Search Documents

By Duclerc Fernandes Parra, Washington Luiz Oliani, Christiano Gianesi Bastos Andrade, Ademar Benevolo Lugão, Danilo Marin Fermino, Francisco R. Valenzuela Diaz

This work concerns the study of the effect of discarded bond paper on the mechanical behavior of polypropylene/organophilic clay nanocomposites. A brown polycationic bentonite from the state of Paraíba, Brazil, was treated with sodium carbonate to transform it into a bentonite that swells in water and then treated with hexadecyltrimethylammonium ammonium chloride to transform it into a bentonite that swells in organic liquids. Polypropylene with 3 % polypropylene graft compatibilizer (PP-g-AM) was mixed with 1 % and 2 % by weight of discarded bond paper and with 1% and 2% by weight of organophilic clay using a twin-screw extruder. The specimens were prepared by the injection process. The clay as received and after organophilization was characterized by XRD, SEM, and capacity of swelling in water and in organic solvents. The nanocomposite specimens were characterized by XRD and thermal analysis. The mechanical behavior of the injected specimens was evaluated by strength, flexural and impact tests. The nanocomposites showed improved mechanical properties compared with the polymer without filler.

Jan 1, 2015

By Steve Johnston, Mowafak Al-Jassim, Fei Yan, Omar Sidelkheir, Alain Blosse, Katherine Zaunbrecher

"Imaging techniques are applied to multi-crystalline silicon wafers and solar cells throughout the production process. Photoluminescence imaging, both band-to-band and defect-band, is used to characterize defects and wafer quality at all process steps. These steps include bricks sawn from ingots, wafer sawing, cleaning and texturing, emitter diffusion, edge isolation and glass removal, anti-reflective coating/passivation, and metallization of finished cells. Bricks, wafers, and cells can be imaged at a rate commensurate with in-line measurement, giving spatial information to characterize quality and defect content. Photoluminescence images on silicon bricks can be correlated to lifetime measured by photoconductive decay and could be used for high-resolution characterization of material before wafers are cut. The defect areas in as-cut wafers are compared to imaging results from electroluminescence and lock-in thermography, and cell parameters of near-neighbor finished cells, showing correlations to efficiency, open-circuit voltage, and short-circuit current.IntroductionImaging techniques can rapidly characterize material quality and defect density. Photoluminescence (PL) imaging can be applied to silicon from the brick level to all wafer process steps [1-8]. At the brick level, material thickness allows for measurement and correlation to lifetime where surface recombination effects are minimized [6, 7]. At the as-cut wafer level where thin unpassivated wafers prevent accurate lifetime assessment due to surfaces, defects can still be categorized and quantified to predict finished cell performance [3-5]. Defect regions can be identified by recombination-limited band-to-band PL or by defect-band emission [9-12]."

Jan 1, 2012

By Marcela C. Santini, Luiz A. Teixeira

"Surface conditioning (also referred as etching) of plastics prior to metallization is generally conducted with sulfuric I chromic acid solutions. Although these baths perform well technically, the presence of Cr (VI) imposes serious operating problems of an environmental nature. The present work reports ·the results of a study of surface conditioning o(ABS using solutions based. on sulfuric acid, with hydrogen peroxide and/or nitric acid, replacing chromic acid, as oxidants. Process performance was evaluated by SEM and by the uniformity and adherence of electroless nickel coatings applied on selected conditioned samples. The results showed that the evaluated types of solutions could be optimized to perform as well as the chromic-based baths, with a much superior environmental quality.IntroductionMetallization of plastics is normally undertaken for either decorative or functional purposes. Through metallization, the specific properties of plastics such as light weight, design flexibility, and low-cost of manufacturing are enhanced by the addition of properties usually associated with metals. These include reflectiveness, abrasion resistance, electrical conductivity, and a variety of decorative effects (1).The available processes that can be used for metallization of plastics are vacuum metallization or vapoµr deposition; indirect metallization and plating (1). Plating can be sub-divided into electroless plating and electroplating. In electroless plating, metal ions in aqueous solution are deposited on the .activated plastic surface by oxi-reduction reactions without the aid of an external electric potential, forming a thin metallic layer. This electroless deposited film has two functions: (a) it provides an electrically conductive substrate that allows further coating by electroplating; and (b) provides a secure bond between the plastic substrate and the electroplated layer (1,2). In case the electroless metallic part requires an additional layer for finishing purposes, or just an increase in thickness, the part can be additionally electroplated with a· variety of metals - in most cases those are copper, nickel or chromium (3)."

