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By Wander. L. Vasconcelos, Virgínia. S. T. Ciminelli, Angela. M. F. Guimarães

"The present work was aimed at synthesizing nanostructured hybrid materials derived from the functionalization of smectite clays with ligands containing thiol (-SH) groups for application in cadmium adsorption processes. An in nature Brazilian bentonite was investigated. The modification route was based on the grafting reaction between hydroxyl groups present on clay surface and the hydrolyzable alkoxy group of the (3-mercaptopropyl)trimethoxysilane in dry toluene under reflux. The present work showed that the proposed modification route was effective for the grafting of the thiol groups in the clay structure. The thiol-functionalized bentonite samples showed average binding capacities 160% higher with respect to Cd2+ to those obtained with the ungrafted material. These results support a mechanism of adsorption involving primarily ion complexation by the thiol groups (specific) instead of cation exchange (unspecific). The proposed modification processes are suggested for the preparation of novel adsorbent materials with controlled selectivity and specificity and therefore with good potential for separation and pre-concentration purposes.IntroductionMany efforts have recently been devoted to the design and preparation of inorganic-organic nanomaterials because of their potential application in novel functional materials. The intercalation of organic species within the spaces between interlayers of inorganic layered crystals provides nanostructures consisting of alternating layers of inorganic and organic compound. The intercalation reactions occur by insertion of mobile guest species (neutral, molecules, or ions) into the accessible crystallographic-defined vacant sites located between the layers (interlayer spacing) of the layered host structure [1}.Silane coupling agents, used widely for the modification of silica surfaces, have also been employed more recently for modification of layered silicates [2,3,4,5]. Modification with organosilane involves grafting reactions by establishing covalent bonds between the reactive groups of the layer, normally hydroxyl groups, and silane molecules. These reactions can be restricted to the external surface (the basal spacing remains unchanged) or to the interlayer surface, in which case an interlayer expansion occurs. The resulting material can be defined as a hybrid material or, more specifically, functionalized inorganic layered material [1]."

Jan 1, 2008

By Guodong Lai, Shixing Wang, Lijuan Chu, Jinhui Peng, Zebiao Zhang

"The beneficiation of poor manganese ores containing phosphate gangue is very difficult by conventional processes, because of the similarities in the physico-chemical properties of the constituent minerals. The shaking table gravity concentration process and concentrated strong acid selective intensified leaching process were used for dephosphorisation of Yunnan manganese ore. The leaching process was effective. The effects of intensified leaching time, solid-liquid ratio and particle size were investigated. The relevant leaching factors were optimized as -0.125+0.088 mm particle size with 68% nitric acid for 24 h when using a solid-liquid ratio of 1:1 at room temperature and atmospheric pressure. Under these conditions, the P/Mn ratio was reduced from 0.0107 to 0.0056, and the grade of manganese was increased from 12.32% to 42.76%. The dissolution of manganese during leaching was negligible.IntroductionManganese and its compounds are widely used in the iron and steel industry as deoxidation and desulfurization agents and as alloying additives [1-2]. Because of the increase in demand, low grade refractory manganese ores are becoming a new source. Many Chinese manganese ores are high in phosphorus, which cannot be used directly for metallurgical purposes. This occurs because phosphorus enters into the metal phase during smelting and its presence sharply deteriorates the mechanical properties of the metal [3-4].Kanungo and Sant [3] investigated the dephosphorization of phosphorus-rich manganese ores by selective leaching with dilute hydrochloric acid. They observed that leaching with dilute hydrochloric acid (0.1-0.6M) could reduce the phosphorus contents to the specified limit of 0.12%. Ye [5] investigated dephosphorization of high-phosphorus manganese ore of the Huayuan type. Using high intensity magnetic separation, roasting and leaching with acid for dephosphorization, as used in the industry, a 40.15% manganese concentrate with a P/Mn ratio of 0.0037 was obtained. Yimin [6] investigated magnetic separation followed by inverse flotation of high-phosphorus manganese ore, and found that the P/Mn ratio could be reduced from 0.046 to 0.002."

Jan 1, 2012

By S. Mondon

Hibi Smelter which is a Copper Smelter lining a blast furnace, produces 2,700 metric tons of anode copper per month. Generally, in a copper refinery, arsenic and antimony are considerably troublesome impurities. With regard to the elimination of antimony, Hibi Smelter has two handicaps described as follows. (1) Smelting under the slightly oxidizing atmosphere in the blast furnace. (2) Recycling the converter slag to the blast furnace after cooling. Therefore antimony and arsenic, mainly antimony, elimination tests, in which the alkaline flux was injected through the two tuyeres in the blowing stage, were carried out in the rotary anode furnace. Antimony and arsenic were respectively removed more than 90 96 from the molten copper, and their high eliminations are discussed by application of the transitory and permanent reaction model with the flux injection, which was presented by T. Lehner.

Jan 1, 1983

By Peng Lv, Shiqian Liu, Bin Xu, Qian Li, Yongbin Yang, Tao Jiang

The treatment process of a low-grade refractory gold ore containing sulfide minerals and carbonaceous matters was studied in this work. The gold extraction of this ore by all-sliming cyanidation was only 11.75%. Hence, a pretreatment was necessary. In this paper, a flotation-preoxidation-cyanide leaching process was developed. The concentrate from the flotation procedure was processed using different preoxidation methods. A concentrate containing 34.08g/t of gold with the gold recovery ratio of 81.20% was obtained by flotation. After roasting, microwave heating or alkaline pressure oxidation, the gold cyanidation ratio reached 82.37%, 81.26% and 71.09% respectively. Roasting was an effective, reliable and mature technique to oxidize sulfide minerals and carbonaceous matters. Roasting and microwave heating both produced dangerous environmental pollutants while alkaline pressure oxidation was eco-friendly.

Jan 1, 2015

By R. Y. Wan, S. L. Chryssoulis

"Gold associations were established in a·biooxidized, chlorinated CIL residue assaying 0.02 oz Ault and in a biooxidized thiosulfate leach residue assaying 0.01 oz Au/t. A detailed mineralogical study involved: assays of screened fractions; light microscopy; ion probe microanalysis to quantify 'invisible' gold in sulfide minerals; proton probe microanalysis to detect and quantify preg-robbed gold. In the CIL residue, most of the gold is preg-robbed (71 %). In the thiosulfate leach residue, gold occurs mainly as submicroscopic disseminations in microcrystalline quartz (chert). In both residues, the 'invisible' gold in pyrite accounts for a minor fraction of the gold assay. Quantitative determination of the gold occurrence in the two residue samples established conclusively that gold adsorption on carbonaceous matter in the thiosulfate leach is of minor importance.Acknowledgement: published with permission of Newmont Gold Company."

Jan 1, 1997

By C. M. Chen

Friction stir welding (FSW) is a pure solid-state joining process, which has been widely used in joining aluminum alloys with improved properties. This paper describes a three-dimensional simulation of FSW process, running the ANSYS package of finite element analysis to study the evolutional stress in the butt-welding of aluminum alloy 6061-T6. The model incorporates the mechanical effect of the tool and thermomechanical process of the welded material. The heat source involves the friction between the material and the probe and the shoulder. Thermal history and the evolution of longitudinal, lateral, and vertical stress in the friction stirred weld are simulated. The relation between the calculated residual stresses of the weld and the process parameters such as tool traverse speed is presented. Keywords: Fiction Stir Welding, Finite Element Analysis, Thermomechanical Process, Evolutional Stress, Residual Stress.

Jan 1, 2003

By John J. Dunkley

Recent years have seen the increased use of hydrometallurgy in the smelting and refining of metals. However this is often used as a final refining step, following an initial pyrometallurgical smelting process. Huge amounts of material are produced as melts which have to be cast, comminuted, and taken up into solution or leached. A common method is to granulate the melt and then grind it. In the case of metallic melts this can be difficult or unfeasible due to the ductility of the granulated particles. Water atomisation is capable of replacing the granulation and grinding stages with a single process step that can process in excess of 30t/hour of melt into particles as fine as 50 microns. Applications in operation in Co, Cu, Ni, Ag, Au, Pt and Rh refining are discussed together with potential applications in copper smelting.

Jan 1, 2003

By Jana Dobrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures al each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 20 graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mn, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Afonso Garcez de Azevedo, Anna Carolina Lopes Rabello, Renan Tavares Vicente, Sergio Neves Monteiro, Amanda Maia Ferreira dos Santos

Civil construction is a sector of extreme impact in the Brazilian economy, with construction and demolition waste (RCD) having an extreme impact on the amount of urban solid waste. In this research it was proposed to propose a way of using these residues in the construction of concrete artifacts for structural use. Concrete specimens with sand substitution by RCD were produced in different percentages as a way to contribute to reduce,recycle and reuse thi large amount of waste from the construction industry. The objective of this work was to study the mechanical properties of structural concrete with total and partial replacement (25, 50, 75 and 100%) in sand mass. The results of the compression test indicate good quality for concretes with mass substitution of up to 75% per RCD.

Mar 1, 2018

By C. Carreno, A. D. Gonzalez Escarcega, M. A. Neri, A. Martinez –Villafane, O. Cobarrubias-Alvarado

"Waspaloy is a superalloy used to manufacture some aeronautical parts subjected to high temperatures and stresses. During thermo-mechanical processing cracks are generated, causing some parts to be rejected. In order to determine the causes of these cracks, this alloy was characterized using techniques such as chemical analysis, optical microscopy, scanning electron microscopy, and EDX analysis. Heterogeneous grain sizes in the microstructure cause a non-uniform strain distribution in these parts, creating cracks in zones with different grain sizes.IntroductionNickel-base superalloys are important materials for high-temperature service applications. The manufacture of components from these materials is typically based on solidification or powder-metallurgy processes [1]. Solidification techniques comprise either the direct casting of parts or the casting of ingots which subsequently undergo a series of thermo-mechanical-processing steps to refine the microstructure. During solidification, microsegregation is usually unavoidable. The primary solidification product is a disordered nickel solid solution with an fee crystal structure (?). In many alloys, the material which solidifies last is a mixture of ã and an ordered fee phase (? '). In prototypical nickel-base superalloys, the ?'-phase is Ni3(Al,Ti) [2-3].Waspaloy is a superalloy that is used in demanding high-temperature environments in which good creep and fatigue resistance are required. One of the most common applications of Waspaloy is for turbine engine rings. To ensure the required mechanical properties, the rings are usually forged and heat treated (Figure 1). Two distinct types of microstructures are usually found to be attractive for such applications: a) A microstructure with a grain size of ASTM 10 to 14 for tensile strength, ductility, and resistance to crack nucleation in low-cycle fatigue; or b) A microstructure with a grain size of ASTM 4 to 8 required for creep strength and resistance to crack propagation [4]. Because it is impossible to refine the grain size through heat treatment, a skillfully designed forging process is crucial for the control of the grain size and, hence the properties of the forged ring [5-6]."

Jan 1, 2012

By S. N. Monteiro, E. B. Zanelato, J. Alexandre, M. T. Marvila, A. R. G. Azevedo, G. C. Xavier

One of the parameters used in the study of mortars is the adhesion resistance, which indicate show much the mortar adhered to the substrate. The usual study is done at 28 days, to worldwide standardization. Few researchers study the adhesion of mortars to ages other than 28 days. In this scenario, the adhesion strength tests of conventional mortar with a 1:1:6 mass scale (cement, and sand) at 7, 14, 28, 56, 91, 182 and 364 days were performed in order to understand the behavior of this material. The usual characterization tests of the mortars were carried out to correlate the values obtained with the adhesion results. The obtained results demonstrate that the mortar continues to gain resistance with the passage of time. For the trait studied the gain was considerable, indicating that over time the cement continues to hydrate, reacting and contributing to the strength of the material.

