Search Documents

By Roald Ysteboe, Finn Olesen

"Elkem has developed a process that utilizes SPL as a raw material for pig iron production. This process will be demonstrated in industrial scale during 2008 and 2009. The process developed produce iron, and the reduction material used, is the carbon present in the SPL. The iron source could be either virgin iron ore or waste/recycled material from the steel industry. The SPLrefractory and bath material is dissolved in the slag produced. The slag is designed so that any leaching of environmentally dangerous elements is minimized. This process can in addition to SPL, consume other types of waste derived from the primary production of aluminium. Elkem intends to supply this demo project with SPL and other waste products from external sources, domestic as well as international ones.IntroductionSpent Pot Lining (SPL) is generated when an electrolytic cell for producing aluminium is taken out of service and the refractory and carbon lining is removed from the steel potshell.The yearly generation of SPL world wide is exceeding 500 000 tonnes. The major amount of this quantity is stockpiled or land filled, unprocessed.SPL contain large amount of water soluble fluorides and some amount of cyanides and is classified as hazardous waste in most countries."

Jan 1, 2008

By Sylvie C. Bouffard

The need for a better understanding of the heap biooxidation pretreatment of pyritic refractory gold ores has prompted us to develop a rigorous mathematical model of the process. The hydrological structure of the model takes the form of lateral stagnant pores in contact with a uniformly distributed gas stream and connected to vertical plug flow channels, as suggested by the results of an independent study of column hydrology. A model of pyrite oxidation kinetics was derived based on electrochemical leaching theory and the results of potentiostatic stirred tank and column tests. The growth rates of attached and planktonic iron- and sulfur-oxidizing cells are modeled with separate Monod expressions over three separate temperature ranges corresponding to mesophiles, moderate thermophiles, and extreme thermophiles. Isothermal column tests validate the model simulations. Excellent fits of several leaching indicators (potential, extent of sulfide oxidation, iron concentration, cell numbers) reveal the rate-limiting step to shift from particle kinetics to oxygen gas/liquid mass transfer with increasing temperatures and pyrite head grades. Competition for oxygen between sulfur- and iron-oxidizing microorganisms lowers potentials and slows down pyrite oxidation. This modeling tool may assist engineers in the design and operation of heaps to give more complete gold liberation in a shorter time.

Jan 1, 2003

By H. Y. Cheng

A pulse column solvent extraction system was evaluated as an alternative to mixer-settlers for the separation and purification of rare earths. The column tested had an inside diameter of 44.5 mm and had 36 sieve plates with a free area of 25%. Pulsing was provided pneumatically using a solenoid valve controlled by a timer so that both pulse amplitude and frequency could be varied. Feed to the column was a mixed rare earth chloride solution containing 10 g RE L-1. The extractant was 5% Ionquest® 801 in Shellsol 2037 diluent. Hydraulic performance of the pulse column was excellent with no propensity towards stable emulsions or crud formation under normal operating conditions. The column was operated in organic-continuous mode with flow rates chosen so that yttrium and the heavy rare earths were extracted with high efficiency while the light rare earths were rejected. Yttrium extraction varied from 83 to 99.2%. Concentration profiles were measured in both the aqueous and organic phases, and, from this data, the height of a transfer unit (HTU), the mass transfer coefficient (Kxa) and the continuous-phase axial dispersion coefficient (Ey) were computed. The HTU ranged from 17-92 an which is within the range of values reported for other (non rare earth) pulse column systems.

Jan 1, 1992

By Vladyslav M. Sokolov

The cost effective and environmentally friendly recycling technology was developed and tested. It enables utilization of the fine nickel-base superalloy scrap in a form of heavily oxidized scarfing granulates. The process of granulates generation was discussed in details. Their properties were investigated. The results of literature search showed anticipated sufficient improvement of the properties of cast iron by its alloying with the elements from the scarfing granulates. The novel alloying approach is based on the two stage reduction operation. Firstly thegranulates were partially reduced in a solid state by their exposure with powdery carbon at the range of 1550 ? 1700°C. Then the gotten product was efficiently introduced into liquid iron since it has a form of fine natural agglomerates for arranging the optimal conditions for reduction of the granulates. The thermodynamic evaluation demonstrates higher reduction efficiency of carbon and silicon dissolved in iron than of the same elements in a form of the separate phases. The considered process partially provides itself by energy since the reaction of reduction of the chromium oxide by silicon dissolved in liquid iron has exothermal character. The mostly complete extraction of Ni was received. The sufficient reclamation of Cr was gotten at the same time.

Jan 1, 2006

By Bruce Cavender

Managers are frequently faced with the decision to perform a task or manufacture an object in-house or to hire an outside vendor to perform the function. Outsourcing decisions are usually driven by economics: work is outsourced if it can be completed at a lower cost or in a shorter time than it can in-house. A technique termed incremental analysis can be used to make this decision. Incremental analysis examines the financial impact of outsourcing decisions as a function of the firm's fixed and variable operating costs. To use this tool, individual components of production cost are identified as being either constant or varying with levels of production activity. The assignment of cost type can be made in several ways: though analysis of historical operating data, understanding of individual expense types, and so forth. Changes in fixed and variable costs resulting from each potential course of action are explicitly identified to project the financial outcome of each alternative. The alternative having the greatest positive impact on profit is selected for implementation. By using the fixed- and variable-cost framework, the analysis is conceptually straightforward and substantially simplified. Production managers can therefore use incremental analysis as a tool for fast economically beneficial decisions on a real-time basis.

Jan 1, 1999

By Abhoy Mukherjee

The Luanshya Smelter is a traditional Reverberatory Smelter which once worked with up to three coal-fired reverbs, and now operates one Reverb and one hot Peirce- Smith Converter, projected to produce approximately 42.000 tons per year of copper anodes. The aim of this study is to select a smelting technology which best fits the upgrading of the Smelter, such that low capital and operating costs are achieved for the projected design production capacity of 60.000 tpy, limited by the available supplies of concentrates. An equally important requisite is the compliance of present and future environmental regulations, which determines the need to install and Acid Plant to treat the smelter primary gases. In the process selection study, the following technologies were analyzed, at a Conceptual Engineering level: the Oxy-fuel Burner Reverb, the Teniente Converter, the CONTOP Cyclone Smelting Reactor, and further, the Ausmelt Furnace, the engineering of which was provided by the proprietary firm. The engineering of the other processes was developed by INDEC, which also integrated the comparative analysis of the four options. The analysis of a comprehensive set of technical factors, including integrated smelter metallurgical models, together with the evaluations of economical features, led to the selection of the CONTOP Smelting Technology for the modernization of the Luanshya Smelter.

Jan 1, 1999

By Pranav Deshpande

The wear behavior of metal matrix composites differs from that of the monolithic metallic counterparts because composite materials have multiple constituents in their structures and these constituents wear at different rates. It was observed that under low wear stresses, abrasive wear prevailed. As the wear stress increases, pullout of reinforcement occurs and both abrasive wear and wear due to pullout contribute to the overall composite wear. A model of wear taking into account both types of wear has been developed. A critical pullout wear stress was suggested for each composite. Below the critical wear stress, no pullout of reinforcement occurs. It turns out that the critical wear stress simply equals to the ratio of the interfacial strength between the matrix and the reinforcement to the friction coefficient between the reinforcement and the wear counter surface. The critical wear stress is independent of the particle size of the reinforcement. From data on wear of 53% WC composites, the equation of wear for 32% WC composites was obtained. Experimental results agreed well with the predicted wear rate of this composites. This provides an excellent verification of the wear model developed by Lin and Deshpande. Wear data from Modi et al. in the literature were also perfectly fitted with the model.

