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By A. M. Alfantazi, M. Boissoneault, D. B. Dreisinger, J. Synnott

"The effects of five commercially available foaming reagents (range of 0 to 25 ppm) namely Dowfroth 250, Saponin, Yucca, Licorice and Meta-Para Cresol on acid mist control, current efficiency, polarization behavior, and deposit morphology and orientation were investigated. The deposition was carried out using a bench scale electrolysis apparatus (cell volume 3L) at 500 Nm-2 and 38°C for 3 hours from Kidd Creek zinc electrolyte. The acid mist control capability of the various reagents was studied and compared by characterizing the foam layer generated during actual electrowinning conditions and by direct quantitative measurements of acid mist levels on top of the electrowinning cells. Within the range considered, the addition of these reagents reduced the current efficiency, refined the grain size of the deposit, and changed to preferred orientation of most of the deposits. Among the reagents tested, acid mist measurements indicated that Licorice and Dowfroth 250 were the best acid mist suppressant at emissions of 0.30 mglm3 and 031 mg/m3 respectively while Yucca and MPC produced the most mist at 3.0 mg/m3 and 33 mg/m3 emission rates, respectively.IntroductionMost of the world's primary zinc is produced via a combined roast-Ieach-purificationelectrowinning process. Depending on the electrolysis conditions, several additives may be added to the electrolyte. Some (e.g. glue, antimony, sodium carbonate) are added to mainly counteract the detrimental effects caused by impurities while others (e.g. licorice, Saponin) are used as foaming reagents to prevent excessive acid mist formation. Acid mist emission is a problem in many electrolysis operations because it corrodes the equipment and is a health hazard to the workers in the tankhouse as well as it pollutes the environment. Due to recent trends towards more environmental protection and more stringent in-plant hygiene, there is an increasing need to minimize these aerosols. In order to eliminate or minimize these aerosols foaming agents are usually added to the electrolyte to produce a foam layer on top of the electrolyte, thus trapping most of the mist. The ideal foaming agent would trap all of the mist and would not interfere with the electrowinning process. It is also evident that the reagent toxicology, cost and availability are important factors that need to be considered.Review of the available literature clearly indicated that very little work has been done in the past on the subject of acid mist control in electrowinning operations particularly in the area of foaming and anti-misting properties of surfactants. Two papers [1,2] have reviewed briefly the existing technologies for acid mist control. Recently, most of the work in this area has focused on the development of special mechanical devices that could be attached to the electrodes and control the mist generation at the source before it is emitted to the cellhouse [2-5]. On the other hand, extensive body of literature exists that deals with the effects of anti-misting reagents on the electrowinning aspects [6-7]."

Jan 1, 1997

By Masayuki Kudoh, Tohru Maruyama, Yohichi. Ito

When hypo-peritectic carbon steel is quenched during unidirectional solidification, the region of fine columnar grain is observed. It is classified into two coexisting phases. One is coexisting phases of liquid, delta and gamma in the upper part of the region, and the other is coexisting phases of delta and gamma in the lower part of the region. To form the coexisting part of the three phases means that solidification in this experiment proceeds in non-equilibrium state. The size of the narrow side of one fine columnar grain coincides with the arm spacing of a primary dendrite and this result is the same as the hyper-peritectic carbon steel. However, the boundary of the fine grain in the hypo-peritectic carbon steel is formed in different location from that of the hyper-peritectic carbon steel. The former is formed in the skeleton of the dendrite, while the latter is formed in the interspacing of the dendrite. The region of the fine grain changes suddenly to that of the coarse grain when the delta phase in the coexisting part of two phases disappears completely. Therefore, the delta phase in the hypo-peritectic carbon steel might prevent the growth of gamma grain. In order to recognize it, ferrite formers such as Mo, V and Ni are added in the sample. Then, the longitudinal length of the fine columnar grain extends in the sequence of the no addition, Mo, V and Nb.