Mar 1, 2018

By D. Zhao

High temperature deformation characteristics of austenitic 304L, and martensitic 410 and 416 stainless steels were investigated by conducting compression tests over a wide range of temperatures and strain rates (950-1250 C and 0.001-20 s-1). Flow behaviors of the three alloys were characterized. Optical metallography was performed to determine the as-deformed microstructures. The flow behaviors were related to microstructural phenomena during high temperature deformation. Dynamic recrystallization was responsible for the flow softening. Both dynamic and static recrystallization were operating, and the recrystallized grain size increased with increasing temperature and decreasing strain rate. Strain rate sensitivity was found to increased with increasing temperature and decreasing strain rate. No defects such as cracking and shear bands were observed at those test conditions. Preferred processing conditions can be selected by considering as-deformed microstructure and strain rate sensitivity.

Jan 1, 1994

By Ernt. W. D.

A membrane based mixed extractant process was developed for selective removal of copper from waste acidic cupric chloride etchant solutions found in printed wire board manufacturing. The process uses a mixture of Adogen 381 (tri-isooctylamine), MOC®-45 (ketoxime) and MOC® 55TD (aldoxime) in a kerosene diluent. The mixed extractants recover the copper from a hydrochloric acid medium and transfers it to a sulfuric acid medium. The process also utilizes unique wetted membranes to separate the aqueous and organic phases. The driving force for these membranes is not pressure but the difference in surface tension between the two phases. By using these membranes, complete phase separation results. There is no physical entrainment contamination as found in conventional systems. The only cross contamination is the solubility concentration of one phase in the other. This however is less than 10 mg/l.

Jan 1, 1998

By Carl C. Nesbitt

A study was conducted to investigate the claims of early observers who noted an increase in the rate of gold dissolution when chlorine was chemically produced in the leach vessel compared to sparging with chlorine gas. This "nascent" chlorine was presumed to be an active intermediate in the production of chlorine (C1,l from chloride ions. The study used UV light to produce an activated chlorine atom intended to recreate the observed increase in the gold dissolution rate. Although no change in the kinetic rate was observed, the reaction mechanism by which chlorine reacts with particulate gold was instead determined. Various concentrations of multivalent cationic chloride salts were added to the leach solution to demonstrate that the increased dissolution rate was due to the increased concentration of the chloride ion and ionic strength of the solution.

Jan 1, 1992

By Jan Dabrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures at each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 2D graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mu, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Catherine Williams-Beam

Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc. Its chemical behavior resembles the alkali metals (K, Rb, Cs). It occurs almost exclusively in natural waters the monovalent thallous cation. The solubilities of thallous compounds are relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. The major sources of thallium are the base metal sulfides and precious metal bearing sulfides. Therefore, it is often present as a contaminant constituent in waters emanating from heavy metal sulfide bearing deposits. Thallium can be effectively removed from wastewater to <2 µg/L by reductive precipitation of thallium sulfide. Effective thallium sulfide precipitation requires a controlled solution potential/pH combination. The required potential can be effectively achieved by utilizing a particulate iron slurry or packed column environment. Experimental results will be presented and discussed.

Jan 1, 2003

By Keiji Okumura, Jiayi Shan, Jian Yang, Masamichi Sano

"A new method of deoxidation and desulfurization of molten iron with magnesium vapor has been developed. An immersion tube, which was filled with pellets of the mixture of magnesia and carbon powders, was put into the molten iron. Magnesium vapor produced by carbothermic reduction of magnesia inside the tube was injected directly into the molten iron with argon carrier gas. The effects of temperature and carrier gas flow rate on deoxidation and desulfurization were investigated. A mathematical model of the reactions was developed. The rates of deoxidation and desulfurization were controlled by mass transfers of magnesium vapor in the gas-phase and oxygen and sulfur in the liquid-phase. This method may offer high efficiency for magnesium deoxidation and desulfurization of molten iron.IntroductionMagnesium is a strong refining agent in steel-making processes1 • At steelmaking temperatures, magnesium has a very low solubility in liquid iron, and a very high vapour pressure2 • Deoxidation and desulfurization with magnesium take place essentially through the interaction of magnesium vapor with oxygen and sulfur dissolved in molten iron, and magnesium can change chemical composition of nonmetallic inclusions3 • However, addition of magnesium to the steel bath is dangerous and does not give high efficiency in the refining process4 • Furthermore, as a refining agent, the price of magnesium is higher than aluminium and CaO fluxes. In the present study, a new method of the deoxidation and desulfurization of molten iron was developed using magnesium vapour in-situ produced by carbothermic reduction of magnesium oxide. Pellets made of mixture of magnesia and carbon powders were charged into an immersion tube, which was made of alumina or graphite. The magnesium vapor was injected directly into the melt. The effects of pellet mass, experimental temperature and carrier gas flow rate were studied on the refining rate. A mathematical model of the refining reaction was proposed on the basis of the experimental results."

Jan 1, 2000

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

By Takashi Ikeda, Masafumi Maeda

"Demand for solar cells is increasing linearly throughout the world. Last year production totaled 3000 tons worldwide. The market size of solar silicon is expected to increase further because of international ""political"" demand to reduce carbonaceous emission from energy consumed. Most elemental silicon is produced by the carbon reduction of Silica in an electric arc furnace. Purity of silicon at this stage is 90-99%. Major impurities are Fe, Ti, Ca· and Al, and minor ones are P, B and carbon. The oxidizing metallurgical process is no longer effective to remove transitfon metals because those are less noble to silicon. Nonmetallic impurities such as phosphorus and boron must be reduced to 0.001ppm for semiconductor use. The most common process for high purity silicon is the Siemens C process, which is basically distillation of hydro-chlorinated silicon followed by CVD of SiHCl3. The cost of such silicon is expensive to allow its popular use in solar cells. Currently scrap silicon -of semiconductors is used for this; however, the supply-of that scrap is limited to just a portion of semiconductor production.In this paper world demand for silicon will be reviewed and some of the processes proposed summarized.IntroductionSilicon is element 14 in atomic number and has an atomic weight of 28.0855. Little elemental silicon is found in the earth, and it is mostly found as oxides or silicate. The Clark number of silicon is very large and the second in its number. If we were discussing the volatility of silicon element on the globe, we would never worry about it. However, it is very difficult to obtain pure elemental silicon because a high purity silicon compound is very rare. In most cases these are silica (silicon oxide SiO2). As shown in Table 1, there are many grades of silica ore classified mainly by their content of iron and alumina."

Jan 1, 2000

By Xavier Kleber, Aude Lamontagne, Veronique Massardier, Daniele Mari

"The thermoelectric power (TEP) technique was used to determine with high accuracy the strain ageing kinetics in heavily cold drawn pearlitic steel. Because of the very high sensitivity of the TEP to solute atoms, this technique allowed the strain ageing to be followed from the very first moments. The kinetics were followed during isothermal ageings performed between 20°C and 200°C for different strains. In order to avoid any ageing at room temperature, the samples were kept at -80°C immediately after cold drawing. TEP evolution versus strain highlights cementite decomposition occurring during cold drawing. During the ageing, a redistribution of the dissolved carbon atoms in ferrite occurred. The TEP increase with the ageing time was attributed to the departure of carbon atoms from ferrite (segregation to dislocations and/or carbide precipitation). The kinetics were analysed using the Johnson-Mehl-Avrami-Kolmogorov approach which enabled to determine activation energies associated with carbon atoms redistribution.IntroductionHeavily cold drawn pearlitic steel wires are commonly used as structural materials for their high strength and their acceptable ductility. However, several previous studies highlight the microstructural destabilization of pearlite mainly due to cementite decomposition during the drawing process, which induces changes of mechanical properties [1, 2]. This phenomenon was detected by several experimental techniques such as Mossbauer spectroscopy [3, 4, 5], themomagnetic analyses [6, 7], TEM [8, 9, 10] or atom probe tomography [9, 10, 11]. Nevertheless, the mechanism of cementite decomposition is still unclear. Several hypotheses were proposed in the literature. The first hypothesis relies on a strong interaction energy between carbon atoms and dislocations involving higher binding energy than that between carbon atoms and iron atoms in cementite [3]. The second hypothesis is the increase of the free energy of the interface between cementite and ferrite due to the fragmentation of cementite during deformation (Gibbs-Thomson effect) [8]. Some authors even suggest that the dissolution of cementite occur during a post-deformation ageing [12, 13]. It is worth"

Jan 1, 2013