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By Tabbetha A. Dobbins

We report studies concerning the time frame for catalytic reactions between NaAlH4 (sodium alanate) and TiCl3 during high energy milling. Spectral features in x-ray absorption spectra were analyzed for samples milled for various times (0 minutes, 1 minute, 5 minutes, 25 minutes, and 125 minutes). A structural transition from Ti3+ to Ti0 is observed within the first 5 minutes of milling. The Ti0 structure persists for samples milled for times longer than 5 minutes?even after those samples underwent a subsequent single hydrogen desorption/absorption cycle. Samples milled for less than 5 minutes retain Ti3+. For samples milled for 1 minute, the Ti-K edge position shifts from Ti3+ to Ti0 after a single desorption/absorption cycle. However, the first coordination sphere around the Ti0 absorber occurs at longer distances for 1 minute milled sample. These results hint at the formation of Ti0 pure metallic clusters upon desorption/adsorption cycling of 1 minute milled sample. Previously reported x-ray absorption spectroscopy studies have demonstrated the structural transition from Ti3+ (in TiCl3) to Ti0(determined to be TiAl3 found at the surface of the alanate powder). Aluminum deficiency on the NaAlH4 lattice is responsible for controlling hydrogen absorption capacity. These time-resolved spectroscopy studies suggest the possibility for controlling aluminum deficiency, while still maintaining titanium activation of the alanate powder, by manipulating the coordination environment of the titanium dopant during the first five minutes of high energy milling. Specifically, a possible approach to mitigating aluminum deficiency during doping would be to introduce an alternative species to which the to Ti3+ catalyst would form a metallic bond after the TiCl3 has attached at the surface of the sodium alanate powder and before the Ti3+ forms the TiAl3 intermetallic species.

Jan 1, 2006

By E. V. Verhoej

The proposed EU directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment promotes the substitution of lead in consumer electronics to reduce emissions from lead in the end of life phase. In this paper, the consequences of substituting lead in solders is assessed using the Eco-Indicator-99 method for the examples. The base metal production system is considered as an interconnected network modeled dynamically in Simulink 4 and Matlab 6 (Mathworks Inc 2000), where the recovery and production of metal components of the assessed product partially overlap. This approach requires global modeling of metal production processes and mass balances and resulting allocation choices. It also reveals the susceptibility of LCA scores to different choices in the modeling and data availability and uncertainty. Besides the comparison between lead-free and lead-containing solders, other side effects are revealed. Lead is carrier material for the recycling and production of many co-elements in the interconnected production and recovery system. Substitution may have adverse effects such as temporary shortages of other connected metals that are often not considered in normal LCA assessments, thus leading to erroneous results. The suggested approach provides directions for including these extemal effects and for further assessment of the environmental effects of substituting lead. This paper shows that in order to assess the environmental aspects of metallurgy, dynamic modeling of the total system is required based on the fundamental thermodynamics in each metallurgical reactor, the basis of this dynamic model. With this the true environmental impact of metallurgy can be explained. In the case of lead free solder, it is shown that the mining of substitutes has a very much larger impact.

Jan 1, 2003

By Björn Saxen

Outotec atmospheric Direct Leaching has so far been implemented for zinc production capacities of around 100,000 t/a. Lately, there has been growing interest for small scale direct leaching plants, producing circa 30,000 t/a of Zn. Such small leaching plants can provide extra front-end capacity in existing roaster-based plants and enable treatment of feed materials not suitable for roasting. In small scale plants the proven OKTOP® 9000 Direct Leaching reactors are not readily applicable, due the large size. For smaller installations a modular approach is proposed providing multiple advantages, such as reducing the construction time and amount of the site work required causing less disturbance to regular plant operation with reduced cost. In this paper, we present advantages that can be achieved by using modular OKTOP®C reactors and discuss also process design when connecting a small scale direct leaching process to an existing zinc plant. Also benefits of direct leaching expansion are presented.

