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By S. C. Grand, T. J. Auping, K. Born

Process control, environmental monitoring, budgeting and accounting are based on process data. Without appropriate tools for data analysis, the process data could remain unused and wasted. This paper demonstrates how data reconciliation can be used as a tool to develop closed mass balances. Mass balances are the initial step in plant optimisation (technical, economical or environmental). From mass balances, fundamental process models can be developed. These balances link process parameters (e.g., feed materials) to process performance (e.g., recovery of valuable elements). Some of these models could find their way into simulators useful to plant operators. Classical regression methods regularly fail when they are applied to complex non-linear problems involving a large number of variables. Alternatively, multiparametrical regression analysis can be successfully applied with the aid of neural networks based on reconciled data. Both methods have been applied to plant data originating from the hydrometallurgical zinc plant at Ruhr-Zink, which in this paper serves as a case study. Very promising and useful results were obtained from this study.

Jan 1, 2000

By Mala Nath, Atjit Mallick, Asheesh Kumar

"The present research work is aimed to focus on the development of chemically stable light weight microporous carbonaceous material, such as activated charcoal incorporated either with titanium n-butoxide, titanium diisopropoxide bis(2,4-pentanedionate), vanadium 2,4-pentane-dionate or zinc 2,4-pentanedionate having varying wt% of the metal (2-8%) using ethanol as solvent at 40--50 oC followed by calcinations at 100, 150 and 200 cC, except the samples with titanium diisopropoxide bis(2,4-pentanedionate) which are calcinated at 80 oC. Atomic absorption studies along with FESEM revealed that the maximum incorporation of metals (Zn, V and Ti) in activated charcoal was observed with 4 wt% of zinc 2,4-pentanedionate calcinated at 150 oC , 4 wt% of vanadium 2,4-pentanedionate at 100 oC, 2 wt% of titanium n-butoxide at 100 oC and 2 wt% of titanium diisopropoxide bis(2,4-pentanedionate) at 80 oC, and equilibration time of 20-24 h was used in each case. Hydrogen sorption behavior in these carbonaceous materials has also been studied at 77.4 K and low pressure up to I bar. The highest hydrogen uptake obtained was 1.45 wt% (164.5 cm3 (STP)/g at P/Po = 1.0) for activated charcoal incorporated with 4 wt% of zinc 2,4-pentanedionate calcinated at 150 oC.IntroductionTwo of the major challenges for humanity in the next twenty years are the shrinking availability of fossil fuels, the global warming and potential climate changes that result from their ever-increasing use. So it is necessary to fmd an energy source that is convenient, flexible and controllable. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles. Hydrogen storage is the bottleneck for the breakthrough of hydrogen as energy carrier in automotive applications [1]."

Jan 1, 2012

By M. C. Ruiz

The conventional pyrometallurgical methods to treat copper sulfide concentrates include generally, one or more oxidizing steps where the formation of SO2 gas can not be prevented. From the economical point of view and the nature of some of the processes in which SO2 is produced, its complete capture is not feasible; therefore an important fraction is released to the atmosphere as fugitive emissions. In this research, the reduction of chalcocite was studied in the presence of lime as an alternative method, which overcomes the pollution problems related to SO2 emissions. The effect of temperature, time, concentration of carbon and CaO on the reduction rate were studied. Among these variables, temperature affects most the reduction rate. Conversions over 95 % can be obtained in less that 20 minutes at temperatures over 1000 ° C. The measured partial pressures of the gaseous components indicated that the chalcocite reduction proceeded through the gaseous intermediate species CO, C02, and the overall kinetics was controlled by the Boudouard reaction. The kinetic model In(1-X)= kt fits well the experimental data. Apparent activation energy of 3 14 kJ/mol was calculated for the temperature range of 900 0C-1050 °C.

Jan 1, 1999

By Akio Ohta

The Hyuga smelter has been producing ferronickel by a rotary kiln-electric furnace process in Miyazaki, Japan. Several approaches to improve our operation have decreased the electrical energy consumption. A new process was developed to decrease the cost of energy even further. Oil and technical oxygen are injected through lances to heat up the calcined ores (calcine) instead of the electric power. Main problems during the development of the process were the short life of the water-cooled lances, the check on security of the safety system and the eruption of combustion gases through the calcine bed. These problems have now been overcome successfully, and stable operation can be maintained. The addition of 1 Litre of heavy oil per tonne of ore can save the electrical energy requirement by 8.6 kwh per tonne of ore. The new process has resulted in a reduction of the electrical energy consumption by more than 10 percent