Jan 1, 2000

A strategy is presented for a relatively. "low-tech" means for decontamination of streams . containing .low concentrations of toxic metals. Metal ion solutions were . circulate through fluidized beds of activated carbon which support bio-films ?of bacteria .that naturally excrete exopolysaccharides. The attached 'biomass is shown to significantly enhance nickel, cadmium and silver extraction from dilute solutions (5- l00mg/l). By heat treating (at 300º C) the metal/biomass/carbon particles, bio-sorbed silver was subsequently fixed to the carbon surface. This approach to metal decontamination may therefore also provide a route for dispersing and fixing catalytic metal particles over an activated carbon surface.

Jan 1, 1991

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 Emil B. Milosavljevic

The photochemical reactions of cyanide ion induced by light were investigated in the presence or absence of a titanium(IV) oxide semiconductor photocatalyst. The light sources employed were the sun and arrays of either mercury or fluorescent (cool white) lamps. The results obtained verify that cyanide decomposes much faster when TiO2 is present in the solution and that it is first oxidized to cyanate. However, contrary to the previous studies, it is established that cyanide is subsequently further oxidized via nitrite all the way to nitrate irrespective of the light source. As expected, the rates of the oxidation processes decrease with the illumination source utilized in the following order: Hg-lamps > sunlight > fluorescent lamps. As nitrate is a significantly less hazardous contaminant than cyanide, complete photocatalytic oxidation of cyanide to nitrate may be a viable method for decontamination of cyanide wastes. Contrary to previous claims, we find that cyanide is slowly photochemically decomposed even in the absence of TiO2. For example, with the mercury lamps as the light source, in two hours, cyanide concentration decreases to essentially zero; up to 7% was converted to cyanate and the remainder to unidentified products.

Jan 1, 1992

By Alexey T. Kovalev, Irina A. Khabarova, Valentine A. Chanturiya, Igor Zh. Bunin, Elizaveta V. Koporulina

"The paper presents new theoretical and experimental results about mechanisms of disintegration of mineral complexes and structural transformations of the sulfide surface under high-power nanosecond electromagnetic pulses (HPEMP). The heated gas outflow from nanosecond breakdown channels of sulfide minerals under HPEMP is considered. It is shown that the gas outflow from channels can be an additional destructive factor in the processes of the electric pulse discharge disintegration of mineral complexes. It is shown that the effect of HPEMP changes chemical surface composition and, respectively, technological properties of pyrrhotite and pentlandite. Morphology and elementary composition of new micro- and nanoformations on mineral surface of pentlandite and pyrrhotite have been investigated using up-to-date methods of SEM/EDX and Scanning Probe Microscopy. Preliminary electropulse effect on mineral products before flotation allows producing optimal conditions for flotation separation of pentlandite and pyrrhotite owing to forming the new nanophases and defects on the surface of sulfides.IntroductionThe effectiveness of High-Power Nanosecond Pulses in the disintegration and liberation of fine disseminated mineral complexes and the recovery of micro- and nanoparticles of precious metals from refractory ores was demonstrated in [1, 2]. Possible mechanisms of selective disintegration were considered in [1-3]. It has been shown both theoretically and experimentally that electric breakdowns can play an important role in the nanosecond pulsed treatment of milled minerals (e.g., semiconductor sulfides and quartz with particle sizes of 100 µm to 2-3 mm) that are carriers of finely disseminated gold and other valuable components. Electric discharges in such minerals are accompanied by a destruction of integrity in the form of breakdown channels and the formation of a system of cracks around these channels [3]. The development of the domains of induced cracks around the channels is determined by the pressure of evaporated material in the breakdown channel. Upon an instantaneous energy release in a channel (nanosecond discharges), the change in its transverse size and in the gas density and pressure in the channel is determined by (i) the radial motion of the evaporation wave, (ii) the radial expansion of the channel, and (iii) the heated gas outflow from the channel. The evaporation wave moves with a speed on the same order of magnitude as the speed of sound (or greater) and travels a distance of around the initial channel radius, i.e., a much smaller distance than the breakdown channel length."

