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By W. -D. Schneider, B. Schwab

Like all metals, zinc can be recycled theoretically without end. To demonstrate environmentally friendly use of zinc, it is necessary to increase the recycling rate. In this regard, the Imperial Smelting Process developed in the forties and fifties in the United Kingdom has become more and more important. This unique process combined with a sinter plant, hot briquetting, and direct injection through the ISP furnace tuyeres offers ideal possibilities to recycle all kinds of zinc and lead bearing materials. Possible secondary materials include Electric Arc Furnace (EAF) dust, zinc-containing sludges and even zinc/carbon batteries. This high temperature process also destroys all organic materials, like dioxin, and can be seen as a sink for many harmful substances.

Jan 1, 2000

By D. Morin

A general study of gold refractory arsenopyrite-pyrite concentrate bioleaching has been carried out including two continuous bioleach testworks at different sizes, namely one at a laboratory scale with a 100 I unit at a 2 kg/d dry solid flowrate and the other at a pilot scale at a 100 kg/d dry solid flowrate. Both tests show a 80% bioleaching of arsenopyrite in about four days of treatment and with the same kinetic. Pyrrhotite is attacked at the earlier stage of the bioleaching but pyrite remains unaffected. The weak potential of oxidation associated with the decomposition of arsenopyrite and the abundance of arsenite leads to a high grade of elemental sulfur in the bioresidue which consumes the major part of the cyanide during the gold recovery. Furthermore. the arsenite and ferrous produced in solution have to be oxidized to obtain a stable precipitate in the waste products and as outlined in previous works of other authors on this subject the addition of iron to obtain a Fe/As molar ratio at least above 3 is necessary. The agitation equipment used in the pilot unit allowed an optimization study calculation for scaling-up the design and power requirements of an industrial installation. For the pretreatment of a gold refractory As high-graded concentrate the reagent cost has the greatest part in the operating cost of the biooxidation step due to the necessary retreatment of the biosolution. In that conditions the power cost is quite marginal. actually it is significant for the treatment of pure pyrite.

Jan 1, 1991

By José R. de Tenorio

The aim of the present work was to investigate the reduction process of MnO~FeO-Si02 slags by carbon-saturated liquid iron. The effect of the initial Mn content in the bath was explored. The initial Mn content was in the range of 0 up to 40 wt. %. The MnO content in the slag was kept constant at 40 wt. %. Tests were performed in laboratory apparatus. Samples of slags and bath were taken. In the first 5 minutes, it was observed a very strong reduction of FeO. This first step promoted a MnO-Si02 enrichment of the slag and a formation of CO bubbles, which increases the slag level. The increase ofMn content decreases the MnO reduction rate.

Jan 1, 1996

By Wenjun Duan, Zongliang Zuo, Qingbo Yu, Qin Qin, Junxiang Liu

Moving bed has been widely used in the field of heat and mass transfer and reaction between solid particles and gas. In order to enhance the heat exchange coefficient, there will be tube banks inserted in the moving bed. In the process of drying ammoniates particles or heat recovery from high-temperature particles with moving bed, the particles flow behavior around the tube banks is significant. In this paper, the particles flow behavior around the tube banks is investigated, and all the results can provide guidance for the design and operation of a moving bed.

Jan 1, 2016

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By A. Patti, S. Reutzel, D. M. Herlach, L. Ratke, I. Egry

Cu-Co shows a metastable miscibility gap in the region of the undercooled melt. Undercooling of the melt below the binodal leads to separation of the melt into a Co-rich LI-phase and a Curich L2-phase. Experimentally, undercooling into the metastable miscibility gap is realised by means of electromagnetic levitation (EML), processing in drop tube (DT) and by melt flux embedding. As undercooling is large in these experiments, the velocity of the solidification front is high and the microstructure is frozen in instantaneously. Samples have been undercooled and solidified in the TEMPUS-facility (container less electromagnetic processing under weightlessness) during parabolic flight under reduced gravity conditions. Microstructures of solidified samples have been analysed and compared to those processed under gravitational conditions. The influence of convection on phase growth is much lower in reduced gravity. The microstructure shows spherical droplets of the minority phase, statistically dispersed in the majority phase.