Jan 1, 2006

By T. I. Arbuzova

The present work presents the original data concerning using a high pressure torsion method and a shock wave loading technique to produce compact oxide nanomaterials and investigations of the effect of severe plastic deformation on a microstructure, crystal lattice and stability of these compounds. This allowed us to compare two ways of deformation action that can be characterized as quasi-static and dynamic effect, correspondingly. Particular attention was paid to a stoichiometry and surface composition changes upon severe plastic deformations. A procedure for studying chemistry of the oxide nanomaterials by means of nuclear microanalysis and Rutherford back scattering has been worked through. For surface studies the X-ray photoelectron spectroscopy has been used. It was shown that both distortion methods permit to produce massive nano-scale oxide materials from the coarse-grained powder during a single technological cycle. Bulk nanocrystalline materials based on LaMnO3, TiOy and ZrO2:Y2O3 were obtained by the quasi-static deformation technique. Nanoscaled ceramics of CuO, Mn3O4 and LaMnO3 were produced by the dynamic deformations. The density of the nanoceramics comes to 99%. Size effects and specific imperfection of the nanoceramics obtained lead to a set of particularities of physical properties.

Jan 1, 2006

By R. Padilla, M. C. Ruiz, R. Villa

"Bismuth is an impurity in copper minerals where it occurs mainly as the mineral bismuthinite (Bi2S3). In smelting of copper minerals, most of the bismuth reports to the white metal, as a result, a substantial amount of bismuth accompanies the copper to the electrorefined cathodes. Thus understanding the behavior of Bi2S3 at high temperatures is crucial to eliminate bismuth before electrorefining. In this paper, some experimental data on the decomposition/volatilization of bismuthinite in nitrogen- oxygen atmospheres is discussed. The results indicated that in nitrogen atmosphere, bismuth volatilization occurs through a fast decomposition of bismuthinite to metallic bismuth and sulfur with subsequent volatilization of bismuth in the range 850-1100 °C. Similarly, in the presence of oxygen, bismuthinite decomposes to bismuth too, followed by oxidation to the non-volatile bismuth trioxide at temperatures higher than 750 °C. Both, temperature and partial pressure of oxygen affect significantly the bismuth volatilization and the oxidation rates.IntroductionCopper sulfide minerals are the major source for the production of metallic copper by pyrometallurgical processes, which are the dominant processes in the production of copper by selectively oxidizing the sulfide sulfur to SO2 and the accompanying iron in the concentrates to iron oxide, which can be conveniently removed as a stable slag.Generally, copper concentrates contain some deleterious minor elements such as arsenic, antimony, bismuth and lead, which are present as sulfides. These elements depending on their concentration may originate problems in the copper smelting processes and they can ultimately lead to a final copper product with unacceptable high levels of impurities.During the treatment of these copper concentrates by smelting, the impurities generally distribute themselves in the condensed and gas phases and they are eliminated mainly through the gas phase [1-3]. Thus, smelter off gases contains substantial amounts of volatilized impurity elements. For example, in the case of bismuth, the estimated distribution of bismuth in flash furnace smelting [2] was 15 % in the matte, 5 % in the slag and 80 % in the gas phase, and recently, for Outokumpu flash smelting Davenport [3] reported the distribution of bismuth as 30-75% in matte, 5-30% in slag and 15 -65 % in the off gas."

