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By Michal Rehor, Vladimir Cablik, Peter Fecko, Tomas Lang

"1. Introduction The North-Bohemian Basin area is known for its largest Czech brown coal deposit. About 50% brown coal reserves have been exploited in the North-Bohemian Basin by the mining company of Severoceske doly, a.s. (North Bohemian Mines, j.s.c.) today. The opencast mining of brown coal naturally led to vast landscape damages. Therefore reclamation work has acquired great significance. The specific feature of Severoceske doly, a.s. mining is the fact that the mining has been realized in two geologically absolutely different localities. This fact demands even rather different methods of reclamations. The main problem at Doly Bilina localities is the occurrence of overburden rocks from the series of rocks of coal seams. These rocks are texturally light but large amounts of coal (cca 5 %) and sulphur (cca below 3 %) which makes the soil reaction extremely acid. If they appear on the surface of the dump, they create a phytotoxic area, reclamation of which requires special methods. Rocks from Doly Nastup Tusimice localities are more suitable to reclamation use, but texturally extremely heavy rocks with large fraction of physical clays appear there that can generate a sterile soil area. Their reclamation requirements are completely different from those on Doly Bilina phytotoxic areas. That is the reason of the application of some non – traditional restoration methods. This report briefly summarises the experience in application of fertilizable soils, power plant stabilizer, power plant ash and aerial sowing of charlock. The results are documented by the monitoring of the physical, mineralogical and pedological parameters of rocks in testing areas.2. Properties of Overburden Rocks in Opencast Mines Bilina and Libous The reclamation work methodology in the North Bohemian Basin is above all determined by the properties of overburden rocks which occur in the top horizon of the reclaimed sites. The research of the rocks reclamation properties dealt with four current mining localities in the central part of the basin. It concerned the Bilina and Libous mines. This chapter states the stratigraphic status properties of these sites with respect to reclamation availability. The total status of the area of interest is shown in the figure No. 1."

Jan 1, 2008

By Peter Willbrandt

Norddeutsche Affinerie's routes date back to the 18th century. NA was established in 1866 as a joint stock corporation. NA's core business covers the production of copper cathodes from primary and secondary raw materials and the processing of them into wire rod and shapes. Part of the shapes are processed into pre-rolled strip and shaped wires within the Group. With some 3,200 well qualified and highly motivated employees, the NA Group produces some 560,000 tonnes of copper cathodes, 370,000 tonnes of wire rod, 230,000 tonnes of shapes, 130,000 tonnes of pre-rolled strip as well as 70,00 tonnes of strips and shaped wires annually. NA's product range is complemented primarily by precious metals, selenium, sulphuric acid, lead and nickel sulphate. The paper will give an insight into the performance of NA and its business units with regard to production, environmental and health protection and occupational safety.

Jan 1, 2006

By Abhishek Lahiri, Animesh Jha

"A new technique for the selective separation of rare earths and impurities from lower grade titaniferous ores has been developed which will reduce the overall reduction in the energy costs, and therefore the CO2 generation by at least an order of magnitude during the chlorination and waste handling stages of TiO2 to TiCl4 reaction. The process includes roasting the ilmenite ore with alkali followed by water washing step, which removes nearly 80% of oxides of lanthanide and actinide elements present in lower grades of titaniferous minerals. In the context of preferential separation of rare- 3+ + earth and actinide oxides, we have examined the roles of Al and K ions on the lattice structures of ilmenite and complex titanate as the product layer forms during the roasting in air in the presence of potash. The composition of the mixtures of oxides derived from the separation process shows that the mixture of rare-earth oxides m ay be a high-value co-product of the overall beneficiation process.IntroductionWorldwide the production of synthetic rutile is carried out either by the sulphate or the slag-making followed by fluidised bed chlorination of TiO2 enriched slag granules. The chlorinated gas is then re-oxidized to make white pigment grade TiO2. The waste generated by the sulphate process is predominantly iron sulphate, which has limited use in the water treatment plant. The remaining wastes from the sulphate process undergo further treatment using filtration followed by evaporation and thermal decomposition after which it is disposed into deep sea. On the other hand the chloride waste is extremely hazardous and requires special case by neutralisation, followed by impoundment in a managed pond, where it is monitored for long-term for potential contamination to the soil and ground water. Rare-earth and prelanthanide wastes often end up in the pond where they are diluted and irretrievably lost for further use or recycle. Certain parts of the world the chloride process wastes are pumped via deep boreholes into porous geological strata. The present techniques of disposal are not only expensive but also pose continued threat groundwater and soil and marine life in case of sulphate waste [1, 2]."

