Search Documents

By Sylwia Zymankowska-Kumon, Rafal Danko, Mariusz Holtzer, Artur Bobrowski, Michal Kubecki

"Moulding sands with furan resin constitute constantly growing part in technologies of producing castings from iron alloys. Due to the presence of harmful substances in resins such as furfuryl alcohol, phenol and formaldehyde, using those mould sands may be hazardous to the natural environment and workers. The general assessment of harmfulness of sands used for molds and cores encompasses 2 basic points: emission of hazardous substances during processes of preparing sands, pouring mold with liquid metals (high temperatures), cooling and shaking-out; possibility of washing out hazardous substances from used sands to the environment, during storage or economic use outside foundries. We present the results of research on the assessment of harmfulness of mould sands with furan resin in the scope of the above points. The research was conducted according to the original method prepared by the authors, which has been used for years in cooperation with various foundries (Poland, abroad).IntroductionSands are used by the foundry industry to create metalcasting moulds, where the individual sand grains are typically bound using bentonite clay and carbonaceous additives or resins. During the casting process, the moulds can be exposed to temperatures as high as 1500°C depending upon the metal being poured. The molten metal causes thermal decomposition of carbonaceous additives or resins, which results in the formation of potentially hazardous organics that are emitted to the atmosphere and condense in the moulding sand [1]. The moulding sands are reclaimed within the foundry, but part of them are eventually discarded in landfills, because it is not longer suitable to make metalcasting molds [2, 3]."

Jan 1, 2013

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

Jan 1, 1991

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By Mikiya Tanaka, Mikio Kobayashi, Mansour A. S. A1Ghamdi, Kenji Tatsumi, Yukinori Saiki, Hirotaka Senba

"In order to recover nickel ion in a spent electroless nickel - phosphorus alloy plating bath and, at the same time, to remove impurities such as iron and zinc, the applicability of solvent extraction with LlX84I as the extractant has been investigated using actual spent solution. Although the extraction efficiency of nickel from the spent solution is considerably lower than that from the nickel sulfate-nitrate solution, nickel in the spent solution is selectively extracted with high efficiency at the pH of 6 - 7. The extracted nickel is effectively stripped by sulfuric acid at a pH of less .than· 3. On the basis of these results, a· flowsheet for recovering nickel from the spent solution is proposed Chemical equilibrium calculations of the spent solution has shown that the complex formations of nickel with anions such as lactate and phosphonate ions become predominant in the pH range between 2 and 6. This results in the depression of nickel extraction efficiency from the spent solution as compared with that from the .nickel sulfate-nitrate solution. By combining these aqueous equilibrium calculations with the· extraction model considering the extraction stoichiometry and the aggregation of the extractant in the organic phase, the extraction behavior of nickel is quantitatively predicted.IntroductionElectroless plating is indispensable for the recent advanced industries such as the electronic and mechanical industries. Electroless plating baths are repeatedly used by supplying the metal salts; however, the accumulation of the counter anions of the metal ions, the components formed by the oxidation of the reducing reagents in the plating baths, and the metal ions as impurities dissolved from the surface of the objective materials degrades the· quality of the plating. Thus, the baths are finally treated by a precipitation method to form a large amount of metal sludge, which is disposed in dumping sites. Therefore, from the standpoints of environmental protection and resource preservation, it is highly desired to establish a recycling process of the plating baths with minimum emission. Solvent extraction seems to be one of the 'suitable methods to recover metals from the spent electroless plating baths, because the concentration of the metal ion in the baths is relatively high, which is advantageous to solvent extraction as compared with the ion-exchange and adsorption methods. Some studies about the application of solvent extraction have already been carried out using simulated spe11t electroless plating baths [1-3]."

Jan 1, 2000

By M. Z. Quadir, M. A. Islam, P. J. Hazell, G. J. Appleby-Thomas, J. P. Escobedo

The mechanical response of closed-cell aluminium metallic foams subjected to low and high strain-rate loading has been investigated. A set of quasi-static and dynamic (shock) compressive tests have been conducted on closed-cell aluminium foams (CYMAT) with densities of 0.50 and 0.30 g/cc. Post-mortem characterization via optical microscopy and electron backscatter diffraction (EBSD) was performed on pristine and deformed specimens to elucidate the dominant deformation mechanisms in these materials. The combination of these techniques allowed for the assessment of critical deformation parameters such as changes in cell geometry and morphology, as well as microstructural evolution and deformation of the aluminium cellular network. These findings aim to aid in the design and development of optimized material structures for impact and blast protection.

