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By Robert L. Stephens

"It can be argued that one of the most important property of any material is cost, since this property detennines the applications for which a material can be considered. Despite growing demand and production for commodity metals such as copper, nickel, zinc, lead, and tin, the cost of these metals has been steadily decreasing in real terms. The only way that metal miners and producers can remain financially viable in the long term is by continuing to lower their cost curve through the implementation of new metals production technologies. This paper reviews technological developments in the production of copper, nickel, zinc, lead, and tin that have or threaten to redefine the cost curves for these metals.DisclaimerThe opinions expressed in this paper the author's, and are not necessarily those held by the author's employer, Cominco Ltd.IntroductionThis meeting will discuss many novel technologies and processes for producing metals and materials with specific properties that will enhance the applications ranges for the material or will allow entirely new applications to be developed. However, in every real-world case, the cost of the new material or process is an important property that determines which applications the material or process can be used in. Other properties that are important depend on the applications.A recent press report (1) discussing the potential replacement of aluminum radiators with copper radiators in pickup trucks and sport utility vehicles provides an interesting example to reinforce the importance of cost in materials selection. In this case, the displacement of aluminum by copper is being considered because of the more favorable heat dissipation characteristics of copper. Heat dissipation has become more important due to the development of hotter-burning V-8 and V-6 engines. For this application, engineers also consider cost, weight, size, durability, and manufacturing process. The report stated that the development by the International Copper Association (ICA) of the ""CuproBraze"" manufacturing process for heat transfer products was an important development. This technology produces 845 radiators that weigh less, are more uniform in quality, and are potentially more compact. They are also expected to cost less in high production quantities than copper units produced in the past, last three to four times longer than soldered copper radiators, and the process also eliminates the use of lead solder from the manufacturing process."

Jan 1, 2000

By P. N. Anyalebechi

A comparative study of the mechanical properties of automotive steering knuckles produced by three different shape-casting related processes has been conducted. It involved the characterization of the tensile and fatigue properties of aluminum alloy A356 knuckles produced by the vacuum/pressure riserless casting (VRC/PRC), pressure counter pressure casting (PCPC), and the hybrid Cobapress (a casting-forging) processes, in accordance with the appropriate ASTM standards. Surprisingly, the knuckles produced by the hybrid Cobapress process exhibited the lowest strength. For example, the average 0.2% yield strength of the Cobapress knuckles was 31 MPa and 40 MPa less than that of the VRC/PRC and PCPC knuckles, respectively. However, between stresses of 150-200 MPa, the fatigue lives of the VRC/PRC, PCPC, and Cobapress knuckles were comparable. But above 200 MPa, the Cobapress knuckles exhibited the lowest fatigue life. The observed differences in the mechanical properties are attributed to the inherently different microstructures of the different knuckles.

Jan 1, 2009

By Sutham Niyomwas

Biomorphic Cellular TiCIC ceramics were produced by vacuum-infiltrating carbon preforms with Ti02 sol and subsequent synthesis by the carbothermal reduction process. The carbon preforms used in the study were obtained by pyrolysis of parawood and neem wood. The effect of infiltration time on the composition and microstructure of the biomorphic TiCIC ceramic was analyzed by X-ray diffractometry and scanning electron microscopy. The biomorphic structure of the TiCIC ceramic is consistent with that of the biotemplate natural parawood and neem wood.

Jan 1, 2008

By A. S. Usrnani

Due to both turbulence and the highly variable geometry of castings, a realistic numerical simulation of the metal flow is prohibitvely expensive with current technology. However, when the chief purpose is to achieve realistic thermal fields a precise How simulation is not necessarily required. In this paper we assume a laminar flow regime and obtain the flow field by solving the incompressible Navier-Stokes Equations using a velocity-pressure segregated semi-implicit finite element method. The free metal surface is predicted by advecting a pseudo-concentration function via the computed How field. This involves an explicit finite element solution of a pure advection equation. The thermal field is calculated by solving the convective-diffusive energy equation by an explicit finite element method using the computed flow field and the location of the free surface. All the advection terms are discretized using a Taylor-Galerkin method. The interface between the metal and mould is modelled using special interface elements. The model is demonstrated by solving practical example problems. The results show that a sharp thermal front is maintained during the course of filling without excessive diffusion. The heat diffusion in the mould can be controlled by varying the metal mould heat transfer coefficient.

Jan 1, 1994

By R. Elliott, H. Bayati

"Effect of time and temperature on microstructure and mechanical properties of an austempered ductile iron, ADI, of composition 3.6%C, 2.6%Si, 0.4%Cu, 0.2%Mn are reported. Xray analysis and. microstructural observations indicate that lowering the working temperature, aging temperature, increases the lifetime of ADI significantly. Results show· that lowering the aging temperature increases the strength and reduces the ductility of ADI. DSC traces for ADI austempered at 340°C are presented. Comparison of the DSC analysis and kinetic measurements demonstrates that the DSC traces can be· used to predict the life time of ADI successfully.IntroductionAustempered ductile iron, ADI, is one of the most significant developments in cast iron technology over the past two decades. Outstanding properties of high yield, ultimate strength, ductility, fatigue and wear· resistance make ADI suitable for a range of applications including gears, connecting rods, crankshafts and agriculture machine components. The austempering reaction in cast iron occurs in two stages, Fig. I, in contrast to the single stage reaction in steel. In stage I the relatively low carbon austenite produced during austenitising transforms into ferritic plates and high carbon austenite, a metastable structure called·ausferrite. The high carbon ailstenite and supersaturated ferrite produced in stage I decompose into ferrite and carbide in stage II: to form a structure similar to the bainitic structure in steel. This behaviour exposes a well-defined processing window, t1 - t2, over which the maximum amount of ausferrite is produced, Figure 1. Whereas the bainitic structure determines the properties of austempered steel, ADI properties are mainly affected by volume fraction of retained austenite (VRA), austenite carbon content (ACC), unreacted or martensite volume fraction (UA V), compositiori and amount of carbides, and morphology of ferritic plates[l,2]. Due to the detrimental .effect of martensite and carbides on properties of ADI, an ideal structure of ADI consists only of ausferrite [l,2]. Thus, it is common to determine the processing window for each austempering treatment in order to identify the optimized austempering time. Decomposition of austenite (stage II) signals the end of the life time for an ADI component, therefore, the aging behaviour of ADI at different working conditions can be studied by determining the t2."

Jan 1, 2000

By Jay S. Gunasekera

Since great emphasis is being placed on the manufacturing science and processing science programs in the Department of Defence and other government research agencies and industries; currently, extensive research on computer aided design(CAD)/ computer aided manufacturing (CAM)/ and computer aided engineering (CAE) is being conducted at Ohio University (OU) . OU has invested over a million dollars in CAD/CAM hardware and software. Design and analysis packages like ALPID, NIKE, STREAM, SHEAR, POLY_FLON, RINGROLL have been developed or modified at OUusing finite element method, finite difference techniques or enhanced slab analysis. Packages like ABAQUS, FLUENT, and NASTRAN have been extensively used.

Jan 1, 1990

By E. J. Peuraniemi

Oxidation of chalcopyrite concentrate and two low-iron copper mattes were studied using a laboratory scale laminar-flow furnace simulating the phenomena taking place in different zones of the reaction shaft of a flash smelting furnace. In the experiments, screened fractions were fed into the furnace and sampled after short reaction time intervals by quenching them into a water film. Experimental conditions included temperatures of 1100 and 1300°C with reaction gas oxygen contents from 21 to 75 vol.%. Samples were analysed chemically for Cu, Fe and S to define removal rate of sulphur. Optical and scanning electron microscopy with EDS-analyser were used to examine the samples. In this paper, oxidation kinetics as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are viewed to closely define the proceeding of the oxidation, and, consequently, to compose a detailed model of dust formation and reaction mechanisms. Data obtained in the experiments broadens the knowledge of physical and chemical phenomena in flash reactions and serves as reference for computer simulations.

Jan 1, 2000

By Katsunori Yamaguchi

A new technique for the removal of tramp-elements from steel scrap has been required from the viewpoint of saving energy and protection of environment. In order to obtain fundamental information on the removal of copper, tin and zinc from molten iron, the extraction method by using of phase separation in the liquid Fe-Pb-C system was investigated at 1453K A mixture of iron, lead and carbon melted in a carbon crucible separates into two phases of lead and iron containing carbon. The compositions on the miscibility gap in' the Fe-Pb-C system are 95A%Fe-4.5%C-0.l %Pb and 99.9%Pb-0.1 %Fe. The distribution ratios of copper, tin and zinc between the lead and the iron phases, Lx=[masso/uX in molten Pb]/(masso/uX in molten Fe), are 2.2, 2.2 and lA, respectively. Seventy percent of copper and tin from iron scrap can be eliminated with comparable lead addition. Gold, silver and palladium are enriched in the lead rich phase, on the contrary platinum and rhodium are more distributed to the iron rich phase than to the lead phase.

Jan 1, 2003

By Dilip Banerjee

"This paper discusses the Advanced Technology Program (ATP)'s support over the last decade to the development and use of process modeling as a tool to address some of the challenges faced by the U.S. metal casting industries. A particular focus will be given to highlight how process modeling can be used to improve the manufacturability of components needed for high performance and critical applications. The challenges associated with the design and production of thin-walled, cast parts with intricate and complex internal geometries will be discussed. Modeling issues associated with the control of the final grain structure in the solidified parts will also be addressed. This paper will describe the advantages of using appropriate mathematical models for designing new alloys for use in various applications.Finally, the role that ATP has played in uplifting the U.S. technological base through partnerships with industry and academia in high-risk research in order to bring to market new and improved products for the broader benefit of the nation will be discussed.ATP's BackgroundIn the 1980s, U.S. industries were losing market share to low-cost, high-quality manufacturers from Asian countries. Corporate leaders and policy makers determined that in order to sustain and grow market share, U.S. industries needed to improve their competitiveness and productivity through product and process innovation. There was evidence that companies were systematically under-investing in leading-edgetechnologies and failing to complete the development of new technologies [l]. There were also arguments in academic circles that pointed to a potential market failure in the area of early-stage technological developments. These concerns provided impetus for creation of the Advanced Technology Program (ATP) within the National Institute of Standards and Technology through the Omnibus Trade and Competitiveness Act of 1988. Through a rigorously competitive, cost-shared partnership with industry, ATP fosters the development and broad dissemination of high-risk technologies that offer the potential for significant broad-based economic benefits to the United States."

Jan 1, 2004

By Corby G. Anderson

Antimony has been utilized by mankind for thousands of years. However, due to recent environmental concerns, antimony is often considered to be an impurity element, Since antimnoy is commonly found in precious metal refractory ore bodies, extraction is essential. The Sunshine Mine in Kellogg, Idaho has recovered antimony from its precious metal tetrahedrite deposits since the 1940's. A plant was initially constructed as a primary antimony source during World War II. This facility also decreased the downstream smelting penalty for the silver copper-lead concentrate and provided an industrial commodity from a potential environmental nuisance.' This paper describes the Sunshine antimony processing- facility. Specifically, the relevant process chemistries involved in concentrate leaching, metal electrowinning, and sodium antimonate production will be discussed. In addition, ongoing areas of research to improve unit operations and treatments implemented to meet environmental' discharge requirements will be covered.

Jan 1, 1992

By A. Shemi

Tungsten carbide scrap (WC–Co) is material generated from the tungsten carbide manufacturing process and worn out or used carbide parts from industry. Tungsten (W) ores contain about 3 wt% WO3 and their W concentrates about 10– 75 wt% WO3. Tungsten carbide scrap typically contains 40–95 wt% W. The high intrinsic value of W and the fact that the least valuable scrap contains more W than the average tungsten ore makes tungsten carbide scrap a worthy material for re-use. This study has investigated the selective dissolution of the cobalt (Co) binder phase, and recovery of tungsten monocarbide (WC) and Co using an acid leach process. The Co component was selectively leached leaving the WC solid particles intact. Further investigation using a complexing agent-aided acid leach process that takes advantage of organic chelating agents that form a soluble tungsten complex in place of the passive insoluble tungsten oxide is envisaged. The optimal dissolution of the Co binder phase using an inorganic acid in conjunction with an organic complexing agent is a novel approach with the potential of reduced leaching times and possibility of regenerating the unreacted organic acid.

