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By Shufeng Yang, Anping Dong, Yongfeng Chen, Jingshe Li, Lifeng Zhang, Liyuan Sun

"Instead of nickel-based stainless steel, a nitrogen-bearing stainless steel was produced to reduce the production cost stemming from the shortage of nickel recourses. Thermodynamic model to calculate the saturation nitrogen content in the stainless steel were developed and the model was validated by experimental measurement. The experiments were performed with a high temperature induction furnace. Nitrogen gas under constant pressure was injected into the crucible with a top lance by which the nitrogen was transferred to the molten stainless steel. The effects of chemical composition, temperature, superficial active elements and nitrogen-flow rate on transferring nitrogen to the steel were investigated and discussed.IntroductionWith the rapid production growth of stainless steels, nitrogen-bearing stainless steel has recently attracted more and more attention for their high strength and excellent corrosion resistance imparted by interstitial nitrogen without decreasing its toughness and ductility. Moreover, the addition of nitrogen to the stainless steel as a substitute for nickel leads a lower consumption of nickel, so significantly lowers the high production cost stemming from the shortage of nickel recourses. However, production of the nitrogen-bearing steel is difficult since nitrogen is a gas element and has a low solubility in the steel. So efficiently increasing the amount of nitrogen in steel continues to be one of the main concerns for the production of nitrogen-bearing steels.Currently there are some special processes to produce austenitic stainless steels with a very high N content, including pressurized electroslag remelting, counter-pressure casting, special induction melting and powder metallurgy, etc [1]. Special expensive vacuum system was required for these processes. Alloying nitrogen at a normal pressure can be performed by alloy addition or gas injection. Blowing nitrogen gas is a more economic and advisable method since the nitrogen-bearing alloy is quite expensive and contains high content of impurities. A number of investigations have been reported on the solubility of nitrogen gas in pure iron [2] but few in iron-based multi-component alloys such as stainless steel.In the current study, the effects of steel chemical composition, temperature, superficial active elements and nitrogen-flow rate on transferring nitrogen to the steel were experimentally investigated with a high temperature induction furnace."

Jan 1, 2011

By Carla Lupi

Zinc electrowinning from sulfate solutions is the traditional industrial method to produce SHG zinc. Over the past few years several efforts have been done to improve process efficiency in order to reach high productivity with low energy requirement. The latter aim can be pursued both by means of a hard purification of the electrolyte and reducing the anodic voltage. This work is a comparative study of the results obtained in several previous researches on zinc electrowinning from both sulfate and chloride solutions. Zinc electrowinning tests on industrial sulfate solution have been carried out by using Pb alloy anodes and by adding organic depolarizers such as ethanol, acetic acid or ethylene glycol. Experiments on chloride solutions, obtained by purification of zinc exhausted electrolyte, have been performed by using DSA anodes and by testing the effect of additives such as TEACI and TBAC\. Comparing the best results obtained with the two methods it can be highlighted that a high quality zinc is electrowon in both cases with comparable energy requirements.

Jan 1, 2000

By M. Kawakami

In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with C02 is expected to occur at as low temperature as possible. In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the Bintyo char, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion of C02. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining al\ the obtained data.

Jan 1, 2003

By M. Kawakami

In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with CO2 is expected to occur at as low temperature as possible. In order to get a highly reaetive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the Bintyo char, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion of CO2. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining all the obtained data.

Jan 1, 2003

By J. M. Brupbacher, D. C. Nagle

"The XD TM * approach to producing metal matrix composites employs an in-situ precipitation technique for the formation of the reinforcement directly in the matrix of interest. Key features include: thermodynamically stable reinforcement; clean particle/matrix interfaces, single-crystal reinforcement; size, chemistry, and shape control; uniform distribution; compatibility with conventