Search Documents

By Zenjiro Asaki, Teruo Tanabe

"To clarify the formation of light rare earth (R =Ce, Pr, Nd or Sm) -Fe compounds in the reduction-diffusion (RD) process, two kinds of experiments were carried out: (a) RD experiment in which briquettes composed of R oxide powder, Fe (particles or wire) and CaH2 were reacted, and (b) immersion experiment, where an Fe plate was immersed into R-Fe melt having the composition of Fe-side liquidus line in Fe crucible. The compound formation was examined by using XRD, SEM and EPMA. The formation rates of RzFe17 measured by the RD experiment were compared with those obtained by the immersion experiment. The growth rates of compounds obtained in the RD experiment for Pr-Fe and Nd-Fe systems were much lower than those obtained in the immersion experiment. This result was explained by the difference of the reduction rates of R oxides by Ca. The parabolic rate constants for the formation of RzFe17 were separated in two groups of (a) Pr-Fe and Nd-Fe systems and (b) Ce-Fe and Sm-Fe systems. This was discussed in connection with the difference of their crystal structures and the driving force of diffusion. The parabolic rate constants for the formation of compounds in Ce-Fe and Sm-Fe systems decreased in the order of RFez, RFe3 and RzFe17.IntroductionTo understand reaction behaviors in the production of rare earth (R) -iron intermetallic compounds, which have excellent magnetic properties, is very important from engineering point of view. And the reduction-diffusion (RD) process<O has recently attracted attention as one of the promising processes to economically produce R-related materials. A few fundamental studies on the compounds formation in the RD process have previously been reported. Qi, Hino and Yazawa(2) observed the formation of R(Nd, Sm)-Fe and R-Co compounds in the process from various view points. Song and Ogawa(3) measured the growth rates of Nd-Fe and Sm-Fe compounds by using Nd or Sm vapor supplied from Nd-Ca or Sm-Ca melts. The authors have also carried out fundamental studies (4)-(8) to clarify the rate and mechanism in the production of R-Fe intermetallic compounds."

Jan 1, 1998

By Cheng Pan, Xuewei Lv, Guibao Qiu, Chenguang Bai, Meilong Hu

"Physic-chemical properties of slag at high temperature play an important role in the pyrometallurgical process of production of ferronickel alloy. It determines the operation efficiency, metal recovery ratio, energy consumption and the distribution of elements like S and P between the slag and metals. In the present work, the effect of MgO content in the slag on melting features and viscosity of the slag was investigated. The MgO content in the SiO2-CaO-MgO-Al2O3 -FeO in the quinary slag system varied from 14.5% to 22.5%. The results shown that all slag samples begin to softening at the same temperature, the softening temperature, melting temperature, flowing temperature decrease with the increase of MgO content when the MgO content is in range of 14.5 and 20.5 pct mass, and when MgO content up to 22.5 percent, the temperatures increase sharply. Besides the inflection point temperature of viscosity-temperature curve increase with the increase of MgO when the MgO content is in range 16 and 22.5 pct mass.IntroductionNickel is very important to modern society, without it, we would not be able to share many things in our daily life, such as airplanes, computers and many stainless steel appliances in our homes and workplaces1.. It is the essential element of the stainless steel making, and about 65% of the nickel consumed in the world is used to make stainless steel2., so with the increase of stainless steel, the nickel production and demand has continued to increase3.Nickel is produced from two distinct ore types: nickel sulfide deposits and oxide nickel laterite deposits. The great majority of world’s known nickel resources are contained in laterite deposits3.. The laterite ores are normal classified into two groups: the high-iron laterite ore and high-magnesia laterite ore1. Typical composition of high-magnesia laterite ore is in the range 1-3%, and these ores are suitable for pyrometallurgical process to produce ferronickel4."

Jan 1, 2012

By Noboru Masuko, Sachiko Ono

"The structure and composition of anodic films formed on aluminum in a borate solution have been investigated by using TEM and SIMS with respect to the effect of current density and electrolyte temperature. The film is composed of a boron-containing outer layer and a boron-free inner layer with disc-like crystals present at the interface. The thickness of the film formed at constant current density up to an identical voltage, decreases with increasing current density. The thickness increases remarkably with elevated temperature. The transport number of Al3+ estimated from the thickness ratio .of the cuter to the inner layers is 0.4 when the film is formed at the current density of 20 Am-2 at 60°C. It increases slightly with increasing current density and decreases significantly with increasing temperature. Content of boron in the outer layer increases 1.5 times when current density .increases 10 times. These changes in film structure and composition with electrolysis conditions must have a significant role in the determination of electric properties of anodic alumina films as a capacitor material.IntroductionThe growth of anodic alumina film in ·a neutral electrolyte proceeds at both film/electrolyte and film/substrate interfaces giving a duplex structure. The oxide layer formed at the former interface includes electrolyte anions while a-pure alumina layer is formed at the latter interface. The thickness ratios of each layer respectively represent transport numbers of Al3+ and 0 2 - (1). The film thickness and the incorporated anion content as well as transport numbers of both ions must affect the dielectric properties of the film as a capacitor material. However, the correlation between film structure and electrolytic conditions is not fully understood (2). For the further clarification of anodic film growth mechanism, more detailed characterization of anodic films in relation to electrolytic conditions is advantageous. In the present paper, therefore, the effect of current density and electrolyte temperature on the microstructure and composition of anodic barrier films formed in a neutral borate solution was studied. The films were characterized by direct observation using transmission electron microscopy (TEM) and depth profiles of constituent elements obtained by secondary ion mass spectroscopy (SIMS)."

Jan 1, 2000

By G. L. Liu

"Deformation Banding ( DB ) in cold rolled mild steel has been experimentally established by microstructure investigation. Deformation banding model includes such deformation mode when it is applied to rolling texture simulation. The cause for the occurrence of deformation banding is the reduction of the total work for plastic deformation through a relaxation of the deformation constraints. In the first DB model, all grains are assumed to band from the first deformation step. Such an unrealistic assumption has been eliminated in the new model by the introduction of a banding criterion based on an energy minimizing approach. The prediction is closer to the measured texture by applying banding criterion and setting critical resolved shear stresses (CRSS) ratio for { 110 } and { 112 } slip modes to 0.85.IntroductionBased on the continuum theory of plastic flow and deformation mechanism of crystallographic dislocation slip, Taylor's FC ( Full Constrain ) theory [1] has been widely used in texture modeling. As the process of cold rolling of sheet materials produces a microstructure consisting of elongated or equiaxed flat grain or cell, the ""lath"" and ""pancake"" relaxed constraints ( RC ) models [2, 3] were introduced as the successful improvements over the classical FC model. It has been also recognized that crystals may split into different orientations during deformation and the term deformation banding is used to describe such deformation processes [4, 5]. Lee et al. [6, 7] pointed out that the success of the RC theory in predicting textures depends on the physical processes of deformation banding. They developed so called Deformation Banding ( DB ) model by considering DB in the longitudinal plane to be accounted for by the RC method and allowing DB in the rolling plane. DB model was applied to simulate the texture development in bee case [8], the predicted bee rolling textures are in reasonable agreement with the measured textures. In the first DB model, however, all grains are assumed to band right upon the first deformation step. A banding criterion was formulated [7] which states that DB will occur if the work used in DB model is less than that in RC model. Such criterion has been incorporated into the original DB model for texture simulation and is referred to as DBC ( Deformation Banding Criterion ) model."

Jan 1, 1998

By Pengfu Tan

A thermodynamic model of KIVCET lead smelting process has been developed. The model has the capability to predict the distribution behaviors of Pb, Zn, Fe, S, O, As, and heat balance in KIVCET direct lead smelting furnace. The compositions of lead bullion, matte, slag and gaseous phases, and heat balance are calculated. The effect of the ratio between oxygen and feed on the chemistry of the smelt and heat balance of the coke checker has been simulated and discussed. The thermodynamic model also helps to understand the tapping issue of the lead bullion. In this paper, some applications of this model in the industry have been presented.

Jan 1, 2006

By Florian Aurelian, Mihai Popescu

"It will be tested four types of “geochemical barriers”. All those mixtures were contacted with mine waters containing uranium, radium and heavy metals. The loading capacity was determined. The optimum mixture was determined and its efficiency was tested within an uranium areal, where the activity was stopped. It was determined the possibility to recover the radioactive elements and the heavy metals from the investigated barriers.IntroductionThe paper presents the results concerning the performances of some “geochemical barriers” used for the decontamination of mine waters from uranium mining sites, which were tested in lab and in situ.ExperimentalThe research activity was carried out in lab and on the site.In the lab a module was constructed in order to follow up the uptake capacity of the “permeable reactive geochemical barriers” used to remove the radiolelements from the contaminated waters originated from the uranium mining industry. The barriers, which were used, are made of cheap natural materials, which can be easily got (wood chips, peat coal, sawdust, iron span, steel and zeolitic tuff). The following types of barriers were tested:•, 1st barrier: peat coal, sawdust, zeolite on weight ratio of 1/1/1;•, 2nd barrier: bentonite, sand, wood chips, peat coal on weight ratio of 1/1/1/1;•, 3rd barrier: iron span, steel, sawdust, peat coal on weight ratio of 2/1/1;•, 4th barrier: iron span, steel, sand, firry wood chips on weight ratio of 1/1/1.Lab researches concerning the uranium uptake capacity of the above described “reactive barriers” pointed out that the 3rd mixture (iron span, steel, sawdust, peat coal on a ratio of 2/1/1) didn’t reach the maximum uranium uptake capacity not even after eleven contact stages (the uptake capacity being of 70.6 mg U/ kg of mixture) and the mixture of peat coal, sawdust and zeolite has an uranium uptake capacity of 26.6 mg U/kg of mixture and becomes saturated after four contact stages.Each one of the components involved in physical-chemical processes of sorption, reduction and precipitation, will determine the diminution of uranium and other metals contents upstream the permeable reactive barrier."