Jan 1, 2011

By R. M. Moon

Neutron scattering has played a crucial role in advancing our understanding of rare-earth materials. It has provided a detailed description of the rich array of exotic magnetic structures; it has confirmed the accuracy of theoretical wave functions for the 4f electrons; and it has provided fundamental data on the collective magnetic excitations in these materials. The fundamental property of the neutron which has been exploited in this work is the magnetic interaction which exists between the magnetic moment of the neutron and atomic magnetic moments on individual rare-earth atoms. This interaction produces scattering of neutrons in a manner closely analogous to the scattering of X rays by atomic charge distributions. In a material exhibiting long-range magnetic order, Bragg diffraction peaks will appear at scattering angles determined by the periodicity of the magnetic structure. The Bragg intensities are determined by the magnitude and relative directions of the atomic moments. The rare-earth metals and alloys are characterized by sinusoidal modulation of magnetic moment components which can be combined in various ways to produce a variety of magnetic structures. The periodicity of these modulations is frequently not related simply to the underlying periodicity of the chemical structure. The major features of these structures are explained by the combined, and sometimes competing, exchange and crystal-field interactions. At a more fundamental level, neutron diffraction also gives information on the spatial distribution of a magnetic moment in a rare-earth atom. This moment comes from the 4f electron shell, and accurate measurements of the neutron scattering amplitudes have been used to check the accuracy of atomic wave function calculations for the 4f electrons. It was found that relativistic Dirac-Fock calculations are in excellent agreement with the experimental results. Collective excitations of ordered magnetic systems are described in terms of spin waves, which are sinusoidal modulations in space and time of the direction of the ordered moments. Inelastic neutron scattering is used to measure the energy and wave length of these collective excitations. Analysis of these data gives direct information on the interatomic interactions responsible for the magnetib properties of these materials.

Jan 1, 1992

By F. Nava-Alonso, O. Alonso-González, A. Uribe-Salas, R. Pérez-Garibay

"Cyanidation is the most used method to recover gold and silver from their ores. In this process, other metals besides gold and silver may sometimes dissolve and interfere with the efficiency of extraction. Copper is one of those metals, reaching concentrations as high as 1000 mg/L in some cyanidation plants, making difficult the extraction and purification processes, and increasing the operating costs.This preliminary work was intended to study the feasibility of using amines to form a precipitate and to eliminate copper from a synthetic solution containing high copper and cyanide concentrations, as is the case of some cyanidation effluents. The solid formed is removed from the solution using conventional filtration techniques. Seven amines were evaluated at different pH values and amine additions. Up to 90% of copper present may be removed at the natural pH of the effluent (alkaline). The remaining copper would permit to recycle the solution back to the cyanidation process. IntroductionCopper is generally considered the most problematic metal in gold leaching due to the rapid formation of copper cyanide complexes when some readily-soluble minerals are processed (e.g., azurite, malaquite, cuprite, chalcocite and bornite). The copper solubilization as cuprous cyanide complexes leads to a significant economic penalty in terms of excessive cyanide consumption and high cost for cyanide elimination. When activated carbon is used to recover gold and silver, the copper-cyanide complexes decrease the efficiency of the process because of the competition of the cuprocyanides with the aurocyanide for the adsorptive sites on the activated carbon (Rees and Deventer, 1999).Several techniques have been developed to attempt to overcome the problems caused by the copper presence in cyanidation solutions, notably: acidification-volatilization-regeneration (AVR), ion exchange-electrolysis or solvent extraction-electrowinning (Lu et al., 2002). In this work the use of some amines is proposed to remove the copper-cyanide complexes by precipitation of a copper-cyanide-amine solid. The process was evaluated for different amine additions and pH values, using copper-cyanide synthetic solutions of composition similar to that presented by some cyanidation plants with high copper."