Jan 1, 2000

By Gil Bourcier

A process has been developed for detoxifying spent potliner (SPL) in which the SPL is blended with limestone and an anti-agglomeration agent and thermally treated in a rotary kiln. The process has been proven and a commercial plant is in operation at Gum Springs, Arkansas. The treated by-product material has been delisted by the U.S. EPA and is now a potential raw material for many commercial applications. Finding uses for a non-hazardous material has many advantages over finding uses for a hazardous material like SPL. Complete usage of the by-product will complete the life cycle and eliminate any landfilling of non-hazardous SPL by-products or residues. Being non-hazardous and containing compounds used in the ceramic and numerous other industries assures many potential uses for the spent potliner by-product.

Jan 1, 1994

By Alice Barreto Bevitori, Felipe Perissé Duarte Lopes, Denise Cristina Oliveira Nascimento, Sergio Neves Monteiro, Isabela Leão Amaral da Silva

"The piassava fiber is one of the most rigid natural lignocellulosic fibers, which has since the last decade been investigated as possible reinforcement for polymeric composites. In the present work, the tensile properties of polyester composites reinforced with piassava fibers with thinner diameters were investigated. Composites with volume fractions up to 30% of continuous and aligned piassava fibers were tensile tested at room temperature to evaluate the ultimate strength, elastic modulus and total strain. For each volume fraction, individually separated fibers with the smaller diameters were tested. The results indicated that the tensile properties tend to improve with increasing volume fraction of the thinner piassava fibers. The role played by the fiber/matrix interaction was analyzed by scanning electron microscopy.IntroductionA significant change in the transportation sectors mainly the aerospace and automotive, occurred last century with the introduction of stronger and lighter materials. The most relevant example was the polymer composite reinforced with synthetic fiber. They are nowadays replacing conventional materials such as the aluminum alloys in airplane body owing to superior specific strength. in recent years, however, environmental problems in a global scale are imposing a reversion in the use of synthetic fiber specially the glass fiber. In spite of its higher specific strength, this fiber and its polymer composites can neither be recycled nor incinerated in a thermal plant to generate electricity [1]. Moreover, the fabrication, processing and transportation of a glass fiber composite are associated with C02emission, the major responsible for global warming [2].A possible substitute for glass fiber without the above-mentioned environmental problems, could be a natural fiber. In fact, natural fibers obtained from cellulose-rich plants, also called lignocellulosic fiber, are already being used in several engineering fields, particularly the automobile industry [3-6]. Figure 1 illustrates an automobile and its many components made of lignocellulosic fiber composite [7]."

