Search Documents

By Shuji Owada, Mayumi Ito, Takehiko Nishimura, Toru Yamashita, Sadayuki Shinozaki, Takashi Ando, Tomoe Ota

Electrical disintegration (ED) was applied to Nantun coal (China) in order to improve liberation of coal substance for the pretreatment of producing “Hyper Coal” of which the combustion gas was planning to inject directly to turbine for power generation. It has been found that many cracks generated in the ED were existent at phase boundaries with mineral matters and liberation of coal substance became much higher than that in mechanical comminution methods such as roll crusher. Since the ED occurred more easily (with lower voltage applied) for the coals of higher mineral content, it is considered that this method could make a better contribution especially to comminute middling coals. We also found that the ED technique could apply not only single particles but also to coal particles assemblage, keeping almost the same or higher disintegration efficiency. In the mineral matters, Si and Al components were preferentially well liberated by the ED.

Jan 1, 2003

By K. W. Stöckelhuber, A. Wenger, H. J. Schulze

"An important elementary step of the flotation process is the forming, drainage and rupture of a thin intervening liquid film between bubble and mineral particle.After the encounter of the bubble with the solid surface a wetting film is formed. The initial thinning of this film is driven by the capillary pressure inside the bubble. When the film has reached a certain thickness rupture can take place.There are two possible mechanisms describing this process:-, Growing fluctuation waves (spinodal dewetting) on fluid interfaces under the influence of any kind of attractive forces (electrostatic, van der Waals). -, Nucleation inside the film.Metastable wetting films on negatively charged, hydrophobic glass surfaces (gaseous phase methylated), or on hydrophilic, positively charged glass surfaces (with Al3+ ions), have been analysed by means of the kinetics of film thinning according to the Reynolds law. These experiments demonstrate that both mechanisms can be responsible for the rupture of a thin wetting film. In the case of hydrophobic surfaces the nucleation mechanism is preferred; in the case of opposite charged silica surface the capillary waves mechanism due to an attractive electrostatic double layer force between silica and air bubble takes place.Hereby the existence of a long range hydrophobic force. on a hydrophobic surface can be excluded. The apparent interaction can be explained by the presence of gas nuclei formed on heterogeneous surface sites. The results provide deeper insight into the mechanisms of wetting film stability, adhesion process in flotation and droplet coalescence."

Jan 1, 2003

By Gabriela Pino, Maurício Torem, Diego Veneu

Because of its simplicity, economy and biocompatibility, research regarding the use of microorganism for decontaminating heavy metals produced by many industries is an area of growing interest. Also, there is a stringent need for the control of toxic metals produced during various production processes and released into the aqueous environment in order to avoid damage relevant to soil or groundwater contamination. Among the available treatment technologies, sorptive flotation has been considered as a promising alternative for the wastewater treatment. In the present study Streptomyces lunalinharesii strain was applied as bioreagent for the removal of copper, cadmium and zinc. The removal of those metal ions depends mainly on the respective pH value, influencing the aquatic speciation during the process, as well as the zeta potential of the system and biomass concentration. Langmuir and Freundlich isotherms have been depicted. Dispersed air flotation was applied as the subsequent separation method for harvesting the suspended metal laden microorganisms, following the biosorption of copper, zinc and cadmium. The investigated parameters (in batch mode, laboratory scale) were in this case the saturator pressure, the coagulant concentration and the recycled flow. Applying the optimum defined conditions, over 60% removal of metal ions have been achieved in one stage and simultaneously, quantitative separation of the used (metal-loaded) biomass has been obtained.

Jan 1, 2014

By Trevor Saldanha, Stephen Grano

A key uncertainty in flotation modelling is determining, a priori, the proportion of each mineral which will develop a certain rate constant for different feeds of variable liberation and hydrophobicity. First and foremost is the ability to predict the proportion of minerals that will not be recovered, even at very long flotation times, and which therefore report to the tailing stream as the non-floatable fraction (i.e., having a zero rate constant). Recent empirical evidence has shown there are at least two factors which contribute to heterogeneity in flotation rates and, in particular, the appearance of a non-floatable fraction - heterogeneity in the distribution of adsorbed collector amount on a particle-by-particle basis, even for the same liberated mineral in the same size fraction, and the existence of a critical contact angle below which the bubble-particle union is unstable. In this paper, inferred measures of the critical contact angle for liberated particles are compared with stability model calculations. This has demonstrated that the dependency of the critical contact angle with particle size and mineral specific gravity are explicable by bubble-particle stability considerations. This argument is further extended to the flotation behaviour of composite particles, as a function of liberation class, in which the wetting perimeter of the attached bubble on the composite particle surface is constrained by the presence of a surrounding hydrophilic domain for the case of simple binary composites. Reasons for the different flotation behaviour of composite particles having different textures, as noted in the literature, are also discussed in terms of the stability of the bubble-particle union.