Jan 1, 2009

By Toshiyuki Hiranami, Keizou Uematsu

"AbstractionSpray freeze drying method was proposed to fabricate ·ceramic: powder granules for high performance ceramics. Obtained granules and their green compact were characterized by SEM and immersion liquid technique. Granules have a spherical shape of about l 00 µ m in diameter, ·and no binder segregation was found with the immersion liquid technique. The granule had sufficient strength for usual handling, while the strength was much lower than that of granules prepared by conventional spray-drying. Unlike the conventional green compacts, granule interfaces were not observed in the green body made with the spray-freeze dried granules.IntroductionIt was well kn9wn that spray-dried granules have binder segregation layer on their surfaces. The trace of this segregation layer survives in the later processes i.e. compaction and firing, and behaves as fracture origins in the sintered bodies. The origin of this problem is solvent drying process from slurry droplet surface in spray drying system. As alternative method we propose a freeze drying process for granule preparation, in which solvent is remove by sublimation though the process, binder segregation can be prevent.In this study, we applied spray freeze drying method to fabricate alumina powder granule, and characterized the obtained granules, and their green compacts and sintered bodies.Experimental procedure.Alumina powders and additives aqueous solution were mixed for 24 hours using a ball mill to· prepare the slurry for spray freeze drying. .The solid loading of the slurry was 30vo1%. Deflocculant (PAA-NH4 type) was added 0.5mass%, and the binder (PVA). 1.0, 2.0 or 3.0mass% of alumina. Obtained slurries were sprayed into liquid nitrogen to make frozen granules. The granules were freeze dried.For the characterization of the granules, immersion, liquid technique observation and single granule strength test were carried out. Strength of individual granule wa5 measured using micro compression testing machine (MCTM, SHIMADZU). Granule strength was calculated from following equation."

Jan 1, 2000

By S. de Vries, B. Wasmund, J. Metric, N. Voerrnann, S. Kasinger

Gulf Chemical & Metallurgical Corporation (GCMC) operates a circular DC electric smelting furnace to treat nickel and cobalt bearing residues at its plant in Freeport, Texas. The furnace, originally built by others, has experienced problems including runouts through the hearth and the lower sidewall. Hatch has designed several improvements to the furnace to alleviate these problems. The single anode at the centre of the hearth was replaced with a patented system of twelve air-cooled copper anodes evenly spaced around the furnace lower sidewall. The DC power supply comprises two transformers and two rectifiers operating in parallel. The water-cooling system on the bottom and lower sidewall shell plates was replaced with an air-cooling system using copper cooling fins. The existing row of water-cooled copper coolers in the metal bath zone was re-designed for greater heat removal capacity and better element joint sealing, and a new row of water-cooled copper coolers was added to cool both the alumina bath and freeboard zones. The existing water-cooled metal and alumina tapblocks were also re-designed for more robust cooling. A binding system was added to provide refractory compression that reduces the risk of liquid leaks. Finally, the furnace tilting frame was relocated to the top of the furnace where it is less likely to be damaged.

Jan 1, 2000

By Jr. Brown, A. Calderara, A. L. Antozzi

"The result of extensive research into fundamental mixed metal oxide catalyst morphology has produced a next generation all titanium Dimensionally Stable Anode (DSA ®). This new DSA ® anode, patent pending, is tailored for electrowinning of non-ferrous metals (copper, nickel, cobalt, zinc) by means of this new coating technology.These DSA ® anodes are characterized by a hanger bar with vertical distributor bars, having primary titanium mesh attached by weldments. The active mesh is provided with noble-metal electrocatalytic coatings, consisting of iridium and/or ruthenium oxides, obtained by thermal decomposition of precursor solutions applied to the titanium substrates. The catalytic activity of state-of-the-art DSA ® anodes is increased by controlling the crystallite size of the noble-metals without decreasing the decomposition temperature. It is known that below a certain value (typically 400°C) the stability of these oxides, and associated lifetime, is seriously compromised. A highly active DSA ® anode, consisting of a quasi-amorphous phase, is obtained at high temperature (above 450°C), therefore not compromising lifetime performance. Through optimization of these design parameters, the manufacture of these novel anodes was identified.DSA ® anode performance advantages include: lead-free ' green' all titanium anodes, true leadfree cathode quality, energy savings of 0.3 to 0.55 V can be realized depending on the EW application when compared to industry standard lead-alloy anodes, eliminate need for cobalt sulphate addition required for lead anodes, sustainability designed into long-life recoatable anode structures, increase plant cathode output through increased current density operations, improve plant on-stream production, no sludge generated or removed, and improve current distribution producing smooth high efficiency cathode.Introduction of ProductThere are many factors to consider when engineering a high performance DSA ® electrowinning anode. Half of the anode's performance is derived from the physical attributes of the electrocatalyst and methods employed when applying this catalyst to the titanium anode structure. The other half of the performance benefits relate to the proper structural design of the anode. In this paper, we will highlight the anode development program in which De Nora has invested to provide the Electrowinning marketplace with a high performance anode product."