By Xuling Chen, Zhiyun Ji, Min Gan, Wenqi Li, Xiaohui Fan, Zhiyuan Yu

"Specularite and vanadium-titanomagnetite are difficult to granulate, and with the increase of their proportions, the permeability of sintering bed is deteriorated together with the combustion velocity of fuel for the shortage of air through the sintering bed, which can lower sintering speed and specific production capacity significantly. The biomass fuel has a higher combustion velocity than coke breeze, therefore the productivity of specularite and vanadium-titanomagnetite ore can be improved remarkably by replacing coke breeze partly with biomass fuel .The results showed that, when the proportion of biomass fuel replacing coke is 40%,the sintering speed and specific production capacity of 35% specularite were improved from 19.06mm/min, 1.33 t/(m2·h)to 21.45mm/min, 1.47 t/(m2·h),and that of 55% vanadium-titanomagnetite were improved from 17.23mm/min, 1.11 t/(m2·h)to 22.80mm/min, 1.44 t/(m2·h). As a conclusion, biomass fuel is effective to strengthen sintering of refractory iron ore.IntroductionThe iron and steel industry of our country has achieved significant development in the recent years. In 2010, the output of steel has reached to 0.627 billion tons. The increasing scale of iron and steel has led to rigorous domestic iron ore environment, and the reserves of hematite and magnetite that have superior sintering characteristics are on the decline with continually exploiting and utilizing [1]. Therefore, the RIO (refractory iron ores) SP (specularite) and VT (vanadium-titanomagnetite) have to be applied vastly. However, the quality of sinters can be deteriorated when utilizing RIO in high proportion due to their poor granulation and metallogenic performances [2, 3]. Generally, the ratio of SP is 3~5%,which should not exceed 10% in our country currently [4]. Though high rate of VT is adopted in PZH steel for a long time, the productivity is obviously low compared with normal sintering [5]."

Jan 1, 2012

By Xie Zhang, Jiang Diao, Xin Qiu, Lu Jiang, Bing Xie, Hong-Yi Li

"Duplex converter process, in which the first converter is used for removing phosphorus from hot metal (De-P), is an important way to produce low P-content and ultra-low P-content steels. In order to improve phosphorization removal and formation of slag with high basicity at relatively low temperature during dephosphorization converter process, effects of temperature, silicon content in hot metal and varied compositions of the De-P converter slag on phosphorus distribution between the slag and hot metal were investigated with thermodynamic calculations and by laboratory scale experiments in present work. Results showed that phosphorus distribution ratio between slag and metal was varied in 10.6~26.6 when basicity of the slag was in the range of 1.5~2.1 at 1370, and the distribution ratio was increased with increasing basicity and Fe10 content in the slag.IntroductionIt is known that phosphorus exists in steel in the form of solid solution, which can significantly improve strength and hardness of steel at room temperature. However, the plasticity and toughness of steel, especially the low temperature plasticity is sharply reduced and leads to high ductile-brittle transition temperature. This phenomenon is commonly known as cold brittleness of steel [1~3]. Hence, phosphorus should be removed as much as possible in the steelmaking process, because it is generally harmful to the iron and steel products."

Jan 1, 2013

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By Shinroku Matsuzaki

Data the measurement sensor installed with spatial distribution on the blast furnace were successively accumulated online from the process computer to the database system over a long period. This is a new system that accurately considers the relation with the installation position of each sensor, and picture computerization of the measurement data was developed. The overall operation state of a blast furnace, which skilled operators can see in their mind?s eye, was objectively visualized as pictorial information.

Jan 1, 2006

By Ari I. Kogut

Impurity minerals in fluorspar ores and concentrates from a deposit in Southern Africa have been studied by reflected light, transmitted light, and cathodoluminescence microscopy. The principal impurities are quartz, calcite, aegirine, apatite, ankerite, magnetite, goethite, and synchysite [Ca(La,Ce,Nd)(C03l2Fj. Cathodoluminescence microscopy was found to be very useful in studying the character of the fluorite and especially for recognizing the presence of apatite and calcite impurities. Fluorite exhibits blue, calcite shows yellow, and apatite has white, light purple, and pink cathodoluminescence. The cathodoluminescent character of apatite varies with its geological environment and position in the orebody. The results of this microscopic study show that phosphorus present in flUorite concentrates occurs principally in binary locked apatite-fluorite particles. Successive fluorite cleaner concentrates contain progressively smaller amounts of locked apatite-fluorite particles. Free apatite has been effectively partitioned to the final tailings.

Jan 1, 1995

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450 °C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Ryszard Prajsnar

During copper production in shaft and flash smelting processes at KGHM Polska Miedz S.A., lead bearing material of sulfide, sulfate, and oxide character is generated in forms such as slime from shaft furnace gas handling systems, converter dusts, and dusts from an electric furnace for copper removal from flash smelting slag. These materials are polymetallic concentrates of Pb, Zn, and Cu, with As, Cl, and Cd as impurities. Shaft furnace slime, containing. about 50% PbS and 15% bituminous substances, is the main lead-bearing material. At the Glogów copper mill, a new plant was commissioned in June 2001 to process 80,000 tonnes per year of lead bearing materials to produce 26,000 tonnes per year of crude lead. The plant consists of a feed conditioning system, three (3) rotary rocking furnaces with a capacity of sixteen (16) tonnes of lead feed fired with natural gas and oxygen-enriched air containing up to 45 vol% O2, and a gas handling system. The gas handling system includes a post-combustion chamber, a gas cooling chamber with Cl neutralization, gas mixing chamber, bag filter, and dry limestone scrubbing system for SO2 removal. The lead-bearing feed is smelted with five (5) wt% Na2CO3 and thirteen (13) wt% iron scrap at a temperature of 950 to 1050°C for three (3) hours. The smelting process consists of four (4) stages; feed drying, firing of gaseous hydrocarbons and solid coal from the feed, lead reduction from slag, and separation of molten products. The flow rates of natural gas and oxygen to the burners are controlled to ensure combustion of the bituminous material in the furnace. The process produces crude lead bullion containing (wt%) 0.1 to 0.5% Cu, 0.02 to 0.5% As, 0.05 to 0.07% Bi, 0.1 to 0.5% Sb, and 0.1 to 0.6%Sn. The process also produces a mixture of sodium silicate slag, Fe-Zn-Pb-Cu-S matte, and Fe-As speiss containing (wt%) 5 to 10% Pb, 2 to 6% Cu, 10 to 15% Zn, 1 to 3% As, 10 to 15% S, 0.5 to 3.0% Cl, 2 to 4% K, 4 to 7% Na, 20 to 30% Fe, and 5 to 10% SiO2. The dust is made up of PbO, ZnO, PbSO4, and PbCI2, KCI, and NaCI with a chemical composition (wt%) of 35 to 50% Pb, 5 to 15% Zn, 3 to 6% As, 4 to 8% Cl, 2 to 5% K, and 2 to 5% Na. The construction of the new lead production plant at the Glogów copper mill will process both current lead-bearing materials as well as lead-bearing material that have been stockpiled over the last fifteen (15) years to give a significant improvement in protection of the natural environment.

Jan 1, 2002

The results of laboratory, large-scale laboratory and commercial scale investigations regarding the process of slag melts cleaning by oxidizing-reduction gas mixtures with a wide range of Po2 and the use of matte of various compositions as an extracting phase are presented. The copper, nickel and cobalt behavior during the cleaning process has been studied based on SEM and x-ray Microprobe of the quenched slag melts. The general cleaning mechanisms have been found. On the basis of the obtained data the most efficient cleaning methods have been proposed.

Jan 1, 2003

By Frederick T. Wallenberger

"Laser assisted chemical vapor deposition (LCVD) is a new containerless fiber process whereby growth of small diameter fibers or microstructures (microsprings, microsolenoids) occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber inside the reaction chamber. Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Continuous fibers and multifilament yams are possible. The use -of high reaction chamber pressures (1-10 bar) and a small wavelength Nd-YAG laser made it possible to fabricate small diameter fibers at growth rates >1 mm/s. This paper describes the synthesis of single crystal, polycrystalline and amorphous fibers by LCVD, and provides a comprehensive analysis of phase transformations occurring during their fabrication.IntroductionLaser assisted chemical vapor deposition (LCVD) is a new containerless fiber process [1-10] whereby growth of small diameter fibers or microstructures occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber in the reaction chamber (Figure 1). The diameter of the growing fiber corresponds to that of the laser focus. Depending primarily on the laser energy (Le., the temperature at the growing fiber tip), it is possible to obtain single crystal, poly crystalline or amorphous fibers by this method.Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Laser assisted CVD is a potentially continuous process; continuous fibers and multifilament yams are possible."

Jan 1, 1994