By Jingbo Liu, Zhimin Wang, Wenchao Li

"IntroductionThe advantages of non-stoichiometric perovskite material are highlighted in many papers[l]and many of this family of materials are well-suited to integration into microsensor devices. Among them, barium titanate is the most promising due to it's piezoelectric, pyroelectric, dielectric properties. Through modification, BaTiO3-based materials can be utilized in many kinds fields, such as surface wave probe; pholoconducting devices, field-effect transistor, permanent memory permanent storage, and ultrasonic transducerl2-3l. In this Paper, a series of BaTiO3-based polycrystals were synthesized by sol-gel processing which appears to be a very promising method for the manufacture of ceramic, because it offers significant advantages such as high purity, chemical homogeneity, controlled particle sizes of ceramics, and lower processing temperatures [4]. In a sol-gel process, alkoxides of the constituent elements show different reactivity toward water so that the preparation of multi-component homogenous system is difficult. In the experiment, inorganic salt was substituted for some of the alkoxides. Acetic acid which is employed for the solvent and catalyst, acts as donor ligand to titanium alkoxide and controls, the hydrolysis polycondensation reaction. Taking these aspects into consideration, we select the system Ba(OAc)2, , La(OAc)3, Ti(O11Bu)4 and acetic acid which is used as both solvent and homogeneous catalyst for the first time.ExperimentalA series of La3+-doped BaTiO3-based nano-crystals were prepared with sol-gel technology using various parameters. The precursor solution was prepared in the presence of barium acetate, lathanium acetate, and titanium tetrabutoxide monomer in butyl alcohol. According to the flow chart (fig. I.), Ba(OAc)2, La(OAch dissolved in the glacial acetic acid (0. lmol/40ml) in a three-neck flask were mixed with a solution of titanium tetrabutoxide monomer in butyl-alcohol(l 7ml/20ml) at room temperature and under constantly, vigorous stirring conditions. In most cases, the resultant solution was golden yellow and stable in the air. To this precursor solution, containing Ba, La, Ti in the desired ratio, water was added incrementally for hydrolysis under continuous stirring until sol was formed. After aging for more than 2 hours, sol was transformed to gel at room temperature. If heated during aging, the gel was formed in a shorter time. The wet gel was allowed to dry at 50°C for more than 10 hours. The dried gel was transparent or light yellow. In order to obtain BaTiO3-based nano-crystals, the amorphous dry gel was calcined at 600°C, 700°C, 800°C, 900°C, 1000°C respectively[5]. The ceramic humidity sensor was formed through the cold-pressed, aged, capsulated routes. The dried gels were crushed in an agate mortar and then pressed into discs of ? 1.5 X l.5mm (l.5mm diameter and l.5mm thickness), then held at about 16.5 MPa pressure for 3 min [6]. The disc was sintered at 1350°C and 1400°C for I hour respectively. During the processing, an Ag-Pt electrode was inserted in the sensor [7]. (See the flow chart.)"

Jan 1, 2000

By E. V. Verhoef

The proposed EU directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment promotes the substitution of lead in consumer electronics to reduce emissions from lead in the end of life phase. In this paper, the consequences of substituting lead in solders is assessed using the Eco-lndicator-99 method for the examples. The base metal production system is considered as an interconnected network modeled dynamically in Simulink 4 and Matlab 6 (Mathworks Inc 2000), where the recovery and production of metal components of the assessed product partially overlap. This approach requires global modeling of metal production processes and mass balances and resulting allocation choices. It also reveals the susceptibility of LeA scores to different choices in the modeling and data availability and uncertainty. Besides the comparison between lead-free and lead-containing solders, other side effects are revealed. Lead is carrier material for the recycling and production of many co-elements in the interconnected production and recovery system. Substitution may have adverse effects such as temporary shortages of other connected metals that are often not considered in normal LeA assessments, thus leading to erroneous results. The suggested approach provides directions for including these external effects and for further assessment of the environmental effects of substituting lead. This paper shows that in order to assess the environmental aspects of metallurgy, dynamic modeling of the total system is required based on the fundamental thermodynamics in each metallurgical reactor, the basis of this dynamic model. With this the true environmental impact of metallurgy can be explained. In the case of lead free solder, it is shown that the mining of substitutes has a very much larger impact.

