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By Federico Chavez

The process for recovering lead from battery residues used in several Mexican Plants include lead blast furnace and rotary furnaces. The formers are basically fed with recycled batteries together with the necessary additives to produce metallic lead. One of the by-products generated in the blast furnace is a dust mainly formed by lead sulfide. The rotary furnace is used to recover lead .from lead batteries, dross from the refining-alloying process and the leady fines produced in the blast furnace. This paper describes thennodynamic analysis made to the rotary furnace process to understand the effect that each component of the system has upon the lead recovery. In order to enhance the process, the influence of iron chips composition and excess coke on slag viscosity is discussed. A computer optimization program . has been developed to design the furnace charge based on material and energy balances, .together with the thennodynamic equilibrium calculation.

Jan 1, 1995

By T. Johnson, B. Q. Li

"Electromagnetic stirring has found a wide application in metals processing for the benefit of obtaining refined solidification microstructures. This paper presents an experimental study on the melt flow and turbulent behavior in an electromagnetically stirred Woods metal pool. The experimental setup consists of metal bath unit equipped with temperature control to allow both cooling and heating, velocity probe positioning unit and data and signal acquisition and processing unit. The whole measuring system is under the control of an IBM personal computer. Velocity measurements are made using the incorporated magnet probes, which are calibrated using a turntable. The measured results showing the effect of the coil positions, coil arrangements and the applied currents on the melt flow are presented. Both mean flow and turbulence quantities are discussed.1. IntroductionElectromagnetic stirring is widely practiced in the metals industry for melt mixing and for casting microstructure refinement. Industrial examples are taken from induction furnaces where the electromagnetic forces are applied to generate desired melt mixing and also various types of electromagnetic stirrers used in various stages of steel and/or aluminum casting processes to produce fine grain solidification microstructure or to eliminate undesired defects such as TCG (twinned-columnar-grain) structure. For ultrahigh purity aluminum or high strength aluminum alloys containing zirconium or lithium, grain refinement can be difficult with the conventional technique, and electromagnetic stirring provides a particularly powerful means to obtain the refined solidification microstructure [1]. A fundamental understanding of the melt flow and the turbulence characteristics in these magnetically-driven flow systems is of significant engineering importance to both process design and product quality improvement.There exists extensive literature on the magnetically-driven melt flows in material processing systems. Nakanish. et al. [2] were perhaps among the early investigators to mathematically and physically model the magnetically-driven flow phenomena in molten metal systems. Subsequent theoretical and experimental work by Tarapore and Evans [3, 4], Szekely and Chang [5], Hunt and Moore [6] and Szekely and El-Kaddah [7] has contributed very significantly to our understanding of magnetically-driven flow in inductively stirred melts. They have developed mathematical models for the electromagnetic field and turbulent flow in induction furnace and validated the models by either laboratory experiments or direct measurements in the industrial-scale induction furnaces."

Jan 1, 1998

By Young-Sool Jin, Heung Nam Han, Hong Joon Kim, Jae Kon Lee

A mathematical model was developed considering non-symmetric cooling' and stress distribution in both thickness and width direction of strip on a run-out table of hot strip mill. In order to solve a transient heat transfer equation including the heat evolved from phase transformation, a finite element method coupled with thermodynamic and kinetic analyses was applied. The heat capacity of each phase and heat evolution due to phase transformation were obtained from the thermodynamic analysis of the Fe-C-Mn-Si system based on a sub lattice model. The phase transformation kinetics of the steels was derived by using an inverse additivity technique with continuous cooling experiments. Heat transfer coefficients of strips on the run-out table were, by applying an inverse method, determined from the actual mill data under various cooling conditions. As for the stress analysis, the density change of strip due to cooling and phase transformation, and the transformation superplasticity were considered. A 90nstitutive equation for the transformation superplasticity, which is related to the phase transformation kinetics and the internal stress due to the density change of strip, was applied. A finite element method was adopted to calculate the deformation behaviour of strip on a run-out table of hot strip mill. Using the models, the temperature-phase-deformation history and distribution of a strip on the run-outtable was calculated.

Jan 1, 2001

By Debbie Marshall

Nickel and cobalt in lateritic ores can be extracted by either a hydrometallurgical or a pyrometallurgical route. The high-iron limonitic fraction of a deposit is best processed' hydrometallurgically while the magnesium-rich transitional and saprolitic fractions are more suited for pyrometallurgical processing. During hydrometallurgical processing, it may be attractive, for economic reasons, to blend the limonitic component with transitional and saprolitic ores, which contain higher nickel levels. However, blending increases the concentration of magnesium in the feed, leading to increased acid demands. The decision on how much ore to process then becomes an economic one. Ore samples with different magnesium contents were prepared for the leach test program by blending limonitic and transitional ores. The ore samples were slurried in seawater and tested in the Falconbridge Hydrometallurgical Pilot Plant. As expected, acid consumption increased with increasing magnesium content of the ore. For target extractions of 95% nickel and 92% cobalt, the required residual free acid concentration increased from 30 g/L at 1.7% magnesium to 50 g/L at 2.7% magnesium. When the magnesium content was raised to 3.8% and 4.6% in subsequent pilot plant testing, the final free acid requirements did not increase beyond what was observed at 2.7% magnesium. Thus, the cut-off ore composition to maximize nickel units and minimize acid requirements is between 1.7- 2.7% magnesium. Keywords: high pressure acid leaching, laterites, magnesium

Jan 1, 2004

By Kazuyoshi Shimakage, Shinji Hirai, Kenji Wada

"An amorphous zirconium oxide coating was prepared by the sol-gel process using zirconium tetra-n-butoxide on the surface of aluminum to improve the corrosion resistance to salt, acid and alkaline attacks. The coating films formed on the smooth aluminum substrates under UV-irradiation indicated an excellent corrosion resistance for salt, acid and alkaline attack tests. For example, the corroded area of coating film in salt attack test for 3600ks in the order of sol-gel coating· film< chromate film <boehmite film, and the sol-gel coating film had the best corrosion resistance. The coating film prepared on the coarse aluminum substrate by a boiling treatment after heat treatment at 573K also had greater corrosion resistance, and a water-avid surface appeared a contact angle of approximately 3°.IntroductionAs given in a previous paper1; a composite film consisting of a porous layer of anodically grown aluminum oxide filled with amorphous zirconium oxide and an amorphous zirconium oxide coating layer deposited thereon via the sol-gel process utilizing the dip-coating technique, was prepared to improve the alkaline corrosion resistance of aluminum. The alkaline corrosion resistance of these composite films was increased in the range of 24 to 50 times those of conventional anodic oxide films anodized in sulfuric acid. As a result, it was proved that heat treatment at 573K after dip-coating was an important process to .remove organic component from gel film and to accelerate the densification of coating layer. Furthermore, the effect of ultraviolet (UV) irradiation at ambient temperature on the densification of coating layer was also examined to lower the heat-treatment temperature2.Then, a sol-gel film prepared by UV irradiation at ambient temperature indicated that alkaline corrosion resistance of aluminum was superior in the range of 2.4 times to 2. 6 times that of the conventional composite film heated at 573K."

Jan 1, 2000

By Dumitru Mitrica, Vasile Soare, Elvira Alexandrescu, Mihai Ghita, Marian Burada, Petru Moldovan, Raluca Maria Florea

"Aluminum metal matrix composite Al-Si /SiCp was prepared by reactive gas injection and subsequent remelting. The influence of the remelting process on the microstructure and physicalmechanical properties of the resulted material was investigated. Samples resulted from the synthesis process contained silicon carbide agglomerations in the vicinity of primary silicon and large pore concentrations. In-situ formed silicon carbide presented mostly a polymorphic structure with particle sizes varying from 1 to lOµm. Physical and mechanical properties were largely influenced by the porosity distribution. The remelting process provided a decrease in the composite material porosity and pore size, with significant improvements in the particle distribution and physical-mechanical properties of the composite material. Additions of up to lwt.%Mg in the starting alloy improved the in-situ carbide formation and particles distribution in the solidified material. However, stable and large particle agglomerations were detected in the material in absence of conventional stirring or controlled solidification techniques.IntroductionThe remarkable properties of composite materials (yield strength, stiffuess, hardness and resilience at a reduced specific weight) make them attractive for applications in automotive, aerospace and military industries. Particle reinforced aluminum metal matrix composites (PAMMC) are known for their high strength to weight ratio. The recent development of P AMMC created the possibility to obtain large particles concentrations, exceeding 10% by volume ofreinforcement (SiC, AIN, Al203, etc.). The improvement ofhigh temperature strength and wear resistance made them appropriate for the use in automotive applications, such as the pistons, rotors, disc brakes, and propeller shafts [ 1]. The present main disadvantage of the P AMMCs is their high costs for obtaining and processing related to the final product performance. In order to benefit from the advantages that offer composite materials properties a reasonable production cost - performance ratio must be obtained [2]. Recent innovations in the manufacturing of aluminum-based metal matrix composites provided notable performance improvements but no feasible solutions were found for lowering their present high prices."

Jan 1, 2014

By Jingyuan Wang, Hengyi Zhang, Peng Lan, Ruitian Zhang, Jiaquan Zhang, Yang Li

"For the determination of mould taper and wall thickness, a 3-D numerical model of ingot-mould-hot top system has been made to evaluate the related ingot solidification process and the final soundness. The effect of mould wall thickness and the taper of its hot faces on the thermal history and the as cast structure of steel ingot has been revealed through the numerical simulation. It is shown that the ingot soundness can be improved remarkably by increasing the mould wall thickness, which is possibly beneficial to the mould life as well owning to an improved mould thermal state. The mould taper is vital to the ingot soundness but much less coherent to the mould temperature profiles. Under given casting situations, a larger mould taper can lead to a less intensity of the shrinkage porosities at the top part of ingot.IntroductionIngot casting is still one of important processes for steel production, which is adopted especially for the supply of large-sized semi-products of high quality special steels. The understanding to the solidification process is vital to both the yield improvement of casting production and the quality control of steel ingots, such as their soundness and homogeneity.The ingot processing and service performance are closely related to its defects, such as porosities and pipes[1,2], which are the most common but serious defects during ingots casting. In the late 1960s, Mahadevan and Murthy et al.[3], Irani and Kondic[4] began to analyze criteria for the prediction of shrinkage porosities in light metal casting. In 1980s, Niyama and Uchida[5], Hansen and Sahm[6,7] et al have successfully presented some related porosities and pipes criteria for steel casting. At the same time, numerical solidification simulation was well developed and applied to ingot quality studies[8-10]. However, due to the quick development of continuous casting, less emphasis has been given to the further study on ingot casting process. There leaves much work to be made for the comprehensive understanding to ingot quality improvement and the mould design by the aid of modern solidification technology[11, 12]. In this paper, the effects of mould taper and wall thickness on its thermal history, ingot solidification and the final soundness are numerically studied through solidification simulation, which has been adopted in mould design and industrial production of both the mould and its steel ingot."

Jan 1, 2012

By Katsunori Yamaguchi

Secondary materials, that contain relatively high concentrations of platinum group metals, (PGMs) are treated in copper smelting process. The PGMs lost in the slag is increasing with increasing quantities of scrap treated amount. To determine the portion of the PGMs chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. An experimental study was carried out to determine the distribution of palladium between the FeOx–SiO2 slag and the liquid Cu2S–FeS matte at 1573 K and a fixed partial pressure of SO2 of 0.1 atm. It was found that the distribution ratios are around 10−3 for platinum and palladium. The distribution ratios show a tendency to increase when the grade of matte is increased above 60 mass% Cu. In addition, the solubility of platinum in FeOx–SiO2 slag equilibrated with a pure palladium and the Pd-Cu alloy was determined at 1573 K and the range of oxygen partial pressure from 10−9 to 10−7 atm. The solubility of palladium in the slag tends to increase with increasing oxygen partial pressure and activity of CuO0.5 in the slag.

By Michael E. Stout

M.A. Industries, Inc. has developed and is now offering on a commercially available basis, complete systems to recover and recycle lead from spent SLI batteries. The system begins with the breaking and separation of the component parts of the batteries and subsequent treatment of the effluent water produced by this operation. The recyclable materials recovered from this process are metallic lead, lead paste and polypropylene. The lead paste is introduced into a process to convert it from a lead sulfate to a lead carbonate. The process also regenerates the salt solutions into reusable carbonate. The lead carbonate is then leached into an acid bath where it is later recovered by a proprietary electrolytic process. The metallic lead is recovered in a short rotary furnace producing metal for further refining and alloying. The polypropylene is further washed and then introduced to a reclaim extruder along with the proper modifiers and additives. The resulting resin can then be sold on the open market to injection molding processors. This complete system greatly reduces the amount of waste to be disposed of and completely complies with all applicable EPA guidelines.

Jan 1, 1993

By N. Choi

The distribution behavior of selenium and tellurium in nickel sulfide smelting was investigated in the temperature range of 1250-1300 °C under an inert gas atmosphere and various oxygen partial pressures. The distribution coefficients of selenium and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag were detennined in terms of matte and slag compositions, temperature, and oxygen partial pressure. The effect of slag additives such as CaO, MgO, and Ah03 on the distribution coefficients of those elements was also investigated. It was observed that the distribution coefficients of selenium and tellurium increased with increasing matte grade and temperature. The solubility of selenium and tellurium in the slag decreased with increasing the partial pressure of oxygen within the range investigated in this study. The distribution coefficients of selenium and tellurium increased with the amount of CaO and MgO. Tellurium distribution coefficients also increased by the addition of Ah03. Meanwhile, the addition of Alz03 decreased the distribution coefficients of selenium at high matte grade.

Jan 1, 1996

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 Yongqi Sun, Zuotai Zhang

Hot slags, at the temperatures of 1450-1650 oC, carry a substantial amount of high quality thermal energy, which represents the largest undeveloped energy source in the steel industry. However, the waste heat recovery rate in China is less than 2%; thus there is a great potential of waste heat recovery. In this study, we investigated a chemical method to extract the waste heat from high temperature blast furnace slags, i.e., sludge gasification. Sewage sludge, another substantial waste produced in the municipal system, need to be timely disposed, the organics of which could be gasified using the waste heat in the slags for the purpose of syngas production. Both the kinetics and thermodynamics of the sludge gasification process were clarified here. Most importantly, an integrated system composed of multiple systems such as the steel industry, the cement industry, the municipal system and the chemical engineering industry, was analyzed in this study.

Jan 1, 2016

By Qian Xu, Xionggang Lu, Xingli Zou, Zhongfu Zhou, Shuhua Geng, Hongwei Cheng

Herein we report an electrochemical route from oxides (SiO2, TiO2)/sulfide (MoS2)/carbon mixture precursors to Mo-Si-Ti-C composites in molten salt. The electrochemical process was carried out in molten CaCl2 at 800 °C with a potential of 3.1 V, and a graphite-based anode was used in the electroreduction process. The reaction mechanism and the influences of the stoichiometry of the initial mixture precursor on the morphology and phase composition of the final products were investigated. It has been found that Mo5Si3/MoSi2/Mo3Si/Mo, Mo5Si3/MoSi2/Mo2C/SiC, and Mo5Si3/Mo2C/Ti3SiC2/TiC/Mo composites can be electrosynthesized directly from their oxides/sulfide/carbon mixture. The preliminary experimental results suggest that the electroreduction process can be used for the controllable electrolytic production of alloys/carbide-containing composites from oxides/sulfides/carbon precursors.

Jan 1, 2016

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014

By Yanlong Li, Lifeng Zhang, Ying Ren

In this work, a multiphase mathematical model for the fluid flow in argon-stirred steel ladles was established and validated by experimental measurement of wood's metal. Alloy dispersion in the molten steel was calculated. The melting and mixing of alloy was faster with smaller size of the alloy particles, larger superheat and bigger slip velocity. The current mixing time is approximately 300 s with 30 mm alloy diameter and 91.5 K superheat.