Jan 1, 2014

By M. A. Hampton

The surface oxidation of sulfide minerals in aqueous solutions is an important sub-process in sulfide flotation and hydrometallurgy, but a full understanding of the oxidation process and products is still lacking. Many oxidation pathways and products involving elemental sulfur, metal polysulfide, metal-deficient sulfide and sulfate have been proposed, confirmed and argued. In this paper we provide further insight into the surface electrochemical behaviour of galena in aqueous solutions. For this research we have developed a novel experimental system, that combines chronoamperometry and AC-mode AFM surface imaging, which allows for in-situ, synchronized electrochemical control and examination of oxidative surface morphology. At pH4, the morphology of elemental sulfur (detected by ex-situ Cryo-XPS) formed on the oxidizing galena surface depends on the electrochemical potential pathway. In multi-step chronoamperometry (i.e. four potential steps from 0 mV to + 350 mV) the sulfur forms as nanoscopic domains, whereas in single-step chronoamperometry (i.e. one potential step from 0 mV to + 350 mV) sulfur forms as a heterogeneous layer. In each case the oxidation is controlled so that the number of electrons (coulombs) passed per unit area is the same, therefore the amount of sulfur produced is also the same. The differences in morphology with electrochemical potential pathway are explained using a nucleation and growth model. The formation of sulfur on the surface increased both advancing and receding contact angle of galena, but the morphological changes induced by different electrochemical potential pathways did not significantly alter the hydrophobicity of the surface. Keywords: galena, lead sulfide, oxidation, Atomic Force Microscopy, electrochemistry, collectorless flotation, hydrophobic

Sep 1, 2012

In this study, the effect of different regrinding conditions on the depression of fine pyrite at the cleaner stage was investigated. The regrinding condition was manipulated by different grinding media (stainless steel and mild steel). It was found that, after regrinding with mild steel grinding media, the flotation recovery of pyrite is much lower than with stainless steel grinding media, and it is more difficult to restore by adding more collector. This means, regrinding with mild steel grinding media may depress the pyrite flotation more strongly. The copper activation of pyrite during regrinding was also studied. It was found, that the mild steel grinding media is more beneficial to copper activation than stainless steel media. Additionally, the analysis of pyrite recovery based on the particle size indicated, that the fine particles are more susceptible to different grinding environments than intermediate and coarse particles and therefore are more easily depressed with a much lower flotation recovery.

Sep 1, 2012

By A. Collings, A. Farmer

Power ultrasound may be used in the processing of mineral suspensions to clean the particle surfaces of oxidation products and fine coatings, mainly through the large, but very localised forces, produced by cavitation. This effect may be utilised in lowering the level of iron contamination in silica sand used for glass making, in improving the sharpness of electrostatic separation of heavy mineral concentrates, in shortening the time of leaching of minerals and in improving the selectivity and recovery of flotation processes. Parameters affecting the efficiency of these processes, such as input power and levels of reagent addition, are discussed. In particular, we present data showing the relationship between power input and the particle size of surface coatings removed, which can be explained by the Derjaguin approximation for the energy of interaction between a sphere and a flat surface. Pilot scale studies, using commercially available components, are currently being used to assess process viability and will be compared with laboratory scale results.