Jan 1, 2003

By E. Burgos Cruz

The behaviour of S, N and P during refining of Fe-18 wt%Cr-10 wt%Ni with calcium carbide was investigated. The effects of the initial contents of C and N in the metal phase, as well as the supply method of calcium carbide to the melt on the removal degrees of S and P were evaluated. Heats were carried out at 1873K, in MgO crucibles, using a laboratory induction furnace. It was observed that simultaneously with S and P, N and O have also participated in the reactions. It seems that, in fact, O governs the behaviour of the other elements dissolved in the melt and that N is had to the removal of P with calcium carbide. It was also noticed that high C content in the metal phase have not altered the dephosphorization and desuffirization degrees, but that the supply of calcium carbide done by injection led to a lower dephosphorization degree than the one obtained by dumping it.

Jan 1, 1995

By Daoxin Wu

In this paper, the rutile TiO2 were prepared under air, Ar and H2 calcination atmosphere by low temperature hydrolysis using Tetrabutyl titanate (C16H36O4Ti) as raw material. Powers were characterized by X-ray diffraction, UV-vis diffuse reflectance and X-ray photoelectron spectroscopy. The influence of the calcination atmosphere on the photocatalytic reactivity of rutile TiO2 for oxygen production was investigated. The photocatalytic reactivity of rutile TiO2 prepared under air, Ar and H2 atmosphere was compared under ultraviolet and visible light radiation with Fe3+ (c=8.0mmol.L-1) as electron acceptor. The results showed that rutile TiO2 prepared under Ar and H2 atmosphere had higher photocatalytic activity for oxygen production than that prepared under air atmosphere. The oxygen production rates under ultraviolet irradiation were 427.5, 378.2 and 357.0µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere. The oxygen production rates under visible light irradiation were 78.2, 52.2 and 13.5µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere.

Jan 1, 2008

By F. Sanchez, A. Mejias, C. Frias, G. Diaz

"Crude zinc oxides are the major source of secondary zinc and are produced from fuming processes like Waelz kilns. The impurities of crude zinc oxides make difficult their processing in primary zinc refineries due to mainly high chloride tenor. Washing with sodium carbonate is a costly operation and chloride removal efficiency is not good enough, so further purification steps are required. The crude zinc oxides are easily treated using ZINCEX™ technology based on leaching, solvent extraction, and electrowinning. The ZINCEX™ process is commercially available and is designed to be a perfect barrier for metallic impurities and halogens, allowing selective zinc extraction in mixed chloride and sulfate leaching solutions. Other valuable components as lead and silver can be efficiently recovered from the leaching residue using PLINT technology in chloride media. Silver is recovered as silver cement and lead is precipitated as pure lead oxide or carbonate, which can be smelted at low temperature.IntroductionZinc is a fully recyclable metal and at present approximately 70% of the zinc produced worldwide comes from primary zinc while 30% originates from secondary materials. Nowadays, the zinc recycling rate is continuously increasing mainly through galvanized steel scrap processing, and crude zinc oxides are the major source of secondary zinc [1]. Secondary zinc oxides are obtained from fuming processes like W aelz Kiln, Rotary Hearth Furnace or Primus Furnace. Waelz is the dominant technology accounting for 80% of total crude zinc oxides production worldwide. In the Waelz process, steel dust is mixed with solid fuel reductant (coke breeze) and pelletized. It is then fed to the kiln and heated to a reaction temperature of l ,200°C. In such conditions, zinc, lead, and other non-ferrous metals are vaporized into the flue gas together with chlorides and alkaline metals. Mixed oxides are drawn from the kiln with the process gases and separated to produce typical crude zinc oxides [2]."

Jan 1, 2011

By A. R. G. Azevedo, G. C. Xavier

"This work has for objective to identify the soil of the neighborhood Codin located in a lacking area of the urban nucleus of the district of Campos dos Goytacazes - RJ, after the identification the best line was determined for the production of soil-cement blocks. In this area it happens habitational deficit and precarious constructions are also verified. The use of soil cement blocks is considered a cheaper constructive method than the conventional (ceramic block or of concrete), because one of the components of the raw material is abundant (the soil) and the constructions can be erect with certain easiness for collective effort regime. Samples of soil of this area were collected for they be characterized with relationship to the physical and chemical characteristics, with I aid of GPS the community's location it was registered. Identified the soil type, the work began the study of lines they to make possible your use in an economical and safe way. For that were made drained blocks in the format 19,5x10x5 cm, with lines containing the addition of 5% and 10% of cement in volume, and as parameter of quality the absorption of water and the resistance to the compression were measured, following the Norms of ABNT.IntroductionWe know that the use of the soil by the humanity come from the antiquity. And ifs confirmed by the archaeology places of the old civilizations of the word. The most remote constructions date from 10.000 years old in Jericoh, in the Jordan River Valley. This work became more intensive at 3.000 B.C. (Before Christ), by people who lived in those valleys with mood areas, a lot of clay and washed by the rivers.Almost all the sectors of engineering of soils choose the stability to use the local soil. Although, artificially treated, offers more economical advantages.The stability of a soil consist of endow it of the condition to resist the deformations and ruptures during the period that it is being used, because these characteristics are necessary in any construction.The application of the natural soil only is possible in places that they are of good quality and attend to the requirements of engineering to the type of previewed application. The granulemeter correction and the chemical stability include cases of inappropriate soils areas, turning the soil able to be used as construction material. Among the stability agents, usually added to the soil for stability ends, the cement is indicated."

Jan 1, 2013

By Dalene Joalet Steenkamp

Excavation of industrial-scale furnaces allows for the systematic study of reaction sequences by identifying the different reaction zones within the furnace. In 2013, Transalloys excavated a 48 MVA submerged arc furnace that was used for silicomanganese production using the ore-based route. The excavation method was reported elsewhere as was observations made in terms of refractory wear and modes of electrical energy dissipation prior to excavation. The paper presented here, reports on the process reaction zones observed during the excavation and subsequent phase chemical analyses of a number of process samples obtained during the excavation. The zones identified were a loose burden zone, a dry coke-bed zone, a wet coke-bed zone, a hard build-up zone, and an alloy zone. The results are compared to observations made in the excavation of an industrial-scale SAF and a pilot-scale SAF in Norway. The presence of the hard build-up zone below one of the electrodes and absence of a slag zone below all three electrodes are unique features of the SAF excavated at Transalloys.

By Marcel Sturzenegger

Though the extraction of copper is well established, generation of sulfur dioxide (S02) is still a troublesome issue. Conventional processes are further challenged by the increasing amount of impurities in the concentrates. Direct decomposition of the metal sulfides into the metal(s) and elemental sulfur under concentrated solar radiation offers a promising path to solve both problems. Thermogravimetric measurements under inert atmospheres have shown that synthetic chalcocite or chalcopyrite yield copper at temperatures as low as 1773 K. Even though optimum reaction temperatures might be somewhat higher, such temperatures are straightforwardly accessible in solar chemical reactors. The absence of oxygen will reduce the extent of slag forming reactions and thereby alter the evaporation characteristics of volatile impurities such as arsenic or antimony. Chemical equilibrium calculations for a chalcopyrite-enargite feed, e.g., have shown that under inert atmospheres arsenic compounds are completely evaporated at temperatures above 1000 K and an effective separation of arsenic from the matte is expected. An important step towards a solar production of copper is the design and testing of prototype solar chemical reactors for this reaction. Numerical modeling is a key tool supporting a rational design but it requires data of the high-temperature properties that prevail in these processes. Development of techniques for determining the essential quantities such as decomposition rates or radiative properties at temperatures up to 2000 K is therefore a main activity in our laboratory in order to control and optimize the process. Though developed in the frame of high-temperature solar technology, the experimental techniques are also suited to advance the understanding of conventional high-temperature processes. Keywords: Solar technology, Sulfur dioxide, Solar Radiation, Thermogravimetry, Chalcocite, Chalcopyrite, Numerical modeling.

Jan 1, 2003

By A. N. Lasseigne

Hydrogen storage capabilities of LaNi5 intermetallic compounds were investigated utilizing the combination of thermoelectric power, Beeghly Ester-Halogen digestion, and Leco hydrogen determination. Thermoelectric power has demonstrated a rapid hydrogen assessment capability and can achieve the equivalent of the pressure-composition-temperature (activity) diagram. Effective use of hydrogen storage materials occurs in the two-phase, alpha+beta region of the PCT diagram. A thorough assessment of the content of each phase in this two-phase region to optimize performance of the hydrogen storage materials is described. Practices using the combination of these three analytical practices for rapid characterization of LaNi5intermetallic alloys are discussed.

Jan 1, 2006

By Tang Chaobo

According to the principles of simultaneous chemical equilibrium and electronic charge neutrality, the system of Mg(II)-NH3-CO32--SO42--H2O at 25°C has been thermodynamically analyzed. And the rule of solubility of MgCO3(s) in the system is discovered, the high dissolution field of MgCO3(s) is discovered too. Furthermore, the solubility of MgCO3(s) is increased with the increase of the concentration of SO42-, but it is decreased first then increased with the increase of the concentration of all the CO32- and the total concentration of ammonia and ammonium, and decreased with the value of pH being higher. Those results will has important significance on prepare magnesium chemical products and other salts carbonate that are strict with the content of magnesium with carburization method.

Jan 1, 2006

By J. Vander Linden, R. De Ketelaere, M. Verhaege

In this paper, results are presented concerning the search to implement Supported Liquid Membrane (SLM) technology for the recovery of copper from electroplating effluents. Acid copper electroplating rinse solutions or effluents resulting from the post-treatment of, for example, cyanide-containing copper electroplating baths all contain copper (2+) in the lower concentration levels. A thorough study of the influence of the individual parameters and of their combined impact on mass transfer in small scale laboratory SLM modules has been performed, enabling to set forward the appropriate operating conditions for a pilot plant installation. The pilot plant, containing two SLM modules. of 18 m2 of surface area, has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that this installation is able to treat 40 l/h of acid copper sulphate rinse solutions· containing 500 ppm of copper. The final copper concentration in the effluent can be reduced to a few ppm while copper metal is recovered by electrolysis of the concentrate. This technology is also applicable to the treatment of solutions with low copper content of origins other than plating shops, such as tailings from copper plants or mine waters.

Jan 1, 2000

By Hiroyuki. Fukuyama

The pseudo-binary phase diagram of the cuspidine (3CaO2?SiO2?CaF2) - CaF2 system has been studied by electron probe microanalysis (EPMA) and X-ray diffractometry (XRD). To prevent fluorine loss in the form of a HF gas by a reaction of CaF2 with water vapor at elevated temperatures, the equilibrium experiments were conducted with the sample hermetically sealed in a platinum tube. By employing this technique, it was successfully revealed that cuspidine exists as a stable phase and congruently melts at 1684 ± 1 K, and the cuspidine - CaF2 system presents a simple eutectic type of phase diagram, of which eutectic temperature has been estimated to be around 1540 K, corresponding to the composition of 40 mass% 3CaO?2SiO2 - 60 mass% CaF2?

Jan 1, 1999

By C. Alexandru Sonoc

Donnan Dialysis uses ion exchange membranes to extract and separate cations. The driving force is provided by differences in chemical potential, rather than by electric fields or pressure. A Donnan Dialysis based process to recover lithium, nickel, cobalt, manganese, and organic acid lixiviant from recycled lithium ion battery cathodes is under development. In this paper we present a model of Donnan Dialysis and results of simulations of the aforementioned process. The simulations show that 170 m2 of membranes can process 1000 L of leachate ([Li+] = 0.285 M, [Co2+] = [Ni2+] = [Mn2+] = 0.095 M, pH 2) in two days and recover 94.1% of the lithium (as lithium carbonate), 99.4% of the transition metals (as mixed sulphates ready for solvent extraction), and all of the organic acid using 423 mol of H2SO4 and 268 mol of KHCO3.

By Matti Leiponen

During the last few years Outokumpu Oy has put forth efforts to develop the material handling in the Pori tankhouse. The final objective is full automation including cell loading. The fully automated material handling provides high quality anodes and cathodes as well as equipment and handling systems capable of very accurate cell loading. The new machines and equipment for accurate cell loading and the methods to produce high quality anodes and starting sheets are described in this paper.