Jan 1, 2012

By T. Wang, R. G. Reddy

"The corrosion of stainless steel SS316L in a low melting point novel LiNO3-NaNO3-KNO3- NaNO2 eutectic molten salt mixture was investigated at 695K. After long-term isothermal dipping corrosion experiments, the SS316L samples were analyzed using scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) to determine the topography and corrosion products. Dense and protective lithium iron oxide scale formed on the surface and prevented the SS316L sample from further severe corrosion. Therefore, SS316L is considered to be suitable construction material for solar thermal energy storage materials containers.IntroductionMolten salt mixtures have been considered as potential candidates for thermal energy storage and heat transfer media in solar energy applications. To apply the molten salt in the energy transfer process, the standard pipes made of stainless steel must be utilized to carry the molten salt mixtures in parabolic trough system of solar power production. The pipes encounter continuous flow of hot and cold molten salt every day. Thus corrosion of stainless steel in molten salt mixtures becomes extremely essential for the long-term utilization of the thermal energy storage media. The corrosion of passivity materials inside high temperature molten salt systems have been studied which gives fundamental understanding of basic mechanism about the corrosion process [1-8].The corrosion behavior of Fe-Ni-Cr alloys in an equi-molar LiNO3–NaNO3–KNO3 mixture was studied [9]. According to the XRD analyses, the major phases in the oxide scales were identified as LiFeO2, Fe3O4 and Cr2O3. A HITEC® salt mixture (NaNO3–NaNO2–KNO3) was also tested as a corrosion medium for stainless steel [10] and the corrosion rate was found to be affected by the protective oxide layer. In most cases, the alloys having more than 10wt% chromium show high resistance to corrosion in molten salts."

Jan 1, 2014

By Sridhar Komarneni

"Microwave-hydrothermal processing is a novel technique which combines the conventional hydrothermal processing with microwave field and we previously showed for the first time, that ceramic powders can be rapidly produced by this technique. This review paper deals with the synthesis of unary oxides such as Fe203, Ti02, Zr02, etc., binary oxides such as BaTiO3, SrTiO 3, PbTiO 3, SrZrO 3, KNbO3, etc., and ternary oxides such as NaTi2 (PO4)3 and pyrochlore phases of Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3 etc. and metal powders such as Cu, Ni, etc. below 195°C. This method can be adopted to the synthesis of a large variety of powders by the appropriate control of pH, Eh, temperature/pressure and concentration of chemical species. The main advantages of this method compared to conventional hydrothermal processing are (a) it increases the kinetics of reaction by one to two orders of magnitude, and (b) it can lead to novel phases especially those with layered structures.IntroductionConventional hydrothermal processing is a well-established synthesis technique which has been extensively used in the preparation of fine ceramic powders [1-5], large single crystals [6-8] and massive cement blocks [9]. Technologically important ceramic powders such as BaTiO 3, Al203 etc. made by the hydrothermal process are now commercially available. Although there are numerous methods for materials synthesis, hydrothermal method is truly a low temperature and environmentally benign process. For example, ZrSi04 (Zircon) which is extensively used in ceramic industry can be prepared hydrothermally at 150·C [10] compared to sol-gel or solid-state method [11,12] which require a temperature of about 1000·C. The hydrothermal method is environmentally benign because hydrothermal reactions are carried out in closed systems at low temperatures and the contents can be recovered and recycled after cooling to the ambient conditions. One of the disadvantages with any low temperature processing method is slow kinetics. For this reason we have combined the hydrothermal method with microwaves to enhance kinetics and we named this method as ""Microwave-hydrothermal"" processing [13- 16]. Although the combination of microwave and hydrothermal techniques has been used in the past few years to dissolve all kinds of inorganic (e.g. alumino silicate rocks) and organic materials rapidly for chemical analysis, we were the first to show its potential value for the synthesis of various ceramic powders [13-16]. In this paper, I show that this novel method is applicable to the synthesis of all unary, binary and multinary oxides by the appropriate control of pH, Eh, temperature, pressure and concentration of chemical species. In addition, this method is also found to be useful for the preparation of metal powders."