Jan 1, 2003

By Wolfgang Öfner

Many technical processes also yield dusty residues which usually contain appreciable amounts of valuable matter. Often they also accumulate substances detrimental to the process. Dumping them entirely in landfills wastes raw material and causes high disposal costs, but recycling them without prior treatment is often not feasible. Physical separation processes are preferable because of their rather low energy demand. In order to develop such treatment systematically, the residues must be characterized properly. The technique for such a characterization is taken from mineral processing: perfect fractionation according to continuous properties of the particles supplemented with chemical analysis are used for plotting the Henry-Reinhardt chart. This represents the benchmark for assessing actual separation processes and tests. Their results are compared in terms of ?selectivity? and plotted in the kappa chart. In this paper, Henry-Reinhardt chart and kappa chart are applied to several different types of residues from iron and steel production and show their potential for being upgraded before reutilization in the production process. This approach is suitable for virtually all dusty residues from other industrial processes as well. Keywords: residue, dust,iron and steel, process development, Henry-Reinhardt chart, kappa chart

Sep 1, 2012

By Kaioeng Wang, Qi Liu, Yahui Xiang

"In the differential metal sulfide ore flotation it is desirable to replace the toxic inorganic depressants with environmentally benign chemicals. Chitosan, as a natural and non-toxic polymer, has been proven to be an efficient depressant for chalcopyrite while allowing galena to be floated by xanthate collectors. However, the poor solubility of chitosan limits its potential applications as the flotation could only be carried out at about pH 4 where chitosan is soluble. A carboxymethyl derivative of chitosan, named N-carboxymethyl chitosan (N-CMC), was synthesized by substituting the amino groups of chitosan with carboxymethyl groups. The substitution significantly improved the solubility of chitosan. The structure of N-CMC was studied and compared with chitosan via Fourier transform infrared spectroscopy (FTIR). Flotation tests were performed on single minerals and mineral mixtures (with weight ratio of 1:1) with the addition of appropriate amount of potassium ethyl xanthate (KEX) and N-CMC. The solution pH was varied from neutral to alkaline. The flotation concentrates and tailings were collected and analysed for the contents of copper and lead. FTIR measurements showed that new peaks of C=O stretching of -COOH and N-H deformation of -NH- appeared in N-CMC, which indicated that the carboxymethyl groups were introduced and the amino groups were the sites for the substitution. Flotation results indicated that N-CMC could depress either chalcopyrite or galena depending on the pH. The results were not affected by the sequence of KEX and N-CMC addition. Therefore, N-CMC is potentially useful in Cu-Pb sulfide separation following a bulk Cu-Pb flotation. The N-CMC was also found to have surface cleaning functions, and was able to remove contaminating copper ions from galena surfaces. Therefore, its application in sulfide ore flotation is expected to be more robust than the original chitosan."

Jan 1, 2014

By W. H. Cheung

Nickel (Ni) plays a major role in the production of steel and other major alloys. There are two sources of Ni: laterite and sulphide ores. Global reserves of sulphide ores are being rapidly depleted, while there are enormous reserves of Ni laterite, much of it in Australia. As well as being present in huge amounts, Ni laterites have the advantage of containing cobalt (Co), a valuable mineral. Over the past decade, these factors have been driving the industry to explore the processing of Ni laterite. A route that has been used commercially in processing nickel laterite ore involves the thermal activation of the minerals by pre-reduction followed by ammoniacal leaching (Caron). Although this process has been effective in processing the goethite rich laterite minerals, the higher-grade serpentine-based minerals have been shown to be less susceptible to this process. This has been attributed to the formation of inert olivine phases. In this study, we examined the use of an alternative lixiviant, sulphuric acid, in leaching pre-reduced limonite and weathered saprolite nickel laterite ores. The specific aim of this study was to examine the sulphuric acid leaching of Ni and Co from pre-reduced laterite minerals, and to understand the role of mineral transformations in this metal dissolution. Synchrotron based X-ray diffraction was used to examine the transformation of goethite (FeOOH) to spinels and serpentine mineral ((Mg,Fe)3Si2O5(OH)4) to olivine. Reduction tests were carried out using CO and CO2 reducing gas mixtures and temperatures from 400 °C to 700 °C. The rate of formation and disappearance of specific Bragg peaks during reduction of specific minerals were used to derive an understanding of these solid-state reactions. Laboratory based reduction tests and leaching in sulphuric acid were used to validate the effect of these mineral transformations. The results suggest the versatility of sulphuric acid in leaching nickel from spinels and olivine, which was achieved at the expense of lower selectivity. Cobalt dissolution was found to be dependent on the nature of ferro-cobalt alloy formed during reduction.