Jan 1, 2008

By Yong Hwan, Wang Jian-Jun, Cai Jiu-Ju, Chen Chun-Xia

"The quantity of residual-heat and its recovery in some Chinese sinter plants are investigated. The main factors affecting energy consumption are analyzed using exergy analysis combining energy level analysis. It is indicated that the “gradation recovery and cascade utilize” of discharged gas and sinter residual heat in different temperature is the direction and the available approach to reduce energy consumption of the sinter process. Taking an iron& steel enterprise as an example, the three-ranked scheme of residual-heat recovery is put forward: ?Part of the sinter gas is used for warm-up and dryness; ?The high-temperature part of the cooler and exhaust-heat boiler are actualized as a closed-circuit, which can produce high-quality steam to generate electricity. ?The waste air in low-temperature part is introduced to sintering machine to support combustion. According to the CDQ which can recover the coal heat, the assumption of pot-recovery is put forward to replace the belt cooler. The two equipments of residual-heat recovery are analyzed in the aspect of energy consumption and CO2 reduction.1. IntroductionEnergy consumption in sintering is only inferior to iron-making in iron& steel enterprises, accounting for 10%~20% of the total energy consumption. A lot of residual heat is produced during sintering, and mostly from the sinter ore and waste gas. Sensible heat of hot sinter ore and discharged gas have accounted for 60%[1] (equals to 40 kgce/t-ore), which are the key point of sintering waste heat recovery. Discharge gas of sintering is mostly composed of flue gas deriving from sinter bed’s combustion, and the content distribution of H2O and O2 and the temperature of the gas along the length of belt-type sintering are shown in Figure1[2,3]. Currently, the sensible heat of hot sinter ore is mainly recovered by circular cooler and cooled by blasting air: the temperature of cooled discharge gas brings down from 350? to about 100? along with the decrease of sinter ore temperature. It is significant to recovery and reuse the waste heat as 4000~6000m3 discharge gas per ton of ore can be produced"

Jan 1, 2008

By Xiangjun Zuo, Lifeng Zhang

"Printed Wiring Board (PWB) is a platform upon which microelectronic components such as semiconductor chips and capacitors are mounted. It is also called printed circuit board (PCB). In the PWBs, the organic substances are approximately 72%. The main composition of organic substances in PWBs is ethoxyline resin bromide or ethoxyline resin chlorinate. Depending on the different application and design of the PWB, various metals may be used in the manufacturing process, including precious metals such as copper, lead, silver, gold, platinum, and toxic metals such as mercury, cadmium, barium, gallium, cadmium, lead, bismuth. The current paper reviewed the recycling process for waste PWB materials, including mechanical recycling, combustion for energy recovery and different pyrolysis processes, such as vacuum pyrolysis, atmospheric inert pyrolysi and flux pyrolysis process, and hydrometallurgical recycling process.Backgrounds of Electronic ScrapsProduction and use of electrical and electronic equipment (EEE), such as TV sets, computers, mobile phones and many other daily-life items, have dramatically increased over past decades, while the lifespan of many products becomes shorter"". The rapid innovation in technology in past decades has resulted in availability of cheaper and better electronic products in the market. Thus the production of waste electrical and electronic equipment (WEEE) is also increasing, with estimates of 20-50 million tons per year being generated worldwide2), and it is a problem that governments and policy makers have to handle W). WEEE is also called ""E-wastes"" or ""E-scraps"". From the points of view of recycling and the valuable materials in the used EEE, ""E-scrap"" is more appropriate than ""E-waste"" since the used EEE are not real wastes to be dumped but had much benefit to recycle. In the US, it was estimated that over 315 million computers between 1997 and 2004 and 185 million computers between 2004 and 2007 would become obsolete 5). E-scrap is the fastest-growing part of the U.S. garbage stream 6). It is estimated that only 20% of the E-scrap generated within the US is currently collected and treated, with as much as 80% being unaccounted for7)."

Jan 1, 2011

By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By Djalma Souza, Rubén Sánchez, Regina Maria Pinheiro, Carlos Maurício Fontes Vieira, Sergio Neves Monteiro