Jan 1, 1992

By Tian Sugui

By means of the long-term aging treated, creep properties measuring and microstructure observation, an investigation has been made into the microstructure and creep behavior of the casting and rolling GH4169 superalloy after long-term aged. Results show that, after the casting and rolling GH4169 superalloy treated by long-term aged, significant amount of " phase are dispersedly precipitated within the grains of the alloy, and some of the NbC, Cr7C3 carbide are distributed along the grain boundaries. In the range of the applied stresses and temperatures, the creep activation energies and stress exponents of LTA GH4169 alloy during steady state creep are calculated to be Q=541.1kJ/mol and n=16.2, respectively. During creep, the deformation mechanism of LTA GH4169 is thought to be the twinning and dislocation slipping within the twinning regions, and the damaging mode of the alloy is the intergranular fracture, and the non-smooth crystal surface is displayed in the fracture regions of the alloy. Thereinto, the carbides film formed along the grain boundaies has a few effect on the strength between the boundaries, which is a main reason of resulting in the alloy possessing a longer creep lifetimes.

Jan 1, 2009

By Okechukwu Anopuo, Gerhard Tober, Petra Maier

"In this study, an investigation on the microstructure of hot rolled steel S355J2+N was conducted to optimize process parameters of complex forming, which combines rolling and bending. The best sets of parameters are worked out based on homogeneous mechanical properties and microstructure within the varied deformation degree with maximum at <p = 1.14 on a 25 mm thick plates. Mechanical properties, especially of heavy plates, are strongly influenced by the local deformation degree, strain rate and temperature. Detailed microstructural analyses showed that the ferrite-pearlite band structure changes near the surface, while maintaining homogeneous microstructure within the deformed work piece. Surface decarburization was also observed and this leads to decrease in hardness. To minimize iron oxide formation which could lead to side cracking, reduction in exposure time to temperature was suggested. On the other hand, temperature reduction below a critical value would risk the accurate forming process.IntroductionThis work presents the preliminary results of research to develop a new complex deformation process of thick steel plates. Complexity is given because the forming process combines rolling to reduce thickness and profiling by bending. The work piece will experience a thickness reduction from 25mm to 8 mm and is double curved. To explain and understand forming of thick plates basics of sheet forming as well as massive forming need to be used. At the moment there is no forming process established to produce double curved plates including reducing thickness in one process step. Technologies nowadays consist of two process steps: flat rolling and pressing in shape. Due to good weldability and formability the final product will be made of steel S355J2+N. This low-carbon steel is well understood and has a low strengthening exponent, which is expected to keep the forming forces down. Reduction of thickness from 25 mm to 8 mm gives furthermore a high deformation degree. Thus, hot forming has to be applied. The determination of process parameters is the main aim of overall research project; temperatures above lOOO°C are expected. Flow curves in literature are given at various temperatures and strain rates [1]. However, experiments with data close to the industrial application are rarely found, especially at low strain rates and high deformation degrees. Pre-test were done by flat rolling, being aware that the influence of bending is eliminated. The microstructure evolution were characterised in relationship to material formability with special attention to grain size change and recrystallization. Representative samples should be selected from specific locations in the deformation zone according to the knowledge about the metal forming process [2]. Due to no further alloying elements in S355, no precipitation hardening is expected to take place during hot forming, which keeps the mechanisms simple and the concentration on the feasibility of the complex forming process is given."

Jan 1, 2012

By Gunnar Eriksson

Computer simulation has become an everyday practice in thennodynamic and materials research. Advanced thennochemical algorithms take into account heat transfer effects and salient reaction kinetics when applied for process models. In particular, the combination of mass transfer or overall reaction rates with multi-component Gibbs energy minimisation provides an effective tool for simulation of industrial thennochemical processes and processing of materials. In this work the combination of rate factors with the Gibbs energy technique was studied by using the novel program ChemSheet, which operates through Microsoft&apos;s Excel® spreadsheets. Such processes as, for example, CVD of pure silicon production, titania pigment manufacturing, vapour pressure of Mercury in amalgams (in Hg-Iamp manufacturing) and melting behaviour of low-temperature alloys have been modelled. Provided that the thennochemical data is available simulations can be performed with any thennodynamic system. The calculation can be performed as an affinity study without a particular reactor model or with a specific reactor scheme.