Jan 1, 2008

By W. L. Dalmijn

Glass recycling in the Netherlands &apos;has grown fr.om 10.000 to 300.000 tonnes per annum. The various advantages and problems of the glass cycle with reference to the state of the art in the Netherlands is given. Special attention is given to new technologies for the automated sorting of cullet with detection systems. In Western Europe the recycling of glass has, become a success story. Because of this, the percentage of ,glass cullet used in ,glass furnaces has increased. To meet the quality demands of the glass industry, automated sorting for the removal of stones, non-ferrous metals and other impurities ,had to be developed and incorporated in glass recycling plants. ;In Holland, Germany and other countries, the amount of glass collected has reached a level that colour-sorting becomes necessary to avoid market saturation with mixed cullet. Recently, two systems for colour-sorting have been developed and tested for the separation of bottles and culletin the size .range of 20 -50 mm. With the increased capacity of the new glass recycling plants, 120,000 -200,000 tpy, the quality systems have also to be improved and automated. These quality control systems are based on tile automated sorting technology developed earlier. for the glass recycling plants. The data obtained are automatically processed and printed. The sampling system and its relation to the theory of Gy will be described. Results of both developments in glass, recycling plants will be described.

Jan 1, 1995

By Janene Barter

Telfer Gold Mine treats both gold/copper oxide and sulfide ores in a remote location in the Great Sandy Desert, Western Australia. Currently, the oxide gold ore is treated in a conventional CIL circuit by blending the low and high grade copper ores to minimise cyanide consumption and allow smooth operation. The sulfide ore is treated through a flotation circuit to produce pyrite and copper concentrates. The pyrite concentrate is treated in the CIL. Copper concentrate is stockpiled and sold to a smelter for further processing. In recent times, as the depth of the pit has increased the copper head grade has also increased, to the point where the ore was becoming uneconomical to treat. In addition, it was desirable to reduce the amount of cyanide reporting to the tails dam both from an environmental and economical viewpoint. Newcrest Mining Limited engaged GRD Minproc Limited to evaluated a process to reduce the amount of cyanide entering the tail dam with consideration given to copper recovery. From this investigation, the Sulfidisation, Acidification, Recycle and Thickening (SART) process was selected. A detailed testwork program for SART was undertaken with the objective to design and construct a SART plant at Telfer. This paper outlines how the SART process was chosen and summarises the testwork that led to the design of the SART plant. It also touches on some of the important issues for designing this type of process.

Jan 1, 1998

By Veneta Groudeva

A pyritic ore containing zinc, lead and copper as? the relevant primary sulfide minerals, .as well as gold and silver finely disseminated in the sulfide matrix, was? leached in percolation columns. Each column contained 30 kg of ore crushed to minus 10 mm. Firstly, zinc and copper were efficiently leached by means of chemolithothrophic bacteria? in acidic sulfate bearing medium. Zinc was leached more rapidly than copper but the final extractions of these metals were similar (about 75% in 300 days). A part of the galena was oxidized to the. insoluble lead sulfate during the leaching. The pyr:ite was, however, relatively slightly attacked. The ore was then leached by means of FeC11 - HCl solutions both in the presence and in the absence of bacteria to solubilize the lead. The chemolithotrophic bacteria grew in media containing both chloride and sulfat~ ions and maintained a high ferric to ferrous ion ratio in the percoiating solutions. The chemical leaching was, however, more efficient since ft was possible to carry it out at higher chloride ion concentrations. About 10% of the lead was leached in this way in 90 days. Finally, the ore was leached by thiourea in the presence of a gold-oxidant (oxone) to extract the gold and silver. Over 60% of the gold and over 55% of the silver were extracted from the ore in 150 days, while. the extractions of these precious metals from an untreated ore sample were lower than 25%.

