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By M. G. Basavaraj, S. Sarkar, G. S. Gupta, P. D. Patil

"Previous experimental study on raceway size hysteresis on two-dimensional cold model showed that the inter-particle and wall-particle friction had a very large effect on the raceway size. Existing literature correlations for raceway size ignore the frictional effects. It has also been shown in the present study that their applicability to the ironmaking blast furnace is questionable. To take into account the effect of friction on the raceway size a stress analysis has been done for the raceway region. Two-dimensional fluid flow equations under turbulent conditions have been developed and solved computationally in order to get the pressure forces. The frictional forces were obtained in terms of stresses. To predict the raceway size a force balance was done for the raceway zone considering the pressure force, the frictional force and the bed weight. The resulting equations from the force balance are able to describe the raceway hysteresis phenomena reasonably well along with the raceway size. A two dimensional experimental set up has been fabricated in order to validate the computer predictions. Predicted values agree well with the experimental values.IntroductionWhen a high velocity blast of air is introduced into a packed bed through a tuyere, a cavity is formed in front of the tuyere. This cavity, formed in the iron-making blast furnace, is called the raceway. Coke tumbles down and bums in this raceway, generating heat and reducing gases for the iron-making process. The raceway is responsible for producing most of the reducing gasses in the blast furnace. In addition, the size and shape of the raceway determines the movement of solids within the blast furnace, the distribution of gases and liquids (slag and metal), setting the location where the primary chemical reactions occur and the temperature profile in the lower part of the blast furnace.Due to the importance of the raceway, many investigators l - 6 have studied it and have predicted the raceway size using the empirical correlations based on experimental (hot & cold) and mathematical models. A number of correlations have been reported in the literature to predict the raceway size by various investigators3 - 6 which are different to each other. Each of the correlations shows a different dependence of raceway diameter (DR) on bed height, particle size, solid density, bed voidage and blast velocity. None of the correlations includes the effect of solid stresses on the raceway size and shape. The magnitude of these stresses will depend on the bulk solids properties (internal angle of friction, wall angle of friction) and the bed dimensions."

Jan 1, 2001

By Tao Li

The development of DP(Dual Phase) steels and TRIP(Transformation Induced Plasticity) steels has received much attention in recent years due to their high strength and simultaneous good ductility, which provides the potential for weight reduce and resource savings on certain components in automobile or other industries. So a controlled rolling process was simulated in the present study by thermomechanical simulator (Gleeble 1500) for producing DP steels on a kind of low carbon steel containing a small amount of Si and Cr. F+M dual phase microstructures have been obtained during continuous cooling processes of a wide cooling rate range from 10°C /s to 60°C /s. The grain size of the dual phase steel developed can be refined to less than 5 m through the mechanism of deformation induced ferrite (DIF) transformation. The ultrafine ferritic grains are equiaxed with high-angle boundary, and the martensite islands of an average size less than 5m disperse uniformly in the ferrite matrix. The ultrafine martensite islands not only inhibit the growth of ultrafine ferritic grains and improve the bonding of F/M interface, but also increase remarkably the strain hardening rate in the processing of the present Dual-Phase steel. As a result, the tensile strength of ultrafine grained Dual-Phase steel reaches higher than 1000 MPa. The result shows that an ultrafine grained Dual-Phase steel of low carbon and low alloy is promised to exhibit desired F+M microstructure by means of this new TMCP process.

Jan 1, 2006

By Chao Zhang, Jian Guo, Chaoquan Yao, Leige Xia, Xinyu Li, Jianliang Zhang

In this research, analytical reagents were used for the sintering experiments. And the sinters were using X-ray diffraction, scanning electron microscope and mineralogical microscope analysis to study the effect mechanism of manganese on the silico-ferrite of calcium and aluminum (SFCA) bonding phase formation during the sintering process. The results indicated that the increasing content of manganese would greatly reduce the content of SFCA, and promote the formation of calcium aluminum silicate and the amount of pores and cracks. The existence of manganese inhibited the silicon form into the SFCA and a great deal of Fe2O3 was participated in the crystal transition to Fe3O4. When the ratio of the added manganese was less than 3% in the mixing, the calcium ferrite was in substantially interleaving corrosion with hematite and magnetite. Both the porosity and silicate glass phase content were low simultaneously, which contributed to the sintering production.

Jan 1, 2015

By A. K. Riihimäki

The description deals with duplex stainless cast steels and austenitic high molybdenum steels used in pumps for severe condition service. The main modem nitrogen alloyed duplex cast steels are presented in the ASTM standard A-890. Two grades of high molybdenum austenitic stainless steels there are presented in ASTM A-744 (-96) standard i.e. CN-3MN and CK-3MCuN. The latest and most corrosion- resistant stainless steel grade is AVESTA 654 SMO?. Avesta Sheffield the trademark owner has granted Ahlstrom Pumps license to produce the material. This new stainless steel as pump material for severe service has improved properties in the hydrometallurgy and electrorefining processes of metal and especially in the copper industry compared to duplex stainless steels. The paper deals briefly with the foundry process to manufacture high alloy stainless steel pump castings. The AOD-method (AOD= Argon Oxygen Decarburization) is an important prerequisite for the melting of low carbon, high chromium and molybdenum alloyed nitrogen steels. The properties of these steels are included. The main topic is the corrosion resistance of the above-mentioned pump materials in severe service. Results of short-time erosion and corrosion tests are discussed and compared with the results of plant tests. Practical results of pump materials performance in severe service for the copper industry are given. The new high alloyed cast stainless steel (main elements; Cr-24%, Ni-22%, Mo-7,3% and N-0,5%) has shown improved corrosion and erosion properties as process pump material in several severe service applications e.g. in the metal industry.

Jan 1, 1999

By M. GONZALES-FERNANDES M

Natural rubber/organophilic clay nanocomposites were prepared and characterized. A brown bentonite from Paraiba’s State, Brazil was modified with a sodium salt and treated with quaternary ammonium salt hexadecyltrimethyl ammonium chloride. The clay in its natural state, after cation exchange with sodium and after organophilization was characterized by XRD, IR, SEM, thermal analysis. Nanocomposite samples were prepared containing 10 resin percent of organophilic clay. The vulcanized samples were analyzed by XRD, SEM. The nanocomposites obtained showed improvement in their mechanical properties in comparison with samples without clay.

Jan 1, 2015

By J. B. Cocanour

Pioneering work at the U.S. Bureau of Mines (USBM) has produced a personal computer (PC)-based, software-driven video photometric color sensor for real time process control of metallurgical streams. The video photometer is an inexpensive optical sensor which operates in the visual area of the electromagnetic spectrum and collects color information through plastic optical fiber. The red, green, and blue (R/G/B) voltage components of the color video signal are digitized and characterized through software and then presented as the control variable for software-based proportional-integral-differential (PID) control. This sensor has been successfully employed in the control of a laboratory copper electrolytic circuit. With this sensor, copper solutions were analyzed on-line without the need for sample removal, dilution, mixing or reagent addition, thereby allowing for the real time control of the circuit.

Jan 1, 1994

By Claudia Gasparrini

Uranium occurs in a variety of minerals, the more common primary ones of which are uraninite-pitchblende, coffinite and a group known as the complex multiple oxides. Identification and description of the uranium-bearing and associated minerals in ore samples may give a preliminary indication of the potential economic importance of the deposit and may also suggest initial approaches to metal extraction. The present paper reviews the common uranium minerals, describes their manner of occurrence and compares the types of deposits with which they are associated. Methods and techniques for their identification are described and their leaching characteristics discussed.

Jan 1, 1981

By Jorge Alberto Soares Tenório, Denise Crocce Romano Espinosa, Luciana Harue Yamane