Jan 1, 2015

Microstructural investigation has shown that grain splitting or deformation banding ( DB ) develops progressively with increasing strains during cold rolling. Of particular significance to simulating texture development in cold rolled BCC polycrystals is the operation of higher order slip systems other than 110 and, the occurrence of DB in the rolling plane since the latter allows a new relaxation of the shears. Deformation banding ( DB ) model includes grain subdivision in the rolling plane and applies the Relaxed Constraints ( RC ) mechanism for the other shears. An energy criterion for deciding whether deformation banding occurs or not has been postulated, referred to as Deformation Banding Criterion ( DBC ). This paper reports the results of the investigations into the effects of different slip systems, i.e., those based on 110, 112 and 123 slip planes and their combinations using RC, DB and DBC models, in developing simulated BCC rolling textures.

Jan 1, 1999

By Lori Bassman, Cassandra George, Cullen McMahon, Md. Zakaria Quadir, Michael Ferry

"Complete and accurate analysis of subgrain microstructural features must include three-dimensional information. Three-dimensional electron backscatter diffraction (EBSD) data can be used to characterize these features; however their boundaries first must be determined. This cannot be accomplished simply with pixel-to-pixel misorientation thresholding because many of the boundaries are gradual transitions in crystallographic orientation. Fast Multiscale Clustering (FMC) is an established image processing technique that we have combined with quaternion representation of orientation to segment this kind of data. Segmentation algorithms often have issues handling images with both distinct and subtle boundaries. Our implementation of FMC addresses this by using a novel distance function and statistical analysis to take into account the variance in orientation of each feature. Although FMC was originally a twodimensional image processing algorithm it can be generalized to analyze threedimensional data sets. As an example, a segmentation of microbands in cold-rolled aluminum is presented.IntroductionThree-dimensional electron backscatter diffraction (3D-EBSD) is a method for mapping the local crystallographic orientations of points in a volume. The technique uses a dual beam platform consisting of a focused ion beam (FIB) and SEM with EBSD, where FIB is used for serial sectioning and EBSD for orientation mapping of 2D slices. These 2D slices may then be stacked to create a 3D volumetric data set.Typical uses of such a data set include characterizing the geometries and crystallographic orientations of surfaces between structures in 3D [1-5]. This involves identifying boundaries accurately, either in 2D slices with subsequent 3D reconstruction (as illustrated in Figure 1) or in the 3D data set. All such data sets present the challenges of i) aligning data slices to correct for instrument drift, ii) identifying relevant boundaries, and iii) implementing appropriate smoothing or interpolation algorithms. The focus of this paper is boundary identification."

Jan 1, 2011

By M. M. Kim

As-electrogalvanized coatings of pure Zn, Zn-11% Fe, and Zn-18% Fe coatings were characterized in terms of initial crystal structure and surface morphology. Samples were then subjected to heat treatments simulating the paint bake cycle of automobile manufacturers. Surface morphology changes were correlated with the process variables, and crystallo.graphic changes were interpreted by mapping heat treatment routes on the Fe-Zn phase diagram. The morphology of pure zinc electrogalvanized coatings with heat treatment from platelets to smeared platelets. The zn-11% Fe coating changes with heat treatment from tetrahedral nodules to a mixture of round and tetrahedral nodules, with the Zn-:18% Fe coating always having round nodules. Regarding crystal structure, a critical transformation time can be defined at any selected temperature, below which the crystal structure does not change. This temperature is related to iron content.