Jan 1, 2011

By Olusegun J. Ilegbusi

"A two-fluid model is used to calculate flow and heat transfer characteristics of a plasma jet. This model accounts for both gradient-diffusion mixing and unmixing that may result from pressure-gradient-body-force imbalance in the system. The unmixedness is considered to be essentially a Rayleigh-Taylor kind instability. Separate transport equations are solved for the plasma and ambient gas velocities, temperatures and volume fractions. The two fluids allowed to exchange mass, momentum and energy through empirical interaction parameters. The empirical coefficients are first established by comparison of predictions with available experimental data for shear flows. The model is then applied to an Argon plasma jet ejecting into stagnant air. The predicted results show the significant build-up of unmixed air within the plasma gas, even relatively far downstream of the plasma torch. By adjusting the inlet condition, the model adequately reproduces the available experimental data on the temperature profile.IntroductionPlasma jets have important applications in materials processing, some of which include spray deposition, melting and refining, heat treatment and materials synthesis. In a typical reactor, the hot plasma stream entrains a surrounding gas and the resulting heat and mass transfer and the condition of operation of the torch, determines to a large extent, the performance of the unit. The entrainment may prevent uniform mixing and produce regions of unmixed hot/cold gases and non-uniform deposits as a result of insufficient melting of deposit in cold regions. This phenomenon may also affect chemical reaction rate in plasma systems for NOx reduction in exhaust gases.The study of plasma phenomena is often conveniently divided into three parts namely, the plasma torch, the plasma jet and analysis of the particles carried in the jet. The present work concerns processes occuring in the near-field of the plasma jet i.e. just downstream of the torch."

Jan 1, 1994

By H. Y. Sohn, Haitao Wang, Moo Eob Choi

"A novel ironmaking technology is under development at the University of Utah. This technology produces iron directly from iron ore concentrate by gas-solid suspension reduction. Hydrogen is the main reducing agent for high reactivity and for the elimination of carbon dioxide release in this ironmaking process. The direct use of concentrates allows bypassing the problematic pelletization/sintering and cokemaking steps in the steel industry.Intrinsic kinetics of the suspension reduction of magnetite concentrate particles by hydrogen has been measured. Experiments were carried out in the temperature range of 1423-1673 K, other experimental variable being hydrogen partial pressure, the amount of excess hydrogen and particle size. Under most experimental conditions, 95% reduction was attained within several seconds, which presents sufficiently rapid kinetics for a suspension reduction process. The reaction kinetics followed the nucleation-and-growth equation, and a rate equation that contains all the effects of the experimental parameters has been obtained.IntroductionWith the rapid increase in steel production, it is critical to control CO2 emissions which is the main greenhouse gas. It is inevitable to release a huge amount of CO2 when coke and/or coal are used as the main reducing agent in producing iron. As one of the methods to reduce the CO2 emission from ironmaking, the utilization of the gaseous reducing agents and fuels, including hydrogen, has been investigated [1-6]. The use of such gases forms the basis for a new ironmaking technology under development for producing iron directly from fine concentrates by a gas-solid suspension technology. This technology would reduce energy consumption by about 40% of the amount required by the blast furnace and drastically lower environmental pollution, especially CO2 emission, from the steel industry [4]. This is accomplished by adopting H2-based reductant and bypassing pelletization/sintering and cokemaking steps. Unlike other gas-based alternative ironmaking processes using shaft furnaces or fluidized-bed reactors, the suspension reduction technology is a high-intensity process because it will not suffer from the problems that other processes do when operated at high temperatures mainly from the sticking and fusion of particles."