Jan 1, 1994

By Zhi-yong Liu

A novel process, which includes hydrochloric acid leaching, iron powder cementation, sulphide precipitation and spray pyrolysis, was proposed to treat iron concentrate recovered from zinc kiln slag for comprehensive utilization. Treated by two-stage hydrochloric acid leaching, the leaching extents of Ag, Pb, Cu, Fe and Zn are 96.78%, 95.14%, 97.72%, 94.51% and 87.74%, respectively. More than 99% Cu and Ag are recovered from the leach liquor when iron powder is 25% higher than the stoichiometric requirement. More than 96% Pb and Zn is removed with three times of theoretical consumption of FeS, and the concentration of impurities of the final solution is less than 500 mg/L. Fe2O3 powder, which is spherical with a mean size of 12 μm and purity of 99%, is prepared with final solution at 700 °C. In this process, not only the metal values can be recovered effectively, but also the iron resources of zinc kiln slag can be converted into high purity Fe2O3, thus, the comprehensive utilization of iron concentrate recovered from zinc kiln slag can be realized.

By Yuanbo Zhang, Zhixiong You, Daoxian Duan, Guanghui Li, Tao Jiang

"Manganese is mainly consumed by steel and battery industries. In recent years, it is essential to utilize the low-grade manganese oxide ores with total manganese grade below 25%, as the high quality manganese ore resources are becoming scarce with the rapid development of the steel industry. Conventional pyro-metallurgical processes for utilizing manganese oxide ores are characterized by high production cost and energy consumption, low productivity, serious environmental pollution, etc. In this study, reduction thermodynamic of MnO2 reduced by sulfur was firstly carried out. Then, a novel process of reduction roasting with sulfur followed by acid leaching was developed to recover manganese from the very low-grade manganese oxide ores. Effects of main factors, including temperature, reduction time and S/Mn mole ratio, were investigated, and a high leaching efficiency of Mn above 95% was obtained under optimal conditions.IntroductionHigh/middle-grade manganese oxide ores are generally used in the metallurgical industries, particularly in steel plants and ferro-alloy units. The consumption of metal manganese in the ferro-alloy industry accounts for 85- 90% of the total Mn demanded [1]. Therefore, high quality manganese ore resources are becoming scarce with the rapid development of steel industry. It is essential to make good use of large quantity of low-grade manganese ores (TMn < 25%) presently available."

Jan 1, 2012

By Prakash Venkatesan, Yongxiang Yang, Seshadri Seetharaman, Aida Abbasalizadeh, Jilt Sietsma

Electrolytic production of metallic neodymium is carried out in fused fluoride salts containing neodymium oxide. Two major challenges pertaining to neodymium production are (a) low oxide solubility and (b) possible fluorine gas evolution. A novel iron-based reactive anode is proposed and tested to overcome fluorine gas evolution during electrolysis of neodymium oxide in molten fluoride salts.

Mar 1, 2017

By Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By Chai Liyuan

Chromium-containing slag was detoxified by the method of microbial treatment using Ch-1bacteria isolated from nature by our research group, belonging to achromobacter sp. and with the characteristic of reducing high concentration of Cr(VI) in alkaline solution. The detoxifying process of Ch-1 to chromium-containing slag was studied by column-leaching techniques respectively. The results indicate that Cr(VI) in leachate can not be detected when chromium-containing slag has been column-leached for 7 days, and Cr(OH)3 content in precipitate is up to 32.8% with great value of resource recycling. Flowchart of engineering experimentation was ascertained based on the parameters of column-leaching experiments. Using the technique of pelletization of chromium-containing slag heap-leaching by Ch-1,the leaching rate of water-soluble Cr(VI) existing in chromium-containing slag reaches up to 100%, while the leaching rate of full chromium is up to 90%, when the process has been operated for 7-10 days under the conditions of 25-40C and consecutive spray by circular leachate. The content of Cr(VI) in chromium-containing slag after detoxified meet the national identification standard for extraction procedure inxicity for hazardous wastes(GB5085-1996) in China, moreover approximately 90% of Cr(VI) existing in chromium-containing slag has been recycled.