Jan 1, 1990

By Kuniaki Murase, Tetsuji Hirato, Yasuhiro Awakura

"Electrodeposition of CdTe was studied using aqueous ammonia-alkaline electrolytic baths in which Cd11-and Te1V-ions are dissolving as Cd11(NH3)/+ and Te1vol-ions, respectively. Ca-thodic polarization curves of the baths suggest the presence of strong interaction between the Cd11-and Te1V-ions; electrodeposition of tellurium is inhibited by the presence of Cd(NH3)/+ ions. The interaction makes it possible to electrodeposit CdTe films with stoichiometric composition. Polycrystalline CdTe thin film of about 1 µm thickness was electrodeposited at 343 K from ammonia-alkaline solutions (pH= 10.7) containing TeO32-(<20 mmol dm-3) and Cd(NH3)/+ ( < 60 mmol dm-3) ions. Increasing Cd(NH3)/42+/TeO32- mole ratio or decreasing total concentration of ammonia/ammonium-ion gave flat and smooth crystalline CdTe deposits at constant cathode potential-0.70 to -0.30 V vs SHE at 343 K.IntroductionCadmium telluride (CdTe) is well-known as a compound semiconductor whose band gap, i.e. 1.44 eV, is suitable for solar energy conversion with a photovoltaic cell. Various methods, such as CVD (chemical vapor deposition) and electrodeposition, of preparing CdTe thin films for solar cells have been investigated.Acidic sulfate solutions with a pH of 1-2 are usually employed for CdTe processing by electrodeposition.1-3) The electrodeposition of compound semiconductors is usually achieved (i) at a higher cathode potential than the redox potential of less-noble species, can in this case, and (ii) under the condition of diffusion-limiting current of a more noble species, Te1Y.4) There-fore, a suitable CdII/TeIV concentration ratio in the acidic electrolytic baths, resulting in the deposition of stoichiometric CdTe, is determined by the diffusion-limiting current density of TeIV- reduction, i.e. the concentration of HTeIVO2+ · Since the solubility ofTe1v species HTeIVO2+ in the acidic solutions is quite low, the rate at which CdTe is deposited from the acidic solutions is extremely slow."

Jan 1, 1998

By Huayi Yin, Wang. Dihua, Wei Xiao, Xuhui Mao, Diyong Tang

"The world production of crude steel reached 1.55 billion tons in 2012,which generated ~2.5 billion tons of CO2. Electrochemical metallurgy especially through high temperature molten salt electrolysis with renewable electricity stands for a great opportunity for producing “green” metals. In recent years, electrolytic production of iron without emission of CO2 in different molten salt systems has been reported. A cost-affordable inert anode is the key to produce acceptable eco-friendly iron by the novel molten salt electrolysis processes. Based on the authors’ research, this paper will discuss iron production by molten salt electrolysis using a nickel alloy inert anode. On the other hand, the paper also covers a novel molten salt CO2 capture and electrochemical transformation (MSCC-ET) process, in which CO2 is effectively converted to value-added carbon and oxygen in a molten bath using a cost-affordable nonconsumable SnO2 anode.1. IntroductionEnergy and materials are cornerstones to support the development of human society. The traditional primary metal production, especially iron and steel, and electricity production are mainly based on the reactions between carbon (coal) and oxygen (represented by equations (1) and (2) respectively), which produce huge amount of CO2.MxOy + 0.5y C = x M + 0.5y CO2 (g) + Q1 ( 1 )C + O2 (g) = CO2 (g) + Q2 ( 2 )In 2012, the world production of crude steel reached 1.55 billion tons, of which 46.3 %, ~0.7165 billion tons were produced in China. Based on the average level of 1.7t CO2 emission per ton steel, more than 1 billion tons of CO2 generated from steel industry in China in the year. Besides the iron and steel industry, thermal power plant leads the CO2 emission in both USA and China. The total consumed electricity in China increased to 4959 billion kWh in 2012, ~70% of it was from coal fired power plant. The average CO2 emission for electricity production in the typical thermal power plant in China is around 0.78 kg kWh-1. It accounts for ~ 3.868 billion tons of CO2 emission from thermal power plant in 2012 in China."

Jan 1, 2014

By John A. Thorpe, Gary R. Maxwell, Kirk M. Schall, Kenneth A. Brunk

"Gold ores containing oxide and some sulfide copper minerals incur significant cost penalties when leached with cyanide, because 4-5 moles of cyanide are consumed for each mole of leached copper. This equates to ~4 kg of NaCN per kg of leached copper. Total cost of excess NaCN consumption plus CN destruction can exceed $4.00 per tonne of ore. AuGMENT Technologies has patents pending on a process that can 1) economically recover 70-80% of the cyanide that is fed to a mill, 2) produce salable copper cathodes, and 3) reduce the need for a cyanide destruction facility. Standard equipment for resin processing and electrowinning are used to recover the cyanide and produce the copper cathodes. Steps have been taken to determine: 1) how to develop the resin kinetics, 2) how much savings are incurred at a mill site, 3) how the novel 'electro-elution' circuit achieves efficient operation.IntroductionWhen gold ores containing nuisance copper are leached with cyanide, a significant cost penalty is incurred because 4-5 moles of cyanide are consumed for each mole of copper that leaches. This is equivalent to the use of -4 kg of NaCN per kg of copper that leaches. The total cost of excess NaCN consumption plus cyanide destruction can exceed $4.00 per tonne of ore.AuGMENT Technologies has a patent pending on a process that can 1) economically recover 70-80% of the cyanide that is fed to a mill, 2) produce salable copper cathodes, and 3) reduce the need for a cyanide destruction facility. This ACCS (Au-.C.u-.C.N Solution) Process Technology involves the novel application of copper cyanide chemistry. Standard resin processing and electrowinning equipment are used to recover the cyanide and produce the copper cathodes."

Jan 1, 1997

By Adrien Antenen, Didier Villette

CITRON has developed a new process for the recycling of hydroxide sludge, household batteries, catalysts, automobile shredding residues, grinding sludge and other metal containing organic and inorganic waste. A pilot plant with a capacity of 1,000 tons per year has started operations in April 1998. In August 1999, an industrial plant became operational with an initial treatment capacity of 23,000 tons.

Jan 1, 2000

By Raymond M. Coveney

Bedded sulfide ores in Cambrian Chinese black shales typically contains at least 2% Ni, 4.5% Mo, 1% As and 0.2% Se. Thin laminae and replaced on colites from the ore contain intimate mixtures of fine-grained Ni-rich sulfides and jordisite complicating ore treatment. The ores contain abundant jordisite, vaesite, nickelian pyrite, and barite and lesser amounts of sphalerite, gersdorffite, millerite, tennantite, fluorite, chalcopyrite, and HgSe (probably tiemannite). At present only ores that are sufficiently rich (>4.5% Mo) for direct roasting are mined and treated to produce, ammonium molybdate. The ores contain Pt, Pd, and Au in amounts totaling up to -2.5 ppm, but these are not recovered.

Jan 1, 1993

By Dae Jin Ha

Sticking phenomenon occurring during hot rolling of two STS 430JlL ferritic stainless steels was analyzed by hot-rolling simulation tests. The sticking started from the initial nucleation stage in which the rolled materials were stuck onto the roll specimen surface, proceeded to the growth stage in which stuck fragments grew further, and reached the saturation stage. The modified 430JlL steel had a smaller number of sticking nucleation sites and slower growth rate than the conventional 430JlL steel because of higher high temperature hardness, thereby leading to less serious sticking. When the simulation test was conducted at 1070 °c, Cr oxides were formed on the surface of the rolled materials, and thus the sticking was drastically reduced because of the increased surface hardness of the rolled materials. In order to prevent the sticking, high-temperature properties of the rolled materials should be enhanced when rolled at 900°C or 1000 °C, and rolling conditions and alloying compositions, under which the oxide formation was promoted, were more important than high-temperature properties when rolled at higher temperatures than 1000 oC.

Jan 1, 2008

By Lev Levin, Sergei Lesokhin

"The formation of titanium carbide during hot filament assisted carburizing of NiTi alloy was investigated. Phase content and morphology of the diffusion zone were examined by X-ray diffraction, X-ray microanalysis, SEM, and Auger electron spectroscopy. The growth of stable and adherent TiC film was observed. A non-planarity of interphase boundary was noticed. The applicability of the chemical diffusion approach to the analysis of the experimentally observed interface instability is discussed. A criterion, taking into account the influence of growth stresses on the stability of the flat interface, is developed by means of linear perturbation analysis.Introduction.Equiatomic intermetallic NiTi belongs to a class of materials exhibiting the shape-memory effect. The unusual property of this compound promotes its application in many fields, from aerospace technologies to medicine. The relatively high ductility ofNiTi also permits its use as a matrix material in metal-ceramic composites. The objective of this work was to investigate the possible incorporation of a ceramic material (titanium carbide) into NiTi by gas carburizing.Free energy calculations indicate the potential to obtain TiC by carburizing Ni-Ti binary phases. The main obstacle to such a process is the high affinity of titanium to oxygen. At moderate temperatures the formation of TiC is preferable to titanium oxidation only if the partial pressure of oxygen is extremely low [1]. This problem was overcome in this work by the use of hot filament assisted gas carburizing. Due to chemical reactions occurring near the hot filament, the gas mixture, initially consisting of methane and molecular hydrogen, was enriched by atomic hydrogen [2], drastically decreasing the content of free oxygen in the carburizing atmosphere.The second part of this article concerns the theoretical analysis of reasons that lead to the development of the experimentally observed morphology of the diffusion zone. In particular, the influence of the growth stresses on the morphology of an interphase boundary is investigated."