Jan 1, 2014

By Kari Niiranen, Andreas Fredriksson

LKAB (Luossavaara-Kiirunavaara AB) is operating iron ore mines, concentration plants and pelletizing plants in Northern Sweden. Geometallurgy, which combines geological and metallurgical information is not a new way of thinking at LKAB, but rather a revised and updated version of an old working process. A project called "Silica in the Mine" which started in 2007, was an important reason to set a new focus at the geometallurgy. The target of the project was to develop a simplified method in laboratory scale to predict SiO2 grade in the magnetite concentrate in Kiruna and further predict the physical properties of the crude ore with respect to processing characteristics. The connection between mineralogy and products properties have started to be even more vital and necessary to examine due to the future exploiting new iron ore deposits. Geometallurgy at LKAB can be described as a mental and strategic framework where the Research and Development department (R&D), and others within the organization of LKAB, aims towards the connection of the minerals-production-products. It could in its basics be called "research & development", but it must be clarified that changes have been made, mainly due to the development on the instrumental analysis side. LKAB’s idea is to work quite broad, with internal educations, an active working process in ongoing projects, together with external parties (such as universities), with several PhD-projects and an upgrading on the instrumental side at the LKAB Research & Development department. This paper is a summary about the concept Geometallurgy at LKAB and some of the actions within its framework.

Jan 1, 2014

By A. Otsuki

This paper describes the evaluation method of dispersion and coagulation of silica nano-particles by means of interactive force apparatus. The apparatus measures the size of fine particles in aqueous solution or organic solvent of high concentration and/or low optical transparency. Other conventional apparatus for size measurements (such as, apparatus utilizing dynamic light scattering) are difficult to measure the size of particles in such conditions accurately, due to multi-scattering of light in the sample solution or solvent. The apparatus measures the interactive force between two surfaces, i.e. the gold-coated glass hemisphere and the brass flat plate, (which is fixed at the bottom of the sample cell). The apparatus has three parts, i.e. main part (which consists of electric balance, hemisphere and flat plate), control part (i.e. personal computer, piezo-stage controller and voltage supplier), and detecting part (i.e. multi-meter and oscilloscope). During the measurement, electric field is applied between the hemisphere and flat plate, and thus dielectric particles are arranged toward the direction of electric field in the area between two plates. When the two plates are close to each other, two different forces (i.e. repulsive force and attractive force) will alternately act on particles due to the structure change of the particles. The repulsive force occurs when the structure of particles is stretched by compressive force; whereas the attractive force occurs when the aggregate structure is broken. The cycle of the repulsive and attractive forces is a primary size of particle or size of aggregate, which depends on the degree of agglomeration. The measured size of particles, which is varied depending on their degree of dispersion and coagulation, determined the characteristics of the silica particles. In this research work, the effect of size and concentration of particles in aqueous solution on the degree of dispersion and coagulation of the silica particles were investigated. Spherical silica particles were selected for this investigation due to their variety of size. This apparatus can be used to evaluate the degree of dispersion and coagulation of other nano-particles in various solvents in many process industries.

Jan 1, 2014

By Erico Tabosa, Kym Runge, Peter Holtham

"The distribution of turbulence in an industrial scale mechanical flotation cell and its effect on flotation kinetics was studied using a fully instrumented 3m³ cell. The cell was operated at a copper concentrator in Australia with different combinations of airflow rates, impeller speeds and sizes and cell aspect ratio providing a wide range of hydrodynamic conditions. An analysis of the overall flotation cell performance showed that the overall copper recoveries were very similar for the conditions tested. However, by decoupling pulp effects from froth effects it was possible to evaluate whether the changes made affected the pulp zone and/or froth zone responses. The analysis showed that the overall recovery has the potential to be up to 7% higher, if not limited by froth recovery. The cell hydrodynamics were characterised by the overall energy dissipation rate and, to understand the distribution of turbulence within the cell, localised measurements were made using a piezoelectric vibration sensor. By comparing the metallurgical performance of the cell with the different hydrodynamic conditions it was found that the collection zone flotation rate constant was not directly related to overall energy dissipation, as is commonly observed at laboratory scale, where energy is usually only changed by varying impeller speed. In this study, energy dissipation rate was varied using not only impeller speed, but also the size of the impeller and the cell aspect ratio. In these circumstances, the best correlation was found to be between the collection zone flotation rate constant and the distribution of turbulence, i.e. the size of the turbulent zone."