Jan 1, 2011

By J. D. Sunderkötter, M. F. Stroosnijder, V. A. C. Haanappel

"TiAI-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 °C. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of such materials.Extended AbstractIntroductionTiAI-based intermetallics are being considered as construction materials for high temperature components, e.g. in aircraft and car engines, due to their low density and substantial mechanical strength at high temperatures, see e.g. [1,2]. The best ductility can be attained with alloys consisting of y-TiAI with around 5-15 vol.% Q2-Ti3AI. However, one major hindrance to industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 aG. In spite of their high aluminium content, TiAI-based intermetallics do not generally form long-lasting protective alumina scales. After longer exposure times the scales, which are initially rich in alumina, deteriorate and scales consisting of mixed alumina and titania predominate, with high growth rates similar to pure titania.It is not the intention of the present paper to present a general overview of the high temperature oxidation behaviour of TiAI based intermetallics, for which the reader is referred to the literature [3,4]. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium. The effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of these intermetallics will also be considered."

Jan 1, 1996

By F. Sekula

Tetrahedrite and siderite are two main valuable minerals present in the silver Mária Bana deposit. The tetrahedrite concentrate prepared from it by flotation has certain specific properties from the metallurgical point of view. Siderite is concentrated in the flotation tailings. The paper presents results of the laboratory and pilot-plant testing of the combined hydrometallurgical and pyrometallurgical methods proposed for treatment of the tetrahedrite concentrate and siderite waste. The testing conditions were based on thermodynamic analysis of the reactions that proceed in the process. The proposed technology makes it possible to separate copper from sulphur, mercury and iron in a straightforward way. Copper, after its refining, can be subsequently treated in the finishing operations. At the same time it is a valuable source of precious and noble metals. The siderite-containing flotation tailings can be converted to iron of the technical purity and slag. The proposed method is a good starting point for the development of the closed-cycle technology.

Jan 1, 2006

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

By Douglas K. Modrow

In the fall of 1993, construction was completed on a state of the art industrial waste water treatment plant at Asarco's East Helena Lead Smelter. Purpose of the plant was to remove arsenic and metals using hydroxide precipitation. Completing of the plant culminated a lengthy process of laboratory bench-scale test work, engineering, construction, and Environmental Protection Agency (EPA) oversight. Unfortunately, the effiuent requirements for the plant were made significantly more stringent as construction was rearing completion. As a result, optimization activities were initiated to determine and implement measures to substantially improve effiuent quality so the new discharge limits could be met. These activities consisted of acquiring a thorough understanding of process chemistry and plant operations, and developing simple, practical methods of automating unit operations associated with the treatment plant. Implementation of these modifications in the second half of 1996 will not only significantly improve the constancy and reliability of treatment plant operations, but also result in operating cost savings and reduced need for increased operator attention at capacity flows, plus allow the treatment plant to meet the new discharge limits.

Jan 1, 1996

By Geoffrey A. Brooks, M Akbar Rhamdhani, Md Saiful Islam

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500-1600oC for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the opencircuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Jan 1, 2014

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste-free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By Ullrich Kammer

Metaleurop's secondary lead smelter at Oker produces 60.000 mtpy of lead and lead alloys. More than 8O2 % of the raw materials are spent lead acid batteries. The other 2O2 % consists of drosses, ashes, scrap lead, type metal, sludges, etc., and is processed in a short rotary furnace (SRF). Also, industrial batteries not fitting in the battery scrap treatment plant are processed in the SRF provided with gas/oxygen-burner. Till Sept. 199O2, a soda ash slag was used in the SRF-smelting similar to the rotary kiln-smelting at Oker. Facing the future problems of handling and dumping soda ash slag, Harz-Metall GmbH has improved SRF-smelting with a non¬hazardous slag, insoluble in water, easy to dump and cheap in fluxes. This slag is based on a CaO-SiO2 -Fe0-type. Aim of the slag smelting is to be within the temperature range of 2 1100° and 1200°C - the eutectic line of Olivine in the corresponding ternary system. Since Sept. 199O2 Harz-Metall GmbH has operated the SRF with an "Olivine-type slag" with good results. Although the material is a "leady" slag. HMG is optimistic of using it as a filling material for construction purposes.