Jan 1, 2006

By Qingwei Wang

This study focused on acidic wastewater from producing sulfuric acid system in zinc smelter containing mercury 21.48mg/L, zinc 55.85mg/L, lead 38.50mg/L, copper 1.68mg/L, cadmium 10.25mg/L, As 29.86mg/L treated by biologics. The factors of pH value, the ratio of biologics to mercury, complexing time, hydrolytic time and temperature were studied in this paper. Experimental results indicated that at pH value 10, quantity of biologics to mercury ratio was 16, complexing time 30min, hydrolyzation time 20min, temperature at 40?, concentration of mercury in treated water was removed to 22.15µg/L. At same time heavy metals such as Zn, Pb, Cu, Cd, As was removed by biologics, the remained concentration in treated water was Zn 0.53mg/L, Pb 0.12mg/L, Cu 0.01mg/L, Cd low to 0.01mg/L and As 0.023mg/L. According to EDAX analysis, mercury content in complexing sediment reached 28.49% easily to recycle as raw material and low concentration of heavy metals in hydrolytic sediment easily to dispose and treat.

Jan 1, 2009

By Qingwei Wang

Heavy metal-containing wastewater from hydrometallurgical processes of lead-zinc was treated by biologics in a 200 m3/h industrial scale experiment. The result shows that Zn concentration declined from 50.28 mg/L~240.81 mg/L to 0.21 mg/L~1.98 mg/L, Pb from 1.00 mg/L~13.47 mg/L to 0.083 mg/L~0.71 mg/L, Cu from 0.24 mg/L~2.38 mg/L to 0.059 mg/L~0.40 mg/L, Cd from 2.12 mg/L~23.47 mg/L to 0.011 mg/L~0.071 mg/L and As from 0.50 mg/L~6.00 mg/L to 0.005 mg/L~0.10 mg/L. The concentrations of the above heavy metals in the treated water were lower than that in Integrated Wastewater Discharge Standard (GB8978~1996) in China. Furthermore, the treated wastewater was recycled and reused in smelter plant. Zinc content in hydrolytic sludge reached up to 34.04%, which indicates that this sludge can be used to recover valuable metals.

Jan 1, 2010

By Richard J. Abitz

Thennodynamic geochemical models have been applied to assess the relative effectiveness of a variety of reagents added to aqueous waste streams for the removal of radioactive elements. Two aqueous waste streams were examined: effluent derived from the processing of uranium ore and irradiated uranium fuel rods. Simulations of the treatment train were performed to estimate the mass of reagents needed per kilogram of solution, identify pH regions corresponding to solubility minimums, and predict the identity and quantity of precipitated solids. Results generated by the simulations include figures that chart the chemical evolution of the waste stream as reagents are added and summary tables that list mass balances for all reagents and radioactive elements of concern. Model results were used to set initial reagent levels for the treatment trains, minimizing the number of bench-scale tests required to bring the treatment train up to full-scale operation. Additionally, presentation of modeling results at public meetings helps to establish good faith between the federal government, industry, concerned citizens, and media groups.

Jan 1, 1996

By Phillip A. Armstrong, Charles A. Lewinsohn, John H. Gordon

"This paper describes the opportunity offered by employing systems based on mixed conductive ceramics, in particular, ceramics conductive to oxygen ions and electrons, in reducing CO2 emissions from metallurgical production. Membranes based on these mixed conducting properties enable commercial viability of several attractive metallurgical processes. One of these processes utilizes modular, ceramic-membrane structures for the generation of pure oxygen, in tonnage quantity. The membrane-based systems offer significant capital savings and operating efficiencies in various metallurgical processes. The current status of this technology is summarized below.IntroductionCryogenic oxygen supply technology is currently the state-of-the-art for applications that require large quantities of oxygen (hundreds to thousands of tons per day). Cryogenic technology, however, requires substantial energy inputs and, hence, adds significant costs and emissions to processes. Furthermore, cryogenic oxygen supply technology is mature and there is relatively little potential for substantial capital cost reduction or efficiency improvement in coming decades. Non-cryogenic technologies offer a means to reduce the environmental footprint and cost of the oxygen supply facility in various applications.Ion Transport membranesCommercially available non-cryogenic air separation technologies, such as adsorption-based and polymeric membrane-based methods, do not afford the economies of scale that the cryogenic distillation enjoys. Therefore, industrial gas industry researchers began searching for alternatives to the relatively inactive and unselective polymeric membrane materials available. In the late 1980’s, Air Products began developing a new class of highly selective membrane materials with exceptionally high activity for oxygen transport. The materials constitute a class of oxide ceramics, and conduct both oxygen (as oxygen ions) and electrons in the same membrane, separating oxygen from air electrochemically. Numerous detailed process economics studies have shown that, based on these ion-transport membranes (ITM’s), the cost of oxygen can be reduced by approximately one-third relative to that obtained from state-of-the-art cryogenic oxygen supply technology, through a combination of capital cost savings and efficiency improvements. [1,2,3]"