Jan 1, 2014

By H. U. R. Kattentidt, W. L. Dalmijn, T. P. R. de Jong

"Research at Delft University aims to develop systems for automatic inspection and sorting of bulk solids which can be applied in the mineral processing and recycling industry. A recent development includes an automatic sorter based on airport X-ray inspection technology. It is designed for continuous inspection and sorting of 5 - 150 mm solids and has as objective a cost effective and high capacity on-line inspection and sorting.Dual energy X-ray transmission imaging provides instantaneous data about particle dimensions and the atomic number distribution. The system provides particle thickness and average atomic number on a pixel level at scanning speeds between 250 and 500 lines / second. With existing X-ray components inspection speeds between 0.5 and 2 m/s at approximately 1-meter inspection width and between 1.5*1.5 and 5*5 mm2 sensor resolution can be achieved.Imaging algorithms that were developed by Delft University for applications in recycling, waste cleaning and other applications acquire shape, size distribution and composition data. Currently on-line processing of a product at a rate of around 200 particles per second is possible using a standard PC. Experiments with a demonstration X-ray unit indicated good potential for various applications in solids processing. They include continuous inspection of organic content, sulphur, chlorine, ash, and metal distribution. It is applicable for coal cleaning, ore sorting, industrial minerals, and various applications within waste cleaning and recycling. Dual energy X-ray transmission fundamentals and recent progress in system development and applications are presented."

Jan 1, 2003

By P. Basarova

The attachment of bubbles onto a collecting surface is an ubiquitous natural phenomenon, playing a critical role in numerous practical processes. The goal of the project is to broaden the knowledge about hydrodynamic interactions between small bubbles and large solids that occur in nature and industrial processes. Focusing on collision processes between a single rising bubble (Db<1 mm) and a larger falling spherical particle in stagnant liquid, the theoretical model describing the bubble trajectory is given here. The model is based on analysis of forces acting on the bubble, and utilizes equation for the bubble motion. Mobile and immobile type of bubble surface mobility are considered. The calculated results are compared with the experimental data; here a high-speed video camera was used to capture the bubble motion and bubble-particle interaction. Very good agreement between experimental and calculated data was found. For both types of surface mobilities, the bubble deviation in the horizontal direction is nearly linear. The proportion constant is bigger for immobile bubble surface and increases with the bubble size. Furthermore, particular forces acting on bubble were studied. A similar course of relative bubble velocity and force impact was observed for identical bubble position. For cases when the bubble centre is close to the particle axis, only deflection in one direction is observed. When the bubble is reaching the maximum trajectory, the force ratio is changed. The bubble is firstly pushed away from the particle, but when it is within close distance from the particle, the bubble is pushed towards the particle.

Sep 1, 2012

By Andries Van Wyk, Steven Bradshaw, Guven Akdogan, Jacques Eksteen, Cornelius Snyders, Cleophace Mpinga

"In order to exploit lower grade and complex platinum group metal resources, cheaper and more efficient alternatives to the conventional mill-float-smelt-refine route are being sought, particularly for resources’ in areas that are water-scarce and where electrification is costly and problematic. Leaching with cyanide is a promising process option and although recoveries are lower than in the conventional process routes, progress into the understanding of cyanide leaching of PGM containing ore and concentrate has been made. Research regarding the feasibility of upgrading the pregnant PGM leach solution using activated carbon has, however, been lacking and hence forms the focus of this paper. Bottle roll adsorption tests for dilute PGM solutions (0.15ppm Pt, 0.38 ppm Pd, 0.1 ppm Au) onto granular activated carbon showed high rates within the first 60 minutes (giving more than 90% recovery of precious metals). Comparison of the Pt isotherm to Au isotherms from literature indicated a similar loading capacity, while that of Pd was found to be significantly lower. The effects of solution pH, temperature, base metal concentration, free cyanide concentration, thiocyanate concentration, initial PGM concentration and activated carbon concentration were investigated and are discussed. Elution of the Pt and Pd, with the AARL elution process, was found to be effective with recoveries of 95% after 5 bed volumes of eluant at the optimum pre-treatment concentrations and a temperature of 80°C. Temperature, NaCN and NaOH pre-treatment concentration and the ionic strength of the eluant were found to be the most important factors affecting elution while base metals concentration, acid-pre-treatment, carbon loading and thiocyanate concentrations to a lesser extent. Simplified combined flow sheets are suggested and the corresponding mass balances are compared."