Jan 1, 2004

By J. Méndez-Nonell

The thermodynamic and chemical properties of SrSO4 and SrS in a gaseous flow of CO and CO2 at high temperature are discussed. The thermodynamic analysis of the system was made using data from the literature. The results obtained from the thermodynamic analysis were experimentally verified using the thermogravimetric technique. The experimental results suggest the formation of a complex compound between SrO and SrSO4. It was also found a change in the chemical mechanism of the process between SrSO4 and CO-CO2 and in the chemical mechanism of the process between SrS and pure CO2.

Jan 1, 1995

By Jaroslav Horskoý, Miroslav Raudenský, Bogdan Filipic, Božidar Sader

This paper describes main elements and practical use of the computational system for automated setting of optimized casting conditions in the continuous casting of steel. The system consists of the heat transfer model of the process, empirical metallurgical criteria, and optimization algorithm. The physical model of the, strand temperature distribution relies on the classical Bennon-Incropera mixture continuum formulation for the convective-diffusive heat transport. Fluid flow effects are considered through enhanced thermal conductivity of the liquid phase. The model is solved by the operator-splitting Crank-Nicolson finite volume version of the Voller-Swaminathan scheme. The solution procedure is coupled with the IDS solidification analysis package. Boundary conditions for the strand cooling rely on combination of the generic and plant-specific mold, spray, and roll heat transfer coefficients ' by coping the effects of the casting speed, casting temperature, casting powder, mold oscillation mode, steel grade, water or air-mist spray type, running water, trapped water on the rolls, and radiation. The caster safety and productivity and the quality of the strand are related to nine empirical metallurgical criteria. The criteria ensure the caster safety and economy as well limit the internal, longitudinal, and transversal surface cracking possibility. The problem of finding optimum casting parameter values is stated as a minimization problem based on the analytical form of the cooling criteria evaluated from the steady-state temperature distribution of the strand. To solve the optimization problem, a genetic algorithm is employed. The algorithm explores process parameters settings heuristically by applying the principles of biological evolution. It starts with a random set of solutions and iteratively improves them through selection and variation. Solutions are evaluated by running the heat transfer model of the process and extracting the values of the empirical metallurgical criteria.

Jan 1, 2000

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

By Claudio Toro, Alex Moyano, Jonkion Font, Carlos Caballero, Pedro Morales

"Codelco-Chile in the last decade has carried out industrially-oriented research as an alternative to the traditional batch-type converting process. In a first stage carried out preliminary evaluations in a rearranged Peirce Smith (PS) converter, and then an exploratory test in a “Convertidor Teniente” (Teniente converter, TC) for the Codelco-Chile Continuous Converting Process. However, the validation test for this process in the TC was delayed up to the second quarter of 2007 where the validation studies were done satisfactorily.Thus, the objective of this paper is to present the results of the campaign tests validating the Codelco-Chile Continuous Converting Process in the TC1 of the Codelco Norte smelter.The results of charging the solid or liquid matte or high grade matte (“white metal”) by Garrgun, or by mouth of the 22 m x 5 m TC1 are presented. Some features of the industrially validated process are discussed, and the pilot test results of the matte injection are also presented."