Jan 1, 1996

By I. Mc Dougall

"The matte/slag tidal zone in a platinum smelting furnace is subject to severe process conditions which can often lead to premature failure of the lining. The MgO-FeO-Si02 slag is aggressive to refractory bricks, whilst the Ni-Cu-Fe-S matte is aggressive to water-cooled copper cooling elements, and can penetrate and sulphidize refractory bricks, particularly at the high matte temperatures often experienced in the PGM industry. A novel approach to the lining design was taken at Lonmin's new 10MW Furnace 2. An indirectly-cooled graphite ring was applied in the matte/slag tidal zone, with refractory bricks on the hot face. Thermal Finite Element modeling was conducted to determine the optimal lining design in this region of the furnace. The resistance of two graphite grades to damage by slag and matte was evaluated experimentally. The graphite lining is not wet by the matte, and is resistant to slag attack at operating temperatures. In comparison to water-cooled copper in various configurations, cooled graphite shows promise as an indirect refractory cooling system in the tidal zone area of furnaces.IntroductionIn South African Platinum Group Metals (PGM) smelting operations, the PGMs are associated with nickel-copper sulphides in magmatic rocks. After ore is mined, it is concentrated by means of a flotation process prior to smelting. Both rectangular 6-in-line and circular 3 electrode AC submerged arc furnaces are used for this purpose. A new 10 MW round furnace is currently under construction by Tenova Pyromet at Lonmin's Marikana Smelter Division. An overview of Lonmin's smelting operations and Lonmin's approach to smelting high chromite containing PGM concentrates is given by Eksteen et al. [1]"

Jan 1, 2012

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998

Reduction of titania and ilmenite ores by Cf4-H2-Ar gas mixture was investigated in a laboratory fixed bed reactor. Titania was reduced to titanium oxycarbide in the temperature range of 12OO-1500°C. At 1400-15000C, the extent of reduction of titania to titanium oxycarbide achieved more than 85% in 90 min. Optimum conditions for titanium oxycarbide synthesis by reduction of titania include temperature in the range of 1300-1450°C, methane content 8 vol% and hydrogen content above 35 vol%. Ilmenite ore was reduced by Cf4-HrAr gas mixture to metallic iron and titanium oxycarbide. Metallic iron catalyzed methane cracking and solid carbon deposition. Titanium oxycarbide formed at temperatures as low as 950°C. The optimum temperature for reduction of ilmenite is 1200°C and the optimum methane content is 8 vol%. Increase in hydrogen content increased both rate and extent of reduction. With 5 vol% CH4-75 vol% Hr20 vol% Ar gas mixture, the reduction of ilmenite completed in 60 min. Reduction of titanium oxides to oxycarbide with following chlorination may be an efficient alternative technology for processing of titanium minerals.

Jan 1, 2001

By Ma Lijuan, Zhang Yubing, Wang Bo, Sun Huilan

The effect of lime ratio on phase composition and alumina leaching property of MgO-contained calcium aluminate clinker were investigated by analytical reagent, the XRD analysis of its mechanism was discussed. The results showed that: when the sintering temperature was 1350 ℃, C/A was 1.4, A/S was 1.3 and the content of MgO was 4%, the increase of the C/A promoted the formation of C12A7 and restrained the formation of Q-phase. The alumina-leaching ratio of the clinker (A/S was 1.3) was increased from 74.33% to 91.34% when the content of CaO was 5.21%.

Jan 1, 2015

By M. S. Moats

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

Jan 1, 1996