Jan 1, 1993

By V. D. Tathavadkar

Natural chromite mineral is a solid solution of spinet end members namely: chromite (FeCr2O4), hercynite (FeA1204), magnetite (Fe3O4), magnesio-chromite (MgCr2O4), (MgA12O4), and magnesio-ferrite (MgFe2O4). A phase transformation in chromite minerals occurs in oxidising conditions during the soda-ash roasting reaction. This phase transformation plays an important role in improving the extraction efficiency of Cr3+ from mineral phase. The extraction efficiency of chromium (Cr3+) from chromite to a water¬soluble sodium chromate (Cr6+) salt depends upon the decomposition kinetics of the spinet phase. An investigation of the phase changes in chromite ores in the absence of sodium carbonate was carried out in air, argon, and in argon +5 % hydrogen gas mixture. The thermodynamics of phase transformation reaction in chromite solid solution phase is discussed using the solution model proposed by Sack and Ghiorso [1]. The microstructural changes and the changes in elemental compositions of different phases were examined by SEM and electron probe microanalysis (EPMA) respectively. The experimental results indicate that the solid solution spinet phase in chromite mineral undergoes spinodal decomposition under the influence of oxygen partial pressure and temperatures. The structure of phases formed and their morphologies suggest that the phase decomposition may be similar to those observed by Burkert et. a]. 121, although the scale of phase separation in chromite appears to be strongly dependent on oxygen partial pressure.

Jan 1, 2001

By M. Okido, R. Ichino, K. Kuroda

"Compound semiconductor, ZnTe, was electrodeposited in an acidic solution with K2TeO3, ZnSO4 and Na2SO4 solution. Since the reduction potential Te(IV)/Te(O) is remarkably noble from the solution comparing to Zn(II)/Zn(O), code position of Te and Zn was thought to be difficult from this solution. Resulting from EQCM analysis, furthermore, Te(IV) reduced to Te(O) and Te(-II) in this order so that Te catholically dissolved from the electrode surface at more negative potential. But ZnTe alloy were formed by the UPD of Zn at -0.7V at 298K on Te surface in lmM K2TeO3, 100mM ZnSO4 and 100mM Na2SO4 solution adjusted at pH 4. Content of Te in the deposits is, however, more than 80%.Electrolytic temperature is well known to affect on the deposits characteristics. The higher bath temperature was, the better ZnTe crystal was detected in this study. Thermal electrode method is a. process of heating only substrate by flowing ac current in substrate. This process makes the surface temperature of substrate higher than boiling point of the solution, 373K. From EDX analysis, deposits without thermal current were Te-rich, Te content in the deposits with thermal current decreased with increasing of thermal current. Te content was 62% for 5A ac current, 51 % for I OA and 45% for 20A, respectively. The deposits that produced with ac current of IOA were closed to the stoichiometric ratio, i.e. ZnTe.Consequently, thermal electrode method is more effective to obtain a good crystallized ZnTe without heat treatment after deposition.IntroductionThe current subject of solar cell materials is silicon. Compound semiconductors including GaAs and II-VI group are generally used in the developing field of digital information such as the rapid cellular phone and car telephone. Compound semiconductors consist of more than 2 kinds of element. There are many materials for these compound semiconductors such a SiC, InSb, CdS for binary system and CuinSe2 for ternary system. It becomes generally difficult, to produce high quality crystal with increasing of kinds of element due to a complicated structure and a compound ratio of element. Semiconductor materials as a device are usually simple binary compounds and/or these mixed crystals. Properties of compound semiconductors have variety of the forbidden band and lattice constant and that can be change easily by addition of another element for the usage of the solar cell. Since most compound semiconductors are direct interband transition type, which has steep optics absorption edge and large light absorption coefficient."