Jan 1, 2009

By Qinghai Pang

"With the increasing proportion of bituminous coal in blend coal, the safety of blend coal during pulverization and transportation is gradually being paid more and more attention. Therefore, the explosivity of bituminous pulverized coal (PC) with different volatile content from 25 to 38% was studied by measuring the combustion flame length after its injection into a glass pipe with the heat source installed in the center. The results indicated that high volatile content bituminous PC is apt to have higher explosivity. By blending different bituminous PC with 10% anthracite, the explosivity of bituminous PC showed a positive correlation with the proportion –OH radical. However, different bituminous PC seemed to have the same explosivity when the addition of anthracite increased to 20%. With the further increasing proportion of anthracite to 30%, the explosivity of bituminous PC with high –OH proportion became negligible while a weak explosivity of high –CH3 proportion bituminous PC still remained.IntroductionWith the increasing iron ore prices and decreasing steel prices, it has become critical for iron and steel enterprises to control the cost in ironmaking and steelmaking process. Blast furnaces (BF) are the main consumer in ironmaking process, which occupies 70% fuel consumption of total steelmaking process [1]. In this circumstance, any means necessary is taken by BF operators to lower the cost of iron in production. Coke and iron ore are the main expense in this process, who takes up a very high proportion in total cost. Pulverized coal injection (PCI) is the most efficient way to reduce coke ratio, which replace coke with relatively cheaper PC.At present, most of BF is injected with blend coal in the consideration of decent combustion property and quantity of heat. Simultaneously, bituminite and anthracite blending is an effective method to obtain blend coals with required composition and performance, such as volatile and ash content, etc. Nevertheless, a very huge gap was found between the price of bituminous coal and anthracite in some regions of China, in which the price of bituminite can be just 70% of the price of anthracite. Thus, iron enterprises in these regions attempt to possibly amplify the proportion of bituminite in blend coal. Increasing proportion of bituminite results in higher volatile content in blend coal, by which the safety of blend coal during pulverization or transportation was deteriorated.Relatively, coals with higher volatile content usually possess stronger explosivity, which means that volatile and explosivity may related to some extent. However, the relationship between volatile and explosivity is not of certainty for some PC with high volatile content around 40% was found to be inexplosive in comparison to the coals with lower volatile content. With the increasing proportion of bituminous coal in blend coal, investigations on the factors of PC explosivity have become more and more important. Therefore, bituminous coals with different volatile content were selected. The explosivity of blend coal and its relationship between volatile content and functionality was investigated in this research."

Jan 1, 2014

By R. G. Henley

Mount Isa copper concentrate was combusted in a laminar-flow furnace. The conditions simulated those likely to be encountered in flames in flash smelters of the Outokumpu (air as oxidant) and INCO (oxygen as oxidant) types. The range of conditions studied was as follows: T 400-1400°C, 02 0-100%, SO2 0-95% for residence times up to 0.23 s. The distribution of sulfur, arsenic and lead between the particles and the gas phase was studied. Combustion was very rapid provided the concentrate was adequately dispersed, i.e., no agglomerates. The importance of the latter is discussed. It was possible to oxidize 80% of the sulfur present in the con¬centrate after only 0.1 s reaction time at 1000°C in an atmosphere contain¬ing 8.5% 02 and 12.5% SO2. Best volatilizations (90% of the As, 52% of the Pb) were obtained under localized conditions attained in an air-type flame. Average volatilizations were: air-type flame, As 50%, Pb 32%; oxygen-type flame, As 40%, Pb 30%. The substitution of oxygen for air reduced the arsenic volatilization. The products of combustion were mainly cuprospinel and cuprite; small inclusions of elemental copper were found in some of the particles. At high temperatures, there was a loss of copper due to vaporization of CU( g) CuO kg) (g)

Jan 1, 1983

By Kiyoshi Shibata

A new assessment model has been proposed for metal production and its recycling system. The model consists of three processes, smelting of ore, cascading and upgrading of metal scrap. The present approach is to assess the total energy consumption of the system, by introducing two equations for describing the relationships between critical impurity content and the mass of production or scrap recycling. The total energy consumption in the system can be described as a function of recycling rate and performance of the upgrading process. The present model suggests that the impurity removal efficiency and yield in the upgrading process are essential to reduce the energy consumption in the systems. Especially, such points should be explicitly controlled in recycling of aluminum. The potential capability of this model was also discussed by obtaining several quantitative information required for the process design and the operational control of beneficial recycling of metals.

Jan 1, 1998

By Chen-Ming Kuo, Esher Hsu

"The importers and manufacturers who import or produce products with packaging containers are charged a recycling fee in Taiwan. The amount of waste packaging containers used for calculating the recycling charge is based upon the amount declared by importers and manufacturers which might be underestimated. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explores its distribution. The sampling survey and ratio estimation are conducted for estimating the recycled amount; while the refuse sampling method for municipal solid waste composition is employed to estimate the un-recycled waste packaging containers. The estimated total amount of waste packaging containers in 2011 generated by households in Taiwan is 696,511 m.t., of which, 79.49% of the waste packaging containers were recycled and 20.51 % were landfilled or incinerated. This study shows that the amount of waste packaging containers declared by importers and producers is underestimated around 20%.IntroductionWaste packaging containers including iron cans, aluminum cans, glass bottles, plastic containers, paper containers, aluminum foiled paper packs are officially announced to be recycled in Taiwan. In order to create the economic incentive for raising recycling performance, associated manufacturers and importers are charged a recycling fee to subsidize recyclers. The amount of packaging containers declared by importers and manufacturers is used for calculating the recycling charge and recycling rate. The importers and manufacturers might underreport their producing (importing) amount to pay less recycling fees. Therefore, the estimated waste packaging containers based upon the amount declared by importers and manufacturers is usually underestimated. Related previous studies about waste packaging containers recycling in Taiwan are done by Hsu and co-workers [1-4]. Hsu and Kuo [1] estimated total production values of recycling and evaluated the performance of recycling performance based upon the estimated production values. Hsu and Liu [5] provided a cost analysis of recycling for waste packaging containers in Taiwan. Bor, Chien, and Hsu [2] presented a market-incentive recycling system for waste packaging containers in Taiwan. Hsu and Kuo [4] provided an amending mechanism for product charge and recycling subsidy in response to the social economic changes for waste packaging containers recycling. Lee and Hsu [ 6, 7] explored the distribution, fee rates, and collection rate of waste containers. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explore its distribution."

Jan 1, 2014

By H. Y. Sohn

"The nonferrous production industry has gone through a remarkable transformation in recent years in terms of developing and adopting new technologies. Technology innovations have largely been driven by the need for greatly improved environmental protection in addition to increased productivity. One of the most notable aspects of the new technologies is their ability to reduce the emission of sulfur and other pollutants to extremely low levels.The current industry trends towards more environmentally friendly technologies are bringing about additional benefits of developing more efficient, technically advanced, and continuous processes in closed reactor vessels. Key aspects of these modem trends include the use of increased oxygen enrichment in the process gas, better process control, reduced manpower requirements, and plant operations with more skilled personnel.Computer simulation and modeling of complex processes have become more reliable, realistic, and thus increasingly useful in metal production. Some of the notable examples are reviewed.Finally, the need and advantages for value-added production in the nonferrous industry are discussed.I. IntroductionMost recently commissioned technologies for nonferrous metals production have been developed largely in response to environmental concerns. One of the most remarkable improvements made by the nonferrous industry in the last decade has been the rapid increase in sulfur capture. Before the start of the last decade, 90% capture of sulfur was considered good. Since then, strict emission regulations have become the norm in advanced societies, although smelters in many parts of the world still operate with limited pollution control. Other emissions and discharges have also been substantially reduced, resulting in much improved working conditions and worker hygiene in addition to the overall environmental protection. The development of the more environmentally friendly technologies has accompanied other advantageous advances made in the nonferrous industry, i.e., the trend towards more gas-tight, continuous processes and larger plants. This has increased the competitive edge enjoyed by the industry in the industrial countries, offsetting the higher costs of labor and pollution abatement that they have to overcome in those countries. Experience has shown that clean technology often leads to a profitable business, because its adoption forces the concomitant advancement of related technologies in addition to the avoidance of penalties imposed by the public on pollution-prone industries. Needless to say, there are other driving forces for new technologies such as reduction of operating and capital costs, improved product quality, and energy considerations in terms of reduced consumption and utilization of readily available sources."

Jan 1, 2000

By M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would, be reduced at the new smelter to about a half of the sum of those from previous two smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive off gases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014