Jan 1, 2008

By Alicia E. Ares, Carlos E. Schvezov

In the present work it was observed the nucleation and growth of grains in the equiaxed zone of metal matrix composites (MMCs) samples directionally solidified wit the presence of columnarto- equiaxed transition (CET) in the samples. In order to do so, first, it was defined the difference between the real temperature at a given instant, which it is used in the analysis, its variation and furthermore, the variation in the solid fraction with time between the beginning and the end of solidification. It was determined a growth law assuming a lineal variation of equiaxed grain radius as a function of time, and also, it was expressed a law of grain density as a function of time, considering the presence of SiC and Al2O3 particles in the matrix. Finally, the results obtained were validated with measured values of grain density at each position of the thermocouples in the equiaxed zone of the solidified samples.

Jan 1, 2015

By Jari Aromaa, Antti Kekki, Olof Forsén

"The deposition of copper on inert substrate depends on the number of active sites that will react at certain overpotential. The critical overpotential depends on surface morphology, surface film resistance and additives on cathode surface. The effects of surface properties on copper nucleation and growth rates were studied for used stainless steel blanks from several tankhouses. The surfaces of the blanks were characterized with electrochemical and mechanical methods. Electrochemical deposition tests were done at current density of 300 A/m2 for 10, 30 and 60 seconds. The nucleation density and copper coverage were estimated using image analysis. The surface film resistance did not correlate with copper growth. Increasing surface roughness correlated with lower copper growth.IntroductionStainless steel cathode blanks in copper electrorefming are usually made of AISI 3 I6L type steel. They have a typical lifetime over 10 years. During use the surface will collect deposits and become rough due to wear and corrosion. These factors can affect the nucleation and growth of copper. The nucleation and deposition of copper on inert substrate depends on the number of active sites that will react at certain overpotential. The critical overpotential can depend on surface film resistance, surface morphology, and additives adsorbed on cathode surface.The deposition potential of metallic ions on a foreign substrate is usually higher than the deposition potential on the electrode made of the same metal due to crystallographic substrate/metal misfit [I]. If the substrate has traces of the depositing metal they will be preferential growth sites. For a smooth deposit a large number of simultaneous nuclei is necessary. However, excessive nucleation density can lead to porous deposits [2]. Surface films of good conductivity are needed for dense nucleation and small nuclei. On cathode blanks the number of active sites increases with increasing surface film conductivity [3-5] and/or surface film porosity [6]. On AISI 3 I6 L stainless steel a more resistive oxide has been found to limit favourable sites for copper nucleation and more conductive film promoted high-density copper nucleation [7]. Also Urda-Kiel et al. have concluded that thicker oxide layers on AISI 304 stainless steel resulted in lower nucleation [8]. Increase in overpotential or current density activates more and more of the potential nucleation sites and this can be seen as higher number of nuclei [9] or smaller average distance between nuclei [10]."

Jan 1, 2012

By M. Urda-Kiel

Stainless steel is increasingly used as a cathode starting sheet. It was shown earlier that even when depositing copper on copper, a substrate-influenced zone appears in the deposit structure, followed by a transition zone and finally by the electrolysis-influenced structure. On copper, the substrate-influenced zone has a thickness of twenty micrometers and on titanium, eventually more than fifty micrometers. Initial nucleation and growth have a considerable influence. In this paper, copper was deposited in a channel cell on four different 304 stainless steel substrates: mechanically polished and anodized, respectively, at 0, +400 and +800 mV/SHE in 1M H2SO4 at 20°C. Copper was deposited under electrowinning conditions after solvent extraction (SX) (40 g/l Cu++, 180 gh/l, H2SO4, 20 or 60°C). The results showed that, although Auger surface analyses of the substrates were only slightly different one from another including the oxide thickness, nucleation and initial stages of growth were very sensitive to the surface treatment of the substrate. Potential step and current step methods gave similar results : progressive nucleation followed by 3D diffusion controlled growth. The highest nucleation frequency was observed on stainless steel anodized at 0 mV/SHE, under various electrolysis conditions. The potential influence of these findings on industrial practice is discussed.

Jan 1, 1999