"The present work investigated the influence of Fe+2 initial concentrations in the bioleaching of copper from printed circuit board using Acidithiobacillus ferrooxidans-LR. Printed circuit boards were collected from obsolete computers and mechanically processed through size reduction followed by magnetic separation. The bacteria Acidithiobacillus ferrooxidans-LR were grown and adapted in presence of printed circuit boards. A shake flask study was carried out on the printed circuit boards samples (non-magnetic fraction) using a rotary shaker under the following fixed conditions (185 rpm, 30°C). The bioleaching efficiency was evaluated by comparison between the concentration in the initial sample and in the leached liquor, pH of the medium and concentration of ferrous iron produced. Inductively coupled plasma optical emission spectrometry (1CP-OES) was used to determine the metals concentration. The results showed that Acidithiobacillus ferrooxidans-LR leached 63% copper from printed circuit boards using supplemented medium with Fe+2.IntroductionThe waste of electric and electronic equipment is generated by discarding of equipment such as obsolete computers and cell phones which is stimulated by the technology innovations and it has been growing each year. Because of the amount that has been accumulated it has become a prominent environmental problem but also can be a source of valuable materials, such precious and base metals [1,2] The printed circuit boards are found in almost all electric and electronic equipment being composed of polymers, ceramics and metals and can be an alternative source to recover base and precious metals. The precious metals are used in the printed circuit boards to protect against oxidation and base metals because of its conducting properties [3]. The heterogeneous composition of printed circuit board is a limiting factor in the recycling processes and the metals concentrations also range."

Jan 1, 2011

By Fernando Guevara

Many smelting and slag-cleaning furnaces operate with cooling systems designed to freeze a slag layer over the refractory to protect it. The fluid flow and heat transfer conditions associated with the freeze layer and mushy zones are poorly understood. These phenomena were simulated with a small-scale room temperature, 2-dimensional model, using an aqueous solution of calcium chloride to simulate the slag. Reasonable similarity with conditions encountered with copper and nickel smelting systems was achieved (Pr 50 and Ra 108, in the laminar-turbulent transition). Measurements of the freeze layer development and velocities were made with the Particle Image Velocimetry (PIV) technique. Direct Numerical Simulations (DNS) were also made of the unsteady fluid flow and heat transfer problem. It was found that the solidification process is well described using an improved model for high molecular viscosity in the mushy zone. Solid front growth, isothermal profiles, velocity profiles and heat transfer through the walls showed good agreement between the PIV and DNS results. Experimental and numerical velocity profiles close to the freeze layer show a parabolic behaviour in the vertical velocity profile which is completely different from the calculation of heat transfer using a sharp interface model. The reason for this is attributed to the effects of the mushy zone with a high viscosity and high shear stresses acting on that area.

Jan 1, 2006

By Nan Zhang, Lei Zhang, Gai-feng Xue, Lina Wang, Pu Liu

"A novel ß-diketone modified silica gel was synthesized by a simple reaction. The prepared material was characterized by diffuse reflectance FTIR spectroscopy and it was used for the adsorption of heave metal ions in the industrial waste water. The main parameters affecting the sorption of heavy metal ions, including pH, water flow rate, and elution, have been investigated in detail. Under the optimized operating conditions, most of the targeted heavy metal ions could be removed. The material could be simply regenerated by hydrochloric acid solution. The method is rapid, selective, economic and applicable to the removal of heavy metal ions from industrial waste water.IntroductionToxic organic pollutants and heavy metals ions mainly from industrial activities such as plating, metallurgy and dyeing industries, are a threat to human health and the surrounding environment, because of their toxicity and persistence after being released into the natural environment [1]. These pollutants must be removed or degraded to an acceptable level, before being discharged to the receiving waters. Therefore, detection and determination of heavy metal ions in industrial waste water is very important.Inductively coupled plasma optical emission spectrometry (ICP-OES) is the most used technique for the determination of heavy metal ions because of its capability for rapid multi-element detection over a wide concentration range and with relatively low detection limits. Compared to other techniques such as neutron activation analysis (NAA), X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES has the above advantages. Some constituents in industrial waters, such as organic compounds and inorganic salts, may cause matrix effects. In order to achieve accurate and reliable results, an efficient preconcentration of heavy metal ions and their separation from the matrix are usually required."

Jan 1, 2012

By Jun Li

Several metal sulfides were examined in-situ by Raman spectroscopy before and after anodic oxidation. Results obtained for chalcocite, chalcopyrite, covellite, galena, pyrrhotite and pyrite electrodes are presented. Under appropriate conditions, sulfur was detected after a potential was applied to the mineral electrodes for a threshold period of time. For all the minerals, application of a negative potential on the oxidized mineral reduced the surface product and the sulfur peaks disappeared from the observed spectra. For those minerals containing sulfur as S< in the crystal lattice, polysulfides were identified as oxidation intennediates.

Jan 1, 1993

By Ilkka V. Kojo

This paper gives an overview of the primary copper smelting business during the years of flash Smelting in the light of various projects taking into account the sustainability of copper production. Also the future challenges of copper smelting are addressed with special emphasis on the environment. Flash Smelting connected with either Peirce-Smith converting or Flash Converting offers the most economical and environmentally friendly alternatives for the smelting of normal and lean copper concentrates. For rich copper concentrates the feasibility of Outokumpu Direct Blister Flash smelting is, understandably, beyond compare. When the total investment costs for building a smelter and acid plant are considered, it is clear that Flash Smelting is the more feasible option compared to bath smelting. Reduction of equipment and operating cost is further achieved by the LUREC-process developed by Outokumpu Technology for operating plants with SO2-contents up to 25 % by volume. As an example the Kennecott-Outokumpu Flash Converting Furnace (FCF) has been in operation at Kennecott Utah Copper for 10 years and has achieved excellent results both environmentally and production vice. The FCF treats the entire output of the Kennecott Flash Smelting Furnace and has excess converting capacity. Furnace life, initially projected at two to three years, is now projected to be more than 5 years. It is likely the life will be essentially the same as a well-operated Flash Smelting furnace.

Jan 1, 2006

By L. Béjar-Gómez

The aim of this research work is to study and characterize precipitates in structural microalloyed steel by transmission electron microscopy and analysis by high resolution (HRTEM). Microalloyed steel with titanium was produced by casting in an electrical induction oven of 25 Kg. capacity. Carbon content in steel was less than 0.1 % and titanium content of 0.04%. Steel was processed thermomechanically; reheated to 1250ºC and hot rolled on a laboratory mill to a 13.0 mm thick plate with a finish rolling temperature of 900ºC and thickness reduction of 80%. Analysis by High Resolution Transmission Electron Microscopy (HRTEM) identified precipitates in the steel; type and morphology. Energy Dispersive Spectroscopy (EDS) analysis was applied to obtain the chemical composition of precipitates and the matrix. STEM-EDS analysis was also applied to obtain the element profile of precipitates. The results showed the presence of carbonitride precipitates of titanium, Ti (CN), with a circular morphology and size of 10 nm and less.

Jan 1, 2006

By KNona C. Liddell

"Many metal recovery processes involve heterogeneous reactions in porous media accompanied by fluid flow and mass transfer. Modeling such systems is difficult because of the number of rate processes involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide an attractive alternative to models based on transport mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.INTRODUCTIONSubsurface mineral leaching, metal ion recovery and environmental remediation are significant modeling challenges. They involve one-, two-, or three-dimensional reactive flow in multi reaction open systems. Dissolution, adsorption, and ion exchange occur at reactive mineral surfaces, and these heterogeneous reactions are accompanied by acid-base, complexation, and redox reactions in the solution phase.Two approaches have been taken to reactive flow problems in geologic media: mixing cell and transport models. Mixing cell models, the subject of this review, are based on a network of connected cells, each with a specified number of input and output streams. Mixing cells are assumed to have no internal solute concentration gradients, that is, each cell behaves like a well-stirred tank. Gradients are represented by step changes between connected cells; this results in a model that is spatially discretized at the outset. Different methods of discretizing the model equations are considered more fully below. Although this is not strictly necessary, it has usually been assumed in subsurface flow applications that all cells in the network have the same volume and identical initial properties."

Jan 1, 1996

By B. G. Thomas

"Mathematical process models can be applied in several different ways to serve industry by inducing beneficial changes to process operation. This paper attempts to summarize the different uses, types, and attributes of these models, and to offer some ideas to consider when developing, using, and reporting on them. Process models range from empirical to mechanistic in nature and vary in complexity from simple analytical solutions to coupled, 3-D transient numerical simulations. They are classified here according to the way in which they are implemented in practice, viz. fully-online models, semi-online models, off-line models, and literature models. The purpose of the model should dictate how choices are made during its development. Ways to validate and compare the model with experiments are suggested. Examples are taken in the context of the author's experience in modeling the continuous casting of steel.IntroductionThe objective of this paper is to provide a partial introduction for this symposium by discussing some basic aspects of the application of mathematical process models in industry. Essentially, the aim is to explore how process models are used to benefit industry, and to offer some general comments and suggestions, based on the experience of the author, on how models can best meet this goal.This work is concerned with process models, which consist of systems of mathematical equations and constants that are solved on a computer to make quantitative predictions about some aspect(s) of the process. The specific variables required as input data and generated as output data are important features of the model. The equations often derive from a numerical solution to one or more differential equations and their boundary conditions. The model also includes the constants, which represent material properties, empirical relationships, and other knowledge about the process, and usually require considerable effort to obtain. Thus, general purpose commercial software packages, (ie. finite-element or finite-difference based codes), are not models in this context. They are useful tools, however, serving as frameworks for the development of process models."