Jan 1, 1991

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By S. H. Amini

The effects of CaF2 and ilmenite on dissolution rate and diffusivity of CaO in calcium alumino-silicate based slag in a temperature range of 1500 ? 1600 ºC were studied by using the rotating disk/cylinder technique. The effect of rotation speed on the rate of dissolution in the base slag indicated that mass transfer in liquid slag played a significant role in controlling the dissolution. At a constant rotation speed, the effect of 5 wt% addition of fluxes tothe slag on the dissolution rate was investigated at various temperatures. While CaF2 had the highest effect, addition of ilmenite increased the rate of dissolution significantly. The diffusivity of lime in these slags was quantified using the dimensionless mass transfer correlations for rotating disk/cylinder in the melt. The diffusivity values were deduced using the data on dissolution rate and solubility of lime in the slags. The measured diffusivity in base slag at 1500 C was found to be about 1.32 10-5 cm2/s and increased to 3.07 10-5 cm2/s at 1600 °C. Addition of 5wt% CaF2 increased the diffusivity by a factor of 3 to 5, while 5wt% ilmenite increased the diffusivity by a factor of 2 to 3 in the temperature range of 1500 to 1600 ºC. The two examined fluxes reduced the activation energy of diffusion.

Jan 1, 2006

By Dale T. Peters

In the United States, the United Kingdom and numerous other countries, copper has long been the plumbing material of choice. This has been the case since the late 1920s in the United States and since World War II in the United Kingdom. However, in recent years the plumbing tube market has caught the eye of the chemical industry, and several plastic resins have been introduced to the marketplace as substitutes for copper in household plumbing systems. One of these, polybutylene tube, had so many failures in the United States that a class action law suit was filed, and the manufactures of this product were forced to create a trust fund of nearly one billion dollars to repair damages caused by their product. Chlorinated polyvinylchloride (CPVC), in rigid pipe form, on the other hand, has been mechanically acceptable albeit its recent introduction precludes the test of time enjoyed by copper tube in this application. This paper reviews the State of California&apos;s portrayal of copper&apos;s environmental effects and will be largely based on the data and information assembled by the Copper Development Association Inc. in its presentation to the State of California in August, 1998 in response to the State&apos;s Draft Environmental Impact Report for Chlorinated Polyvinyl Chloride (CVPC) Pipe for Use for Potable Water Piping in Residential Buildings. The paper is intended for use as a model for the use of other copper organizations and individuals in responding to similar situations.

Jan 1, 1999

In this study, the method of chemical co-precipitation?reduction?diffusion was developed for the preparation of magnetic SmCo5 alloy. In the chemical co-precipitation process, the effects of solution pH, the reactant concentration, the dispersant on the process were investigated. The optimum conditions of the process were determined, and the SmCo5 alloy oxide precursor particles with fine crystalline structure, narrow size distribution was obtained. Then, by reduction-diffusion treatment of the precursor particles, the SmCo5 alloy with high quality was produced. It is anticipated that the co-precipitation-reduction-diffusion is a novel method available for SmCo5 alloy production.

Jan 1, 2006

By Othon do Rêgo Monteiro Neto

[The present study has investigated the extraction of copper from a chalcopyrite flotation concentrate using an adapted strain of Thiobacillus ferrooxidans and shake flasks, tank leaching and Warburg respirometer techniques. From the shake flask experiments, the activation energy and the frequency factor have been determined to be ?ka = 59.4 kJ and A = 3.3 x 105 S-1, respectively. The temperature coefficient was found to be Q10 = 2.2 in the range of 20 to 35°C. It was suggested that the reaction mechanism of chalcopyrite leaching by T. ferrooxidans involves the formation of an activated complex. whose thermodynamic values have been calculated to be ?G? = 92.1 kJ, ?S? -148.8 J K-1 and ?H$ = 47.8 kJ. The maximum volumetric oxygen mass transfer coefficient for the reactor leaching was found to be achieved by using an optimum air flow rate of 1970 cm min l at a rotational frequency of 1000 min-1. The highest copper extraction in tank (reactor) leaching experiment was 86.8% after 17 days of leaching, while in the sterile runs the corresponding copper extraction was only 40.1%. The copper extraction was suggested to be diffusion controlled. The power requirement of the aerated reactor was calculated to be Pg = 2.02 watts. During leaching, the oxygen saturation concentration was found to be C* = 6.70 mg dm-3. Using the gassing out method the critical oxygen concentration was assessed to be CCrit 0.05 mg dm 3. From the Warburg experiments, the kinetic parameters of the Monad equation were derived with a new evaluation technique to be Vmsp = 9.0 µm3 02 min-1 mg protein-1 and K = 7.4% pulp density for the effect of substrate concentration. The order of reaction and the overall reaction rate constant were determined from the modified van&apos;t Hoff plot to be n = 0.0 and k = 1.49 p dm3 02 min-1 mg Protein -1 for the chalcopyrite concentrate oxidation by T. ferrooxidans. On the basis of this experimental work, a preliminary flow sheet has been proposed for the bioextraction of copper from flotation concentrates.]

Jan 1, 1985

By Xiaofei Guan, Adam C. Powell, Uday B. Pal, Srikanth Gopalan

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM– Inconel inert anode current collector for production of Mg and O2 at 1423K. The electrochemical performance of the SOM cell was evaluated by using various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scans, and potentiostatic electrolysis. The effects of Mg solubility in the flux on the current efficiency and the YSZ membrane stability during SOM electrolysis were discussed and examined through experiment and modeling. The electronic transference number of the flux were measured to assess the Mg dissolution in the flux during SOM electrolysis. A negative correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed.

Jan 1, 2014

By A. Lackner

Using the CFD software package FIRE, the smelting process inside a cyclone reactor is modelled. The fluid flow is calculated 3 dim., using different turbulence models. The effects of design parameters (length and diameter of the cyclone, concentrate feeding tangentially or from the top,..) and operating conditions are investigated. Single particle traces illustrate how to increase particle retention time before the particles reach the liquid film flowing down the cyclone wall. Moreover a two phase flow approach is developed, based on the "Discrete Droplet Model". The position, velocity, diameter and temperature of each reacting particle is described. The results show the advantages of top concentrate feeding, large height/width ratio of the tuyeres and increasing number of tangentially gas inlets.

Jan 1, 1995

By Joachim Ulrich

The spreading and splashing behaviour of single tin, lead, copper, aluminium and steel droplets impacting on a solid surface were experimentally examined. The droplet impact was observed using a high speed video imaging technique. The onset of splashing and the mass of the secondary droplets of impacting tin and lead droplets was quantified by the weight difference of the droplets before melting and the splat after the impact. The spread factor and the mass of the secondary droplets in dependence of the impact velocity is shown for different droplet materials, initial droplet diameters, target temperatures in ambient air and inert gas atmosphere. An empirical found correlation predicting the transition from spreading to splashing is presented by means of dimensionless numbers.

Jan 1, 1999

By B. M. Satish

The aim of the present work is to study the effect of annealing on the vibration damping capacity of high-chromium (16%) ferromagnetic steel. The alloys were prepared from raw materials of 99.9% purity melted in a high frequency induction furnace under high vacuum. The samples were heat-treated in vacuum at various temperatures (800 to 1200°C) for 1 hour followed by slow cooling (120°C/h). The inverted torsional pendulum method was used to evaluate the vibration damping capacity. The results indicated that the vibration damping capacity of the alloys is influenced by annealing and there exists a critical annealing temperature after 1000°C. The damping capacity increases quickly below the critical temperature since the magnetic domains move more easily.

Jan 1, 2009

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at AVR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. In the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003

By Michael Sheedy

Sulfuric acid is widely used as an electrolyte for the electrorefming and electrowinning or metals. Impurities in this electrolyte are controlled by continuously bleeding solution from the tank house. In addition to the contaminant these bleed streams contain high levels of sulfuric acid and the metal being recovered. Subsequent treatment of these bleed streams often requires neutralization which generates large volumes of solid waste. Absorption resin technology employing a novel ion exchange technique known as Recoflo® allows the separation of the mineral acid from dissolved metal salts. The recovered acid is suitable for recycle back to the electrolyte circuit. The metal salt and other contaminants leave the process free .of the sulfuric acid. In this process, known commercially as the APU®, ion exchange resin is used to sorb sulfuric acid while excluding the metal salts. The purified acid is then removed by washing the resin with water. The process has been extensively used for the recovery of waste pickling acids in the steel industry and anodizing solutions in the aluminum industry. In the mining and metallurgical industries the process has been successfully evaluated for the separation of excess sulfuric acid from copper electrolytes, the removal of magnesium and manganese contaminants from zinc electrolytes, and nickel and copper from copper electrolytes. A full scale installation on a copper refinery bleed stream at Palconbridge's Kidd Creek plant in Timmins, Ontario has now been operating successfully for more than 1 year while pilot field trials have been successfully completed on other applications.

Jan 1, 1997