Jan 1, 2014

By Ali P. Gordon, James Williams

Joints gasketed with viscoelastic seals often receive an application of a secondary torque, i.e., retorque, in order to ensure joint tightness and proper sealing. The motivation of this study is to characterize and analytically model the load and deflection re-torque response of a single 25% glass-fiber reinforced polytetrafluorethylene (PTFE) gasket-bolted joint with serrated flange detail. The Burger-type viscoelastic modeling constants of the material are obtained through isolating the gasket from the bolt by performing a gasket creep test via a MTS electromechanical test frame. The re-load creep response is also investigated by re-loading the gasket after a period of initial creep to observe the response. The modeling constants obtained from the creep tests are used with a Burger-type viscoelastic model to predict the re-torque response of a single boltgasket test fixture in order to validate the ability of the model to simulate the re-torque response under various loading conditions and flange detail.

Jan 1, 2015

By Bart Blanpain, Muxing Guo, Zhuangzhuang Liu

In order to stabilize free lime in the basic oxygen furnace (BOF) slag to achieve high value products, quartz sand and other additives are injected into slag. However, the current hot stage slag stabilization does not work in case of slag (before treatment) with a liquid fraction lower than 90%, where the slag containing solid particles is too viscous. Therefore, it is essential to understand how solid phases affect the viscosity of the slag system. In this study, the industrial BOF slags were investigated with respect to the correlation between volume fraction of solid phases and its viscosity. Slag viscosity was measured with a rotating type viscometer at temperatures below the liquidus. The volume fraction of solid phases was quantitatively calculated with FactSage. The Einstein-Roscoe equation was employed to predict the viscosity of BOF slag.

Jan 1, 2016

By Chen Chen, Wang Yanze, Hong Xin

Furnace superalloy was applied in harsh environment within the erosion of high temperature and oxidizing atmosphere. With plasma powder surfacing technology, iron-based alloy powder was sprayed on the surface of 310S stainless steel to form oxidation layer that increases the oxidation resistance and reduces the cost of materials. With optimum technological parameters, in this paper, oxidation test of 100 hours on iron-based cladding alloy and furnace alloy were carried out at 1200 . The technique of XRF, XRD and EDS were used to characterize composition, oxide morphologies and surface mechanical properties. The results showed that Element composition of cladding layer formed by Plasma powder surfacing was well distributed. Its oxidation weight gain rate of 100 hours was 0.4552g/m2h, belonged to antioxidant level. The oxidation weight gain rate of furnace alloy was 1.4617g/m2h, belonged time-antioxidant level. And on the mechanical comparison test, surfacing alloy is relatively excellent than furnace alloy.

Jan 1, 2016

By Jiangwei Shen, Cong Wang, Haibin Zuo

The research on the formation of Silico-Ferrite of Calcium and Aluminium (SFCA) in the process of cooling and solidification is rarely reported. The crystallization process was observed by using scanning electron microscopy (SEM) and optical microscope in this paper. The effect of different cooling system on the microstructure and phase composition of the sinters was investigated to obtain the appropriate cooling rate to improve the metallurgical properties of sinters. The experimental results show that the crystallization of calcium ferrite is getting better when the cooling rate is decreased from water quenching to cooling in the air. There are a large number of hematite phases with interconnected crystal structure in the sample cooled in the air. In the case of the compressive strength, it was determined by the mineral composition and pore structure, higher SFCA and hematite contents in sinter cooling in the air lead to a higher strength. Glass phase in the water quenching sinter was the major reason for the lowest strength. High porosity contributes to a decrease in compressive strength for the sinter cooling in the furnace. Therefore the air cooling was the appropriate cooling rate to achieve high quality sinter under this experimental condition.

Jan 1, 2016

By P. R. Taylor

Titanium carbide and titanium diboride powders have been successfully synthesized by direct treatment of ilmenite concentrates in a non-transferred arc thermal plasma reactor. Methane gas was used as the reducing agent and boron oxide was used as the boron source in these processes. Free energy minimization plots were used to predict the behavior of each system under different molar ratios and operating conditions. Products were characterized by XRD, SEM and chemical analytical techniques. The average size of the ceramic product is in the submicron range. Metallic iron apparently is finely deposited on the surface of the titanium carbide or titanium diboride particles. Minor impurities such as silica, manganese and zircon were converted to the carbide form.

Jan 1, 1995