Jan 1, 1994

By Zhangm Mingming

Three samples received from the EAF shop were characterized by chemical, X-ray diffraction (XRD), optical microscopy (OM) and scanning electron microscopy (SEM) methods. The objective of this characterization work was to investigate the occurrence of nickel, copper, zinc, sulfur and phosphorus and to identify their origin and associations with iron minerals in the concentrate samples from the mines. The samples were identified as MINERAL, PELLET, and HRD. The latter is the DRI product. All three samples were received as fine powders. The results indicate that, in the mineral sample, magnetite is the major iron oxide mineral with hematite as a second phase based on the OM and XRD studies. Pyrite [FeS2], chalcopyrite [CuFeS2] and bravoite [(Fe,Ni)S2] are the major sulfide minerals. Trace amounts of apatite [Ca5(PO4)3(F,Cl,OH)], wardite [Na4CaAli2(PO4)8(OH)8 6H2O], giniite [Fe;(PO4)4(OH)3 2H2O] and vivianite [Fe3(PO4)2 8H2O] were identified by SEM and XRD. Microscopic studies also indicated that most of the sulfide grains in the mineral sample are present either as liberated fine particles (about 10 microns) or as inclusions within the magnetite and hematite grains. XRD studies revealed magnetite as the major mineral with subordinate amounts of hematite and pyrite confirming the microscopic findings. Copper, nickel, and zinc are mainly present as chalcopyrite, bravoite, and franklinite [(Zn,Mn,Fe)(Fe,Mn)2O4] in trace amounts in the mineral samples, respectively. Impurities carry over to the pellet and HRD samples. Chemical analyses of the three iron-bearing samples indicate that sulfur and phosphorus in the pellet sample exceeded the specification. Since liberated pyrite and chalcopyrite particles were observed in both the mineral and pellet samples, magnetic and flotation processing routes should be effective for sulfide removal but at the cost of iron losses. The high phosphorus content of all three samples indicates that there are phosphates which are difficult to remove by the current concentrating processes (magnetic separation and flotation).

Jan 1, 2012

By Toshiaki Nakai, Kunihiko Takeda, Kimio Imaizumi, Hiroaki Shirasaka

"The new type of nano-porous silica particle was considered to be constructed by the spinodal decomposition-type process which was found to have narrower pores than those of conventional porous silica prepared from boron silicate or ""Shirasu"" balloon. Nano-porous silica particles were fabricated by the calcination of silica gel mixed with well-dispersed complex salts composed of phosphorous and molybdenum compounds. Both silica and inorganic salts were not perfectly dissolved in the suspension solution. After removing of the water, the silica-inorganic salts complex was volatized and successively calcinated at a temperature ranging from 650 °C to 800 °C. Then, the inorganic salts were removed by dissolving in hot water. Other inorganic salts such as potassium halides were also found to be effective as a pore-size controller.IntroductionControl of structure has an important role in the field of industry as well as in the separation and purification technology for metals and organic syntheses. Many studies on the control of material structures have been reported regarding porous materials with pores ranging from nanometer to micrometer scale. 1 ) One example is zeolite as a naturally yielded porous inorganic material. Various types of synthetic zeolites have been studied as ""molecular sieve"" materials with ordinary pore-size of less than one nanometer. In 1992, crystalline meso-porous material with a large surface area named MCM-41 was synthesized through the use of template synthesis. 2) In direct relation to our study, amorphous borate glass having 4 to 100 nm of fine pores known as Corning glass 3l or SiO2-Al2OrB2O 3-CaO porous glass having large pore dispersity ranging from 4 to 10,000 nm have been reported. 4 ) S) 6 ) Some examples of several reported studies are as follows: phase-separated porous glass consisting of B2OrAl2O3-ZrO2-RO-R2O complex oxide 7 ) glass with finer pore induced from hydrolysis of silane alkoxide, porous material attained by condensation polymerization through the use of sol-gel process 8), alumina meso-porous material 9 ) 10), silica-zirconia material 11), carbon porous material 12), etc.."