Jan 1, 2000

By Alicia E. Ares

316 L Stainless Steel samples were solidified directionally under conditions which produced the columnar to equiaxed transition. The position of the transition was located in each sample and the distance from the bottom of the ingot was measured. During solidification the distribution of temperatures were measured by means of thermocouples located strategically. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solidus fronts. Comparing the location of the transition and the values of these parameters it was found that the temperature gradient reaches negative values of as low as -13.44 "C/cm, and velocities of the fronts of around 0.1 cm/s. Also, a supercooling of 5.81°C were measured which was associated with the supercooling for the nucleation and growth of the equiaxed grains ahead of the columnar front. In addition the primary and secondary dendritic spacing was measured in both regions. The spacing was compared with the predictions from available models. The results are presented and discussed in the frame of the results obtained for other alloys

Jan 1, 2002

By Rolando Campos

In August 1993, the operation of Refimet Chile's copper custom smelter commenced at La Negra, near Antofagasta in northern Chile. Design smelter throughput corresponded to 235 000 tonnes of concentrate, calcines and copper cements arising from suppliers in the north of the country to produce 90 000 t/y of blister copper. Refimet had initially gained experienced in building and operating leaching, roasting and a blast furnace facility at Rungue, near Santiago, followed by Roasting at La Negra. The initial smelter project was based on conventional reverb- smelting and Peirce-Smith converting and the majority of equipment was 'purchased second-hand and rehabilitated or modified. After only 3 years in production, the treatment capacity was significantly improved by introduction of technical improvements to the original plant operating scheme. Recently, the plant was further expanded to an annual smelting capacity in excess of 400 000 t/y feed, corresponding to around 160 000 t/y copper production. This expansion, referred to as Phase 2, was achieved by modification of the reverb to oxy-fuel firing, addition of a further (second-hand) acid plant, fire refining and anode casting facilities. Parallel development of concentrate injection into enlarged converters-also took place. Following successful commissioning of Phase 2 expansion, initial engineering studies for a third expansion phase have been completed. This aims to use leading technology based on bath smelting of bone-dry concentrates in a Continuous Reactor. This paper provides an overview of the relatively short plant history, its development and improvements together with operating indices achieved.

Jan 1, 1998

By T. Watanabe, T. Fujiwara, S-Wan Song, Y. Nakagawa, R. Teranishi, M. Yoshimura

"We have tried a new method to fabricate cobalt oxide films onto porous films directly by an electrodeposition method at low temperature. The porous substrate films (membrane-filters and paper) were placed between a LiOH solution and a CoSO4 solution and treated under electricalcurrents of ~1 mA/cm2 using carbon cathode and anode. Effects of temperatures, flow rates and electrical currents have been investigated. As a result, we found that the LiCoO2 films and Co3O4 films were successfully fabricated on paper and/or porous PTFE filters at 120 °C, while CoOOH films were deposited at 80 °C. Furthermore, LiCoO2 films did not cover whole the substrates, but was fabricated just over the anode. The chemical reactions of electrodeposition were also considered from these results.IntroductionRecent agreements on global environment require rapid progress of low energy and low waste processings for the fabrication of thin films that succeed to the mass production with the high consumption of the fossil fuels (such as physical vapor deposition°, chemical vapor deposition2), dip coating with firing3) etc.). The total energy consumption in aqueous systems should be the lowest among all these processing routes, because a much lager excess of energy is necessary to create melts, vapor, gas, or plasma than to form an aqueous solution at the same temperature4)The ""Soft Solution-Process"" (SSP) was one of the best concepts to realize the low energy and low waste fabrication of inorganic materials. 5) Generally speaking, SSP gives similar results to any other processing using fluids (such as vapor, gas plasma) and/or beam/vacuum processing. However, the total energy consumption of all these possessing routes should be the lowest in aqueous systems, because a much larger excess of energy is necessary to create melts, vapor, gas or plasma than to form an aqueous solution at the same temperature (Fig. 1). This idea can be easily demonstrated, using the simple example of BaTiO3. The energy diagram for the formation of BaTiO3 from various precursors is shown in reference 4. The driving forces (AG) for representative synthesis reaction of (1), (2), (3), (4) and(5) are 38, 727, 3685, 17 and —14kcal/mol, respectively at room temperature. 6' 7"

Jan 1, 2000