Jan 1, 1987

By Ann M. Hagni

Electric arc furnace (EAF) dust from the secondary steel industry contains lead, cadmium, and chromium that causes it to be classified as a hazardous waste. Pyrometallurgical treatment of EAF dust is directed at recovering zinc and simultaneously rendering the dust non-hazardous. The mineralogy of the EAF dust is important in determining the occurrence and phase relationships of the zinc, lead, cadmium, and chromium contents. The principle phases in EAF dust as determined by reflected light microscopy, SEM-EDS, and XRD are solid solutions of the iron spinels (franklinite, magnetite, and jacobsite), zincite, hematite, and Ca-Fe-Si glass. Chromium is present in small amounts in solid solution in the spinels. Cyclone sizing of the minus 53 pm particles shows that more than 50% of this size fraction are less than 10 pm in diameter. The <I0 pm particles contain zinc as both franklinite in solid solution with magnetite and jacobsite, and zincite as determined by transmission electron microscopy and XRD. Auger electron spectroscopy did not detect coatings of volatile phases on the surfaces of EAF dust particles.

Jan 1, 1994

By Xue Wang, Callie Babbitt, Chelsea Bailey, Matt Ganter, Gabrielle Gaustad, Brian Landi

"Current trends, motivated by fossil fuel dependence and unprecedented greenhouse gas (GHG) emissions, show lithium-ion batteries (LIBs) emerging as a competitive energy storage technology due to higher power and energy densities compared to Pb-acid and Ni-metal hydride chemistries. These trends may be of concern, however, as environmental impacts are not well understood for either the LIB itself, or for the nanoparticles consumed or released during the battery's production, use, or end-of-life. This study combines economic modeling, dynamic material flow analysis, and fundamental material characterization methods in order to quantify some of the economic and environmental trade-offs for LIBs at their end-of-life. As expected, results show that as chemistries transition from Li-Co based cathodes to Li based Fe, Mn, and S cathodes, LIB recovery value correlates to the value of the raw materials used. These initial results aim to inform collection policies being proposed currently as well as enable future deployment of novel recycling techniques.IntroductionGlobal fossil fuel dependence and unprecedented GHG emissions have led to increasing attention on energy alternatives, for both electricity production and personal transportation. However, development of renewable energy systems is contingent on concurrent technological development of energy storage systems, primarily batteries used for power grid load-leveling, renewable energy storage, and hybrid and battery electric vehicles. In this sector, lithium-ion batteries (LIBs) are emerging as a competitive technology due to higher power and energy densities compared to lead-acid and nickelmetal hydride chemistries[!]. LIBs represent close to 20% of the total rechargeable battery market and 75% of the portable rechargeable battery market, which is the fastest growing segment of the rechargeable battery market, with a 20% global growth in 2008 [2].This surge in production ofLIBs indicates a looming waste problem; total waste from Li-ion batteries has likely grown substantially from the 500 metric tons estimated in 2003 [3]. Figure IA shows the substantial increase in world-wide lithium production that has occurred in the last several decades with batteries making up the largest share of applications (Figure lB). California and New York state legislators have attempted to proactively address this looming waste by issuing diposal bans on rechargeable batteries in their states[4, 5]. However, quantification of the costs involved in collection, transportation, and processing of these materials has not been examined in depth."

Jan 1, 2012

By Tiejun Chun, Marcus Emrich, Jian Pan, Deqing Zhu, Vinicius Mendes

"Joint projects of studies of hematite acid pellet have been implemented to develop technological solutions for using Vale hematite pellet feed in Chinese palletizing plant. Beneficial improvements on the pellets quality were achieved by adjusting the blends composition and using new technology of pre-treating the blended pellet feed with HPGR (High Pressure Grinding Roller) on rotary kiln pellet technology. The drop strength of green balls increased from 3.4 to 6.0 times from 0.5m height, at the same time, the bentonite dosage decreased from 1.5wt% to 0.7wt%. The compressive strength of roasted pellets reaches 2500 N/pellet. The reduction swelling index of roasted pellets is below 15%.IntroductionWith the fast development of steel industry in China, the production of pellets has been further expanded. Pellets are used as a high quality charge for blast furnace and the annual output is around 80Mt pellets [1]. According to the developmental trend, sinter will be replaced by pellets due to the larger environmental impact of sintering plants when compared to pelletizing plants. For example, the specific CO2 emission in sintering process is around 2.5 times higher than in pelletizing process. However, the steel industry of China has been confronted with a serious shortage of domestic pellet feed due to the low iron grade of Run-of-Mine ore despite of huge reserves of iron ores [2]. Therefore, more pellet feed, mainly hematite, has been imported to make pellets."

Jan 1, 2011