Jan 1, 2000

By Charles Washburn

The authors review mercury sources, and contaminant streams, with particular emphasis on mercury that is extracted from precious metal ores. The design and operation of both large and small mercury distillation facilities are detailed. The relevant properties and characteristics of mercury and mercury vapor are presented. Facility engineering with respect to industrial hygiene, area ventilation, and material handling is presented.

Jan 1, 2003

By Noboru Masuko, Sachiko Ono

"The structure and composition of anodic films formed on aluminum in a borate solution have been investigated by using TEM and SIMS with respect to the effect of current density and electrolyte temperature. The film is composed of a boron-containing outer layer and a boron-free inner layer with disc-like crystals present at the interface. The thickness of the film formed at constant current density up to an identical voltage, decreases with increasing current density. The thickness increases remarkably with elevated temperature. The transport number of Al3+ estimated from the thickness ratio .of the cuter to the inner layers is 0.4 when the film is formed at the current density of 20 Am-2 at 60°C. It increases slightly with increasing current density and decreases significantly with increasing temperature. Content of boron in the outer layer increases 1.5 times when current density .increases 10 times. These changes in film structure and composition with electrolysis conditions must have a significant role in the determination of electric properties of anodic alumina films as a capacitor material.IntroductionThe growth of anodic alumina film in ·a neutral electrolyte proceeds at both film/electrolyte and film/substrate interfaces giving a duplex structure. The oxide layer formed at the former interface includes electrolyte anions while a-pure alumina layer is formed at the latter interface. The thickness ratios of each layer respectively represent transport numbers of Al3+ and 0 2 - (1). The film thickness and the incorporated anion content as well as transport numbers of both ions must affect the dielectric properties of the film as a capacitor material. However, the correlation between film structure and electrolytic conditions is not fully understood (2). For the further clarification of anodic film growth mechanism, more detailed characterization of anodic films in relation to electrolytic conditions is advantageous. In the present paper, therefore, the effect of current density and electrolyte temperature on the microstructure and composition of anodic barrier films formed in a neutral borate solution was studied. The films were characterized by direct observation using transmission electron microscopy (TEM) and depth profiles of constituent elements obtained by secondary ion mass spectroscopy (SIMS)."

Jan 1, 2000

By Harry Littleton, Jr. Scarber, Wanliang Sun

"The Lost Foam Casting (LFC) process is relatively immature when compared to other casting processes. To make the process more robust, computer modeling is needed to reduce lead times and casting defects. In this study, metal filling of lost foam aluminum castings was visualized using state-of-art real time X-Ray technology. Metal filling of the lost foam casting was simulated using a commercial software package. The result of the computer simulation was compared with the results of the real time X-Ray visualization. Some of the computer simulation results agreed with the real time X-Ray visualization, but some did not. Based on other studies using real time X-Ray technology, new input variables, such as foam density variations, were developed for the computer modeling. With the new variables, modeling of the lost foam casting process becomes more realistic. IntroductionMold filling of the Lost Foam Casting (LFC) process is an important step toward making a quality part. In the LFC process, molten metal is poured against a refractory coated foam pattern surrounded by dry sand. At the pouring temperature of aluminum, the foam pattern is decomposed into 30% (wt) gaseous and 70% (wt) liquid foam pyrolysis products. Existence of the gaseous foam decomposition products significantly increases the back pressure on the metal stream compared with the conventional open cavity sand mold. Entrapment of the liquid pyrolysis products during the metal filling generates many casting defects, such as internal pores, fold and blisters. Existence of these casting defects sometimes seriously degrades the quality of the components manufactured by the LFC process. Understanding and controlling the metal filling of the LFC process will certainly make this process more robust."

Jan 1, 2004