Jan 1, 2001

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem&apos;s reduced chaotic temperature &apos;tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system&apos;s possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the &apos;tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By B. Ozturk, K. Ito, R. J. Fruehan

"A simulation model for bath smelting processes for the production of iron was developed which predicts the coal, flux, ore, and oxygen consumptions and the off gas volume, temperature and composition. The model is comprehensive in that it takes into account all of the important variables including coal composition, metal composition, ore composition, slag basicity, post combustion ratio, (PCR), prereduction degree (PRO), heat transfer coefficient (HTC) , flux, scrap charge, and heat losses. Four basic cases were considered: I. 30% PRO-50% PCR; II. 90% PRO-O% PCR; III. 60% PRO-30% PCR; and IV. 0% PRO-50% PCR. Several different coals were considered and a sensitivity analysis of the critical variables was performed. The model also estimates the sulfur content of the metal. The major conclusions included:1. Post combustion significantly reduces coal consumption but above 20% PCR little reduction of FeO to Fe can be performed with the off gas.2. Prereducing to FeO (Case I) and having as much post combustion as consistent with good heat transfer is an attractive process. This process only requires a simple pre reducer, uses less coal, and is relatively insensitive to the type of coal used.3. High off gas temperatures may pose a potential problem. The off gas temperature can be reduced by using an 02-Air mixture for post combustion, limiting post combustion or adding water to the gas.4. The use of CaC03 in place of CaO or of supplemental electricity does not appear attractive.5. The melting unit is theoretically an energy efficient scrap melter. For Case I using 200 kg of scrap as part of the charge the coal consumption decreases by about 80 kg.6. With PCR > 30% the FeO content of the slag is expected to be 2-5%, and the metal will not be saturated with carbon. These factors and the increased sulfur load since coal is the fuel indicate the sulfur content of the metal may exceed 0.25%"

Jan 1, 1988

By Neil E. Izatt

The use of Molecular Recognition Technology (MRT), a selective separations technology using specifically designed ligands, has been established as an effective process for removal of metal ions found in many hydrometallurgical, chemical, and wastewater streams. The MRT process has been proven to be highly efficient and effective for indium extraction and recovery from zinc acid leach, electrolyte, chemical process and waste streams. A high percentage of the indium is recovered in a solid product format. MRT has also proven effective for germanium extraction and recovery from similar feed streams. This paper provides the indium and germanium metal recovery flow sheets and analytical results of the metal load and recovery steps.

Jan 1, 2006

By Garry W. Warren

The brass foundry industry produces a significant amount of waste sand containing Cu, Zn and Pb which is often classified as a hazardous waste due to Pb content. The potential application of a hydrometallurgical process to treat the sand by extracting metal values and thus detoxifying the material has been investigated. The process involves leaching of metal values followed by cementation. The emphasis of this investigation was on the leaching step, although some preliminary cementation experiments have been performed. In order for any alternative treatment scheme to be successful, the smaller size fractions of the sand must be addressed. Experiments have been performed on five individual size fractions using various lixiviants HCI, acetic acid and HCI/NaCI. Cu extraction was found to be slower than either Zn or Pb. Results obtained in this investigation indicate that copper is present in two forms, an oxide form which dissolves rapidly and is insensitive to the level of oxygen, and a less soluble form, probably metallic which dissolves more slowly and requires an oxidizing agent. The presence or absence of oxygen had no influence on the rate of Zn dissolution indicating that zinc is present mostly in oxide form. Toxicity Characteristic Leaching Procedure (TCLP) tests showed that residues could be produced which meet the toxicity limit for lead. Preliminary cementation experiments have also demonstrated the feasibility of Cu and Pb recovery.

Jan 1, 1991

By J. L. Liow

Studies have been carried out on the causes and effects of slopping in an annular cylindrical geometry such as the top submerged combustion reactor. Properties of standing waves formed such as the wave profile, period, pressure distribution and velocity have been derived analytically. The wear profile due to wave erosion was calculated based on the assumption of linear motion and that the wear is a dissolution process. The use of the j, factor showed that the wear was proportional to the square root of the wave velocity at any point. Using the dimensions of the lsasmelt reactor given by Errington et al. (1987)[11, the wear profile due to wave erosion was calculated using the analytical solution. The wear profile calculated was shown to have a maximum just below the initial bath surface. The wear was found to be concentrated in the region where the first asymmetric standing wave was most active. The results showed that the refractory near the bath surface will be affected by wave erosion, more so than any other parts of the reactor. The contribution of wave erosion on wear must be accounted for in assessing the total refractory wear of a vessel in which slopping exists.

Jan 1, 1991

By Christina Viklund-White

Life Cycle Assessment has been used to compare the environmental performance of landfilling versus recycling of the zinc used for galvanizing steel. Hypothetical process routes were com-posed involving four different EAF dust treatment processes; Waelz kiln, DC-furnace, EZINEX and slag fuming, as well as scrap dezincing. The study shows that recycling of zinc used for galvanizing steel has environmental benefits in that it saves zinc resources. However, zinc recovery does not necessarily decrease the potential impact on global warming and acidification. The magnitude of these two impact categories is tightly correlated with the amount and type of primary energy consumed in a process. Due to the high electricity consumption in the dezincing process, this route has the highest impact on Global Warming Potential as well as Acidification Potential. The major part of the energy requirement for the production of zinc from primary and secondary sources is consumed in the reduction of ZnO to Zn. The consequence is that the theoretically possible savings in primary energy by recycling zinc-containing materials are relatively minor. The impact categories "land use" and "waste generation" are not considered in this study, but most likely the evaluation of such impacts would further increase the potential environmental impact of the landfill alternative. The results also show that the location of an electricity-intensive process highly affects the potential environmental impact. Comparing process and material alternatives in LCA studies where branch average data is used, is considerably more complex than when LCA is used within a company.

Jan 1, 2000

By F. J. Arriagada

Where gold is present in a finely disseminated form within sulfide particles, the porosity and surface area of the calcined material strongly influence leaching since they control the penetration of solution inside the gold-bearing grains. On the basis of a stability diagram for the Fe-O-S in the temperature range of 400 to 750aC, the expected sequence chemical transformations associated with the oxidation of pyrite is discus-sed. By using analytical techniques which include scanning electron microscopy, X-ray diffraction and BET gas adsorption, the chemical and structural changes experienced by auriferous pyrite-arsenopyrite concentrates and pure pyrite samples are studied under an oxidizing roasting atmosphere of com-position 80% N + 20% O2 in the temperature range of 450 to 750°C. The results indicate that as the roasting temperature increases, the surface area of the calcines decreases sharply after a maximum value attained at about 450-500°C. SEM micrographs show that the needle-shaped tips which characterize the surface of the oxide product become wider and the size of the pores between them is decreased when the roasting temperature is in-creased from 550 to 750°C. This effect suggests that the formation of a more "closed" hematite product at higher temperatures is due to sintering associated with a faster growth and crystallization of the oxide. A strong correlation is shown between increasing roasting temperature and increase in gold lost in cyanidation tailings, an effect which may be partly attributed to the loss in surface area of the calcines.

Jan 1, 1982

By Georgios N. Anastassakis, Nickolaos Georgiou

"Soil contamination by oil as well as by other organic pollutants poses a major problem to the environment. Various methods have been used to remove organic contaminants from soil, such as: biological, thermal, chemical and physical. Methods based on Mineral Processing principles have also been used (cyclone separation, gravimetric separation, attritioning and washing). This paper studies the possibility to remove a rich-in-contaminant soil fraction by applying flotation. The contaminated soil was artificially prepared by mixing soil with diesel fuel. Sodium dodecylsulfate (SDS) and a tertiary amine (TA) were used as collectors. The effect of collector quantity added and conditioning time was studied. The results showed that the removal of a rich-in-contaminant soil is feasible while a clean fraction is also obtained. In several cases, the removal of oil-contaminated soil approaches or reaches 100%. Introduction Human activities are intimately associated with environmental pollution to the air, water and soil, as well. Soil pollution from inorganic and organic compounds is of equal importance with that of air and water, as it results in soil degradation and its concomitant problems with respect to meeting the human needs (house building, agriculture etc). Heavy metals along with their compounds are encountered among the most usual soil inorganic pollutants. The corresponding organic soil-pollutants are oil, oil-derivatives, pesticides, various aromatic (benzene, phenols, cresols, toluene etc) and poly-aromatic (naphthalene, anthracene etc) hydrocarbons, as well as various other organic compounds (pyridine, cyclo-hexane etc). Oil remains the basic energy source sharing 38% of the global needs, being followed by coal and gas with a share of 26 and 21% correspondingly [1]. The entire activities related with oil production, transport and consumption promote pollution in the air, water and soil. Consequently, soil pollution from oil is favoured at refineries, storage sites (due to possible pipe and tank leakage, tank cleaning works, loading and transportation) and, finally, at the oil-selling sites. Oil (or diesel-oil) fuel is a mixture of hydrocarbons, with 10-20 carbon atoms in the chain of each. It is mainly composed of paraffins, naphthenes and various aromatic compounds. In general, oil is composed of 20-30% in aromatic compounds, 5-6% in naphthenes and the rest is paraffins [1]."

Jan 1, 2008

By Chang-hong Peng

Solubility phase equilibrium in the ternary system of Me2+-NH4+-SO42--H2O (Me2+ represented Mn2+, Zn2+ and Fe2+) was studied by the isothermal method at 298K and physicochemical properties of the saturated solution such as density, refractive index and pH were also investigated. The experimental results show that the solubility isothermal phase diagrams of these systems consist of three invariant branches, two invariant points and three crystallization fields. Corresponding to the three crystallization fields, there have three phases of solid, that is MeSO4?nH2O, (NH4)2SO4 and (NH4)2Me(SO4)2?6H2O, respectively. At the eutectic point, the concentration and the refractive indexes of the saturated solution change evidently. Otherwise, the pH value change slowly in all the systems. The calculated results of the density and refractive index agree with the experimental results.

Jan 1, 2006

By David Bequette, Ray D. Peterson, Cynthia K. Belt

"With a need to cut production costs in the metals industry, cost savings from energy efficiency improvements are critical. Opportunities can be found by reviewing furnace systems and practices so that the melting and holding processes operate at the highest energy efficiency. Many of the changes can be implemented with a minimum of expense or capital investment. This paper will review several low cost methods to optimize energy efficiency on reverberatory melting or holding furnaces. These five methods (furnace utilization, idle procedures, fire rate, controls, furnace pressure) will be explained and information given to implement these changes. Included are several rules-of-thumb and benchmarks for aluminum reverb furnaces.IntroductionEnergy can be a significant portion of the total manufacturing costs for metals and materials manufacturing involving thermal processing such as heat treating, melting, and high temperature processing. Natural gas prices have dramatically varied over the last few years. While no one can foresee the future, prices are expected to increase from the current low prices. More recently, emphasis is being put on the reduction of greenhouse gases with the potential of additional costs to industry.One of the first steps in an energy management program is to measure the energy usage of the process [1]. The results are typically understood in relation to the mass melted in kWh / mT [BTU / lb]. For the purposes of this paper, furnace energy efficiency is calculated over a month or even a year and thus includes hold times. This efficiency is typically different from the values quoted by furnace manufacturers. Those values are for limited short term tests at highutilization.Once you know the performance for your furnaces, these should be compared to industry benchmarks. For aluminum melt furnaces with cold air burner systems, a benchmark value or goal is 1800-2000 BTU/lb [1160-1290 kWh/mt], though some of the best have reached 1600 BTU/lb [1030 kWh/mt]. Furnaces with regenerative burners can attain 1100-1200 BTU/lb [710- 775 kWh/mt]. There are some designs of multi-chamber furnaces or oxygen furnaces that have improved on these numbers, perhaps as low as 950 BTU/lb [615 kWh/mt]. Typically, as the degree of sophistication and energy efficiency of the furnace increases, so does the cost."

Jan 1, 2010

By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By Shun Myung Shin, Dong Hyo Yang

Cobalt is recovered from square type of spent lithium ion batteries (LIBs) containing 5~20 % Co, 5~7 % Li, 5~10 % Ni, 15% organic chemicals, and 7% plastics together with Cu, Al, Fe, and Mn. The waste LIB was prepared by physical treatment. After screening, the crushed LIBs were separated to +8 mesh, -8/+16 mesh, and -16 mesh powder. Among these, -16 mesh powder was selected for leaching. The leaching test was investigated at 2 M H2SO4, 6 vol.% H2O2, reaction temperature 60 ?, agitation speed 300 rpm, solid/liquid ratio 50 g/ 500 ml, reaction time 1 h. The leaching efficiency of cobalt was more than 99 % and its concentration was 24.9 g/L. For removing of impurities such as copper, iron, and aluminum in the leaching solution before cobalt solvent extraction, the impurities were eliminated by pH control with alkali solution. For selective extraction of cobalt, the aqueous phase removed impurities was equilibrated with different volumes of 0.4 M Cyanex 272 saponified of 50 %. Extraction efficiency of cobalt was about 80 % at first step. Separation coefficient (ßCo/Li) of cobalt and lithium extractions was 206.5. Over 9.0 % of pure cobalt sulfate solution was obtained after stripping with H2SO4 solution.

Jan 1, 2008

By Yonggang Liu

Microstructure and precipitates in hot rolled low carbon steel sheet by CSP were investigated in this paper. It is pointed out the precipitates in low carbon steel sheet by CSP are different with that by traditional hot rolling. The bainites were found in CSP hot rolled steel sheet by TEM testing and these bainites could maintain in the sheets even after batch annealing. The selected area electron diffraction analyzing indicated that there were many CrB2BN and FeB4BN phases precipitated in hot rolled steel sheet and no AlN grains precipitated. The nitrides forming can limit AlN grains precipitating during the batch annealing processing, and this could do harm to the texture pipeline along orientation line forming with formed properties.

Jan 1, 2006