Jan 1, 2014

By John Nell, Paul den Hoed

Carbochlorination tests were conducted with matched particle-size fractions of rutile, ilmenite and high-titania slag in a small bubbling fluidized-bed reactor. The effects of temperature, the type and proportion of solid reductant in the charge, and the fraction of Cl2 in the fluidizing gas were investigated. Tests confirm the need for solid carbon in the bed if chlorination is to run at high rates. With solid carbon in the bed, CO supplied with the fluidizing gas does not increase significantly the degree of chlorination after 75 minutes. Ilmenite is chlorinated more quickly than titania slag, which in turn is chlorinated more quickly than rutile. Rates of chlorination at 1100°C and 1000°C are much the same and significantly higher than at 900°C. Chlorination is associated with significant increases in particle porosity (even for rutile), which is brought about by the rapid initial chlorination of FeO and MnO (in ilmenite and slag) and (it is argued) by the chlorination of Ti2O3 which forms at high-energy surface sites. A reaction mechanism is presented; where possible, its validity is demonstrated by the support of empirical observations.

Jan 1, 2003

By M. Maldonado

A flotation bank is a serial arrangement of cells. How to optimally operate a bank remains a challenge. This article reviews three reported strategies: air profiling, mass-pull (froth velocity) profiling and Peak Air Recovery (PAR) profiling. These are all ways of manipulating the recovery profile down a bank, which may be the property being exploited. Mathematical analysis has shown that a flat cell-by-cell recovery profile maximizes the separation of two floatable minerals for a given target bank recovery when the relative floatability is constant down the bank. Available bank survey data are analyzed with respect to recovery profiling. Possible variations on recovery profile to minimize entrainment are discussed.

Sep 1, 2012

Sedimentary deposits such as sandstone are formed by the aggregation of cemented sand grains. Phosphates and laterite present similar aggregation of mineral grains. Grains and cement have different mineralogy and chemical characteristics. During size reduction through crushing or coarse grinding, the rocks are crumbled. Mineral grains and cement are then liberated, and the produced size distribution reflects their ?natural size distribution?. Mathematical modelling of these concomitant effects of crumbling and mineral liberation necessitates a specific material description and the adaptation of the commonly used theories of breakage kinetics and population balance. The coarse particles are mainly agglomerates made of mineral grains and cement particles whereas the fine particles are grains and cement with a natural grain size distribution. The population balance between the different particle size and particle types during size reduction takes into account the breakage rate and the progeny size distribution. The breakage rate can be described by a simple probability function or by a first order kinetics whereas the progeny size distribution is described by a breakage matrix. The model proposed here considers that the agglomerates will produce other agglomerated particles, liberated grains and cement particles; the two latter having their natural size distribution. The liberated grains and cement particles are subject to size reduction and follow the most commonly used theory of breakage. The present paper describes the theoretical approach of the concomitant crumbling and liberation effects. The application to a mathematical model for the cone crusher is presented. The advantage of such approach is then demonstrated through a simulation study for the optimisation of a crushing plant. Keywords: mineral liberation, modelling, crushing, sedimentary ore

Sep 1, 2012

By S. Fiore, M. C. Zanetti, C. Clerici

The processes and fluxes of a cast iron foundry plant located in the North of Italy were analyzed in order to determine the amount and kind of wastes produced from the different activities. The main fractions are the molding sands, furnace muds and powders coming from the dust abatement plant, the exhaust lime, the furnace refractory, the metallic shotting and the sludges and powders coming from the dust abatement plant of molding lines for a total production equal to 800 t/d. All wastes were sampled and particle-size and chemically characterized to evaluate the best recycling or reuse solutions. Wastes were sieved and divided in three categories according to the particle-size dimensions: below 0.1 mm, between 0.1 and 0.6 mm and above 0.6 mm. The fraction above 0.6 mm dimension underwent magnetic separation to recover and quantify the potentially available iron fraction. The fraction between 0.1 mm and 0.6 mm was chemically characterized in order to understand if it could be fed to the sand regeneration plant. The below 0.1 mm fraction was characterized to evaluate the following recycling and reuse solutions: additive for molding sands and/or raw material for the concrete industry.

Jan 1, 2003