by the flash ironmaking process would have much lower sulfur contents than the typical hot metal produced by the BF.IntroductionGiven the issues related to large carbon dioxide emissions and energy consumption in the existing ironmaking technologies, a novel flash ironmaking technology was conceived by Sohn [1-3] at the University of Utah. This technology is the first ironmaking process that will convert iron ore concentrate directly to metallic iron in-flight. This process will produce iron directly from concentrate without requiring pelletization or sintering and avoid the need for coke. In addition, this process concept takes full advantage of the fine particle size of concentrate with a large surface area, which permits rapid reduction by a gas. In this novel ironmaking process, potential reductants and fuels are H2, natural gas, and coal gas. Therefore, an iron-slag bath is expected to be at equilibrium with gas atmospheres of mainly H2/H2O or CO/CO2/H2/H2O, respectively, corresponding to the use of H2 or natural gas/coal gas. Since the effects of an H2O- containing atmosphere on slag properties have not been studied before, it is critical for the development of the novel flash process to determine these effects. In H2-H2O-CO-CO2 gas mixtures under ironmaking conditions, H20 was found to have the most pronounced effect on the slag chemistry [ 4, 5]. In addition, it was found in this laboratory that water in the gas atmosphere affected the distribution of Mn between slag and molten iron [6]. Most previous work used CO/CO2 gas mixture to control oxygen partial pressure (p02) [7, 8]. Others used only inert atmospheres [9], although Kor and Richardson [10] used a mixture of C02/H2 to control p02. For phosphorus, previous research focused on Ar [11], Ar-CO mixture [12], CO [13], CO/CO2 [14] or N2/CO [15]. Therefore, it was necessary to investigate the effect of water vapor content in H2-H2O-CO-CO2 mixtures on the equilibrium distribution of sulfur and phosphorus between CaO-MgOsatSiO2-Al2O3-FeO- MnO (0.2-0.8 wt%)-P2O5 (0.1-0.9 wt%) slag and molten iron as part of the development of the novel flash ironmaking technology."

Jan 1, 2014

By Anand Kumar, Pradeep kumar Jha, Suman Kant, Pradeep Kumar

"It has been a major challenge to reduce the intermixed grade formation during ladle change-over operation in continuous casting process of tundish steelmaking. The F-curve generated by step input of the tracer (new grade steel) tells about the intermixed grade amount for different grade specifications. Use of flow modifiers is beneficial in reducing the intermixed grade because of the change in slope (in different time zones) and position of the F-curve due to their placement at tundish bottom. Present study aims at investigating the role of dam placed before the outlet in a multi-strand tundish with reference to the slope behavior of F-curve in different time zones during the teeming operation plays an important role in determining the intermixed amount.Introduction In Continuous casting process, the old grade steel remaining in the tundish (reservoir between ladle and mould) from the old ladle gets mixed with new grade steel from new ladle and leads to intermixed grade which is considered to be of inferior quality. Although formation of intermixed grade is inevitable with the sequential method of casting, its amount can be controlled by changing the flow behavior of steel inside the steel. Intermixing in a slab caster tundish was simulated using 3-D numerical model based on k-å turbulence equation and compared their result with that of water model experiment Yeh and Hwang [1]. Huang and Thomas [2] reported that quantity of residual fluid in tundish affects the composition distribution in the transitional slab and thus the intermixed length. Huang and Thomas [3] developed three sub models to predict mixing in tundish, liquid core of strand and solidification. Thomas [4] developed a one dimensional model to simulate the final composition distributions in slab caster of continuous casting and investigated the effect of process variables on the intermixing. Alizadeh mehdi et al., [5] simulated of the intermixing phenomenon for slab casting for three different sub models. Goldschmidt et al. [6] developed a numerical model that predicted the location of the intermixed steel in a four line round caster. Lan and Khodadadi [7] studied for the transient fluid flow of liquid steel, heat transfer and solidification during the flying tundish change process. Cho and Kim [8] developed a mixing model to predict the outlet concentration of the tundish during grade transition. Most of the work reported in the literature has dealt with intermixing in slab caster tundish. Billet caster units are more often being used by steel industries due to growing demand of billets. The multiple outlets lead to varying degree of intermixing with time owing to their different distance (location) from the inlet. Use of flow modifier to minimize the intermixed amount, however has also not been discussed in detail so far. Further no work has been reported regarding effect of slope of F-curves obtained through different outlets on intermixing. Hence keeping these objectives in mind attempt has been made by authors to analyze the slope of Fcurves after dividing them into three different time zones and the effect of these time zones on intermixing."

Jan 1, 2012