Jan 1, 2011

By Donald P. Ziegler, James F. Klausner, Srinivas S. Garimella

"By 2015, nearly half the world's population will live in ""water stressed"" areas. Production of fresh water utilizing waste heat from industrial processes has been identified globally as a research priority.About 15% of the electricity required to produce aluminum is lost as waste heat in the off-gas. However, the low temperature (low grade) of the heat limits reuse. The off-gases contain 50-150 ppm SO2 ; tightening regulations coupled with increasing coke sulfur levels are motivating SO2 control, for which seawater scrubbing is attractive for smelters with suitable access.We describe a process that produces fresh water, utilizing the waste heat while scrubbing SO2 . It uses direct contact between seawater and off-gas to humidify the off-gas. The vapor is subsequently condensed. In smelter trials, a unit treating a slip stream produced high quality water in the anticipated quantity, attaining over 95% SO2 scrubbing. Future work involves scaling the process to be economically attractive.BackgroundPopulation growth, coupled with industrialization and urbanization, are increasing demand for water. Water scarcity already affects every continent. Around 1.2 billion people, or almost one-fifth of the world's population, live in areas of water scarcity, and 500 million people are approaching this situation. By 2025, 1.8 billion people will be living in countries or regions with absolute water scarcity, and two-thirds of the world's population could be living under water stressed conditions (< 1,700 m3 per person annually) [1]. An assessment by the U.S. General Accounting Office revealed that under normal conditions, by 2013, water managers in 36 states in the USA anticipate water shortages, and that the number might grow to 46 states under drought conditions [2].The obvious choice to alleviate water scarcity is the 97% of available water in the oceans, which is saline and requires desalination for use in biological, agricultural and industrial applications. Technologies developed for desalination include Thermal Distillation, Reverse Osmosis (RO), Electro-Dialysis, and Vacuum Freezing. Distillation and RO are the most commercially prominent. Thermal distillation technologies include Multiple Effect Distillation (MED) and Multi-Stage Flashing (MSF). The report commissioned by the World Bank [3] is one of the many excellent references on desalination technologies. According to the International Desalination Association working paper [4], there were more than 17,348 industrial scale desalination plants installed or contracted by 2004. The total production from these plants is on the order of 8.3 billion imperial gallons per day. RO provides 47.2% of the total capacity. The leading thermal process, MSF, provides 36.5% of the total capacity. Although MSF and RO technologies currently provide the most cost effective means for desalination, their drawback is that they are very energy intensive, and whether or not they remain cost effective strongly depends on energy prices and energy supply."

Jan 1, 2012

By Nagahiro Saito, Takahiro Ishizaki, Daisuke Yata, Akio Fuwa

"Ternary compound-semiconductor, CuInTe2, film was deposited cathodically under potentiostatic conditions on titanium substrate from aqueous solution containing CuCl2, InCl3, TeO and HCI in this study.The deposition parameters such as electrolytic solution composition, potential and temperature were optimized· for electrodeposition of CulnTe2. Structural characterization of the: deposited film was also carried out using XRD and SEM. Electrodeposited films Were prepared and analyzed for their chemical composition using ICP. The ICP analyses showed that the stoichiometry of the films could be controlled by (1) the deposition potential and/or by (2) the electrolytic bath composition.1. IntroductionThe ternary chalcopyrite type compound semiconductors exhibit such electrical, chemical and optical properties that make them promising for photovoltaic devices (Kazmerski and Wagner 1985)(1). Many researches have been devoted to the characterization of these materials for over one and a half decades. High efficiency solar cells based on p-CulnSe2/n-CdS have been reported (Mickelson and Chen 1983)(2).The electrodeposited fil ns of semiconductors have more advantage than other physical and chemical deposition techniques; it is relatively easy and economic technique and the semiconducting properties such as band-gap variation, concentration of dopant stoichiometric composition and so on can be controlled with some accuracy. The electrodepositions of the ternary CuInS2, CulnSe2 have been reported by many workers (Hodes and Cahen 1986, Bhattachaya 1983, Singh et al 1986, Lokhande and can be prepared as both p-type and n-type. Therefore, its potential for application in optical and photovoltaic devices is one of the great interests. Bhattacharaya and Rajeshwar (1986)(9) reported the electrodeposition of CuInTe2 from an acidic bath· on indium tin oxide (ITO) and Mo substrate. Triethanolamine (TEA) was used as a complexing agent for indium. The electrodeposited CuInTe2 films were non-stoichiometric in composition under all their experimental conditions by electron-probe micro analysis (EPMA) and Auger depth profile analysis. In this paper, we report our results on the behavior .of Cu-In-Te electrodeposition from ·acidic baths; the preparation of CulnTe2 and the effect of bath composition on electrodeposited films obtained."

Jan 1, 2000

By James J. Komadina, Robert R. Beebe

"Heap leaching of gold ores has enjoyed wide acceptance in the arid and semi-arid regions of the western U.S., Australia and South America. There are areas, however, where cold weather or excessive precipitation can limit the usefulness of heap leaching. Even in Nevada difficulties can be encountered which call for special operating procedures.The paper discusses the general climatological limitations and some of the techniques used to extend heap leaching into colder conditions. A case history of the Cripple Creek and Victor Gold Mining Company operation in Colorado examines 'valley-fill"" technology as an ideal cold-climate solution, where topographical conditions permit.AcknowledgementsThe authors gratefully acknowledge the management of Independence Mining Company for their permission to present this paper. The contributions of Golder Associates; Pikes Peak Mining Company Environmental Affairs Department staff, and the Colorado Department of Mines and Geology were all invaluable in successfully concluding this project.BackgroundWhen heap leaching of oxidized gold ores was introduced in the rnid-1970s it was aimed at large tonnages of low-grade material which could not, in general, be developed via conventional milling. Normally, the reasons for this were economic rather than technical: capital and operating costs for milling were simply too high. At first, grade was almost the only criterion, but deposits too small to justify milling were also potential targets for heap leaching.Renewed interest in gold was centered in the western United States and Australia, where exploration for milling-grade deposits had never really died. When heap leaching came along, it was in these areas that the first developments took place. Coincidentally, these same areas were favorable for heap leaching: climates were temperate for most of the year and competing land uses were limited. Even so, in the western United States in particular, winter temperatures were low enough to complicate operations. Precipitation was less a problem, although heavy snowfalls could periodically interfere as well."

Jan 1, 1997

By Michael L. Sorokin

The various methods of converter slag cleaning operation are analysed from the thermodynamk point of view: cleaning using coal, cleaning using combustion products of natural gas and cleaning in presence of matte. All calculations were done, applying the developing computer procedure based on the free energy minimisation algorithm. Three-suffix Margules equations were used to calculate thermodynamic properties of melts; The calculations resulted in recommendations for the practical appliance.

Jan 1, 1995

By Youngkook Lee

The precipitation kinetics of NbC in ferrite matrix of the Nb microalloyed steel was investigated experimentally and numerically. The mole fractions of NbC precipitates formed at different isothermal temperatures were measured as a function of holding time by electrical resistivity test and were compared with both a mathematical model based on time-dependent nucleation and growth rates and the hardness. There is a good match among the calculated and measured precipitation kinetics of NbC and the hardness. The isothermal precipitation-temperature-time diagram of NbC in ferrite matrix of the Nb microalloyed steel was newly generated. Keywords: Precipitation, Carbide, Ferrite, Nucleation, Growth, etc

Jan 1, 2003

By C. Ek

In bismuth metallurgy, low-copper high-sodium mattes are by-produced. Different charges containing mixtures- of crude mattes, oxidized matte, and/or copper sulfide concentrate and/or copper silicate ore have been smelted to give a rich matte and a disposable slag, then converted to obtain blister copper with high recovery and a rich slag to be recycled.

Jan 1, 1983

By Arvind Thekdi, Cynthia Belt2

"Waste heat from industrial operations in metals industry represents 20% to 50% of the total energy used in most manufacturing plants. Reduction and recovery of waste heat offers the most attractive and cost effective method of reducing energy intensity for an industrial plant to meet corporate energy saving goals. It is possible to reduce or recover 30% to 60% of the available waste heat by using conventional and readily available technologies. Projects to reduce or recovery waste heat may offer less than 3 years payback to as short as a few months. This paper presents information on most commonly used methods for waste heat reduction and recovery in the metals industry operations. It describes the methods and use of analysis tools that would allow a user to estimate energy savings, CO2 or GHG reduction potential, and economic benefit and includes appropriate case histories.Waste Heat SourcesSources of waste heat abound with the metals industry. While the overall quantity of energy is high, the sources are distributed throughout a plant. The largest source within the metals industry is within furnace exhaust / flue gases. This includes the high temperature gases from burners in process heating such melting, calcining, and sintering operations. It also includes lower temperature gases from heat treat, dryers, and heaters. Lower temperatures are also found after post processed hot gases. This could include heat left after heat exchangers, regenerative systems, thermal oxidizers, and emission control systems. Other hot gases include air used in direct and indirect cooling.While waste heat in form of exhaust gases is readily recognized, waste heat can also be found within liquids and solids. Waste heat within liquids includes things such as cooling water, heated wash water, and blow down water. Solids can be hot product at discharge after processing or reactions are complete. Indeed, not only is energy wasted in the hot metal that slowly air-cools, but additional energy may be used in providing air or water-cooling to increase the speed of cooling. Other waste heat sources are not as apparent and include things like hot surfaces, steam leaks, boiler blow down water, etc. Table 1 and Figure 1 show several major sources along with the temperature range and characteristics of the source."

Jan 1, 2011

By Ludwig Hermann

"Phosphorus is required by every cell of living organisms and essential for plant growth. It is a non-renewable resource that must be mined from natural deposits, going gradually into depletion. Abundant secondary resources are available in sewage sludge and meat and bone meal, with the highest exploitable P concentrations in ashes that remain from their widely used combustion with energy recovery. ASH DEC has successfully removed heavy metals and transformed sewage sludge ash into a marketable P fertilizer by application of a thermo-chemical treatment process. Pilot scale investigations in which ash was treated proved that generally heavy metal limits required by fertilizer legislation can be attained. To achieve a high P availability for crops – an essential fertilizer quality feature – was a more challenging R&D task. Our presentation demonstrates the scientific approach and R&D results that lead from assessment of market requirements to licensed products.IntroductionPhosphorus (P) is required by every cell of living organisms. It is one of the major elements for plant nutrition and therefore essential for crop production. P supply in plant nutrition depends entirely on external inputs into soils [1]. This is achieved by P-fertilizers deriving from rock phosphate deposits that are gradually going into depletion. Serious prognoses anticipate that rock phosphate will be the first low running resource in the world [2]. In the EU, last year 2.530 kt of phosphorus (P2O5 in fertilizers) was consumed and only 313 kt (P2O5 in rock phosphate) was mined. Since 2007, rock phosphate prices have increased by 500% because of a tight supply situation [3].For these reasons, P recycling is becoming an increasingly important issue. Suitable secondary raw materials with regard to their high P-content and abundance are sewage sludge and meat and bone meal. In the EU 989 kt P2O5 are accumulated annually in theses materials, of which 632 kt P2O5 are permanently lost to landfills and other forms of disposal. The main reasons for their limited recycling are concerns on heavy metal contents and organic pollutants that may incite health hazards. As an additional shortcoming, the availability of P from these materials to plants is poor and storage and transportation are problematic issues [4, 5]."

Jan 1, 2008

By Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

By Mark E. Schlesinger

Engineering design follows a six–step sequence. Demonstration of this sequence in materials engineering is less common. A case study is presented, using the 1989 paper by Gafner on the development of 990 gold-titanium alloy. This paper identifies a need, develops the problem, identifies alternatives, demonstrates the use of metallurgical principles to identify alternative responses, and shows how more favorable options are selected. The paper can also be used to illustrate engineering design as an iterative process. The paper is also useful as a starting point for more in-depth examination of specific elements of the design process, and lends itself to the creation of student exercises.

Jan 1, 2014

By L. Yin, R. B. Haber, N. Sobh, D. A. Tortorelli, R. W. Hyland Jr.

"We optimize continuous quench process parameters to produce a desired precipitate distribution in aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include a cost function, constraint functions and their sensitivities with respect to the process parameters. These functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine a discrete precipitate particle size distribution. Both the temperature and the precipitate models are solved via the finite element method. Since we use a discrete particle size model, there are as many as 105 degrees-of-freedom per finite element node. After we compute the temperature and precipitate size distributions, we must also compute their sensitivities. This seemingly intractable computational task is resolved by using an element-by-element discontinuous Galerkin finite element formulation and a direct differentiation sensitivity analysis which allows us to perform all of the computations on a PC.1 IntroductionThis work addresses the need for an integrated design capability that links microstructure evolution to the process parameters. It is motivated by the manufacture of lightweight aluminum-alloy extrusions for use in automotive structures. Aluminum alloys offer obvious benefits, however, care must be taken to manufacture favorable microstructures that ensure acceptable structural performance. For example, the manufacturing process for 6000-series components involves hot extrusion of cast aluminum billets followed by either an air or water quench process. The bill~t's initial grain structure is dramatically altered during extrusion by massive mechanical deformations and recrystallization processes. The microstructure continues to evolve during the quench, as complex chemical processes determine the formation of precipitates. The control of the precipit'ate size distribution is vital. Indeed, large precipitates located on grain boundaries serve as crack initiation sites which adversely effect structural crash· worthiness."

Jan 1, 2000

By Ben Hogg

Since the development of the top-submerged lance (TSL) technology for copper and lead smelting by the cooperation of Mount Isa Mines (MIM), now owned by Glencore, and the Commonwealth Scientific Industrial Research Organisation (CSIRO) the core of the ISASMELT™technology has always resided in the lance system. Through continuous innovation and operation of our own smelters, first at MIM, subsequently at Mopani, and also at both the Kazzinc Copper and Kazzinc Lead smelters, Glencore Technology have expanded the core equipment supply to enhance the plant operability. The success of Glencore Technology’s expertise can be directly measured by the success of the Kansanshi Copper Smelter plant, which achieved 100% nameplate capacity within three months of start-up. This paper describes the ISASMELT™ core equipment and how it is applied to smelt sulfide materials. It highlights the strength of the ISASMELT™: continuous innovation to facilitate the versatility and continued increased capacity with every plant implementation.

By Deventer Johanna van

Ore bodies around the world are declining in grade, whilst increasing in complexity. The level of impurities relative to the valuable metal is steadily increasing, posing new challenges to existing operations. Ion exchange is widely used in the hydrometallurgical industry for both primary recovery of metals and the removal of impurities. The superior selectivity of ion exchange resins makes them exceptionally suitable for the removal of target impurities to very low levels, thereby saving operating costs, increasing the value of the final product and significantly improving revenue. The ion exchange process in these applications is very simple, using standard ion exchange equipment and acid regeneration. The process can be fully automated, requiring minimal operator interference and supervision Examples of impurities that are successfully removed via ion exchange include iron, antimony and bismuth from copper electrolyte. In the copper electrolysis process, antimony, bismuth and arsenic tend to form slimes which are dispersed in the electrolyte. These slimes contaminate the cathode and/or decrease the quality of the copper deposition. A special chelating resin was developed to remove antimony and bismuth, while at the same time ensuring minimal chloride leakage to the sulphate matrix. The work is described in more detail in this paper. Ion exchange is also used to remove copper, zinc and nickel from cobalt electrolyte. This paper addresses a few of these examples in more detail.

By Dimitrios Fillippou

Magnesium hydroxide is used in a number of industrial applications, from the neutralisation of acid effluents to the production of pharmaceuticals. High-quality magnesium hydroxide powders can be produced by hydrating slow-reacting magnesia in dilute magnesium acetate solutions. The process of magnesia hydration shows many similarities with a typical hydrometallurgical leaching operation; however, its kinetics are crucial not only for process design and control, but also for the production of powders with a desirable particle morphology. This article shows the results of an experimental work whereby industrial heavily-burned magnesia powders were hydrated in 0.01 to 0.1 mol/L magnesium acetate solutions at temperatures ranging between 333 and 363 K. Examination of the magnesium hydroxide produced and the analysis of the kinetic data suggest that the hydration of heavily-burned magnesia in magnesium acetate solutions is a dissolution-precipitation process controlled by the dissolution of magnesia particles. The activation energy was estimated to be 60 kJ/mol, while the reaction order with respect to magnesium acetate concentration was found to be about one.

Jan 1, 1999

By D. Zhao

High temperature deformation characteristics of austenitic 304L, and martensitic 410 and 416 stainless steels were investigated by conducting compression tests over a wide range of temperatures and strain rates (950-1250 C and 0.001-20 s-1). Flow behaviors of the three alloys were characterized. Optical metallography was performed to determine the as-deformed microstructures. The flow behaviors were related to microstructural phenomena during high temperature deformation. Dynamic recrystallization was responsible for the flow softening. Both dynamic and static recrystallization were operating, and the recrystallized grain size increased with increasing temperature and decreasing strain rate. Strain rate sensitivity was found to increased with increasing temperature and decreasing strain rate. No defects such as cracking and shear bands were observed at those test conditions. Preferred processing conditions can be selected by considering as-deformed microstructure and strain rate sensitivity.

Jan 1, 1994