"This work has for objectives to characterize a waste generated in the form of sludge during the treatment of the effluent of a paper making industry and to evaluate the effect of its incorporation up to 10 wt.% on the properties of a clayey body used for brick production. For the characterization of the waste the following techniques were used: X-ray diffraction, X-ray fluorescence, differential thermal analysis and termogravimetric analysis with mass spectrometry. Specimens were prepared by uniaxial pressing at 20 MPa before firing at 750 °C. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The results showed that, in agreement with the characteristics of the waste, its recycling into red ceramic can contribute to decrease the consumption of fuel during the firing stage. However, the waste changes the physical and mechanical properties, generating a deleterious effect on the water absorption and flexural rupture strength of the ceramic.IntroductionAccording to the Brazilian Association of Pulp and Paper, in the last 10 years, the global production of paper grew 35%. Brazil produced 8,2 million tons of paper in 2004 and held the position of the seventh largest world manufacturer of pulp, with about 9,4 million tons per year [1]. The pulp and paper industry generates effluents that present problems related to their disposal, even after the treatment. Among the solid wastes generated by this industry, the main waste is the primary sludge from the effluent treatment plant (ETP).After the initial treatment the decanted solids go through a dewatering stage, generating the solid form denominated primary sludge. This sludge resembles a paper paste of dark gray color when humid, and clear gray color when dry. This primary waste is composed basically of kaolin, pulp, traces of chemical substances and water. This waste generated in the pulp and paper industry depends on the characteristics of the process and of the employed techniques. It can vary significantly from one industrial unit to another, even in the case that the final products are similar. Its composition is approximately 60% of kaolin and 40% of pulp, and these percentages can vary in some moments as a function of the process [2,3]."

Jan 1, 2008

By Guo Xueyi

The nonferrous metal industry is facing the resource depletion, energy crisis and environmental deterioration. The resource recycling is a correct way to promote the nonferrous metal industry development towards sustainable. To realize the resource recycling, the technical support is most important. In this paper, the techniques barrier for nonferrous metal resource recycling are summarized, the fundamental on resource recycling of nonferrous metals are proposed.

Jan 1, 2006

The Port Kembla Copper (PKC) copper smelting facilities were commissioned during 2000. Numerous difficulties were encountered during the commissioning such as multiple reactor tuyere line failures, absorbing acid tower refractory collapse, and Noranda Reactor and Mitsubishi Converter process control problems. These problems are described along with the actions taken to overcome them. Process development is described particularly for the Mitsubishi Converter and Acid Plant.

Jan 1, 2002

By Ligang Zhang, Wen Chen, Xinghua Liu, Jialin Li, Xiaoyin Liu, Zhenhong Liao

A research-scale fluidization and magnetization roasting device was developed to evaluate a processing option that might offset the complexity and high cost of the conventional magnetization roasting process on siderite. In this study, the operating parameters of the fluidization and magnetization roasting device for siderite were evaluated through cold-flow tests and magnetization roasting tests. The reaction mechanism functions of the fluidized roasting process are revealed with kinetic studies.

Jan 1, 2015

By Ryokichi Shimpo, Akio Fuwa

"In order to elucidate the present status of process-control technology, survey study has been made on the present process control schemes of representative copper smelting and converting processes in Japan. Conceptual control flow diagrams have been deduced and shown on respective functional reactors, i.e. drying, smelting, converting and fire-refining units, where the objective OUTPUT items are correlated to the INPUT variables through respective CAUSE-AND-EFFECT RELATIONSHIPSFuture view has been also discussed on several feasible and desirable improvement and refinement ~n measurements and control system for better copper smelting and converting operations.INTRODUCTIONIn other to seek for the better and efficient operation in copper smelting and converting process, survey study has been first conducted on the present process-control schemes of respective functional unit processes, i.e. drying, smelting, converting and refining unit processes, of representative copper production processes in Japan. Conceptual process flow chart of control scheme has been then deduced where output items are correlated to input items through the respective cause-and-effect relationships.After this survey study, future view has been discussed on the feasible and desirable improvement and refinement in the measurement and control system in these processes. Emphasis has been placed on the better and precise measurements of temperature, oxygen partial pressures in respective furnaces and end-point in converting and refining unit operations."

Jan 1, 1989

By J. C. Agarwal

Rare earth metal alloys are becoming increasingly important, particularly those of neodymium, because of their magnetic properties. This paper will present a generalized approach to the production economics of the metallic rare earth alloys. With appropriate regard for the chemistry of different rare earths and the large impact of economies of scale, it is possible to make fairly accurate estimates of the production costs of other rare earth alloys as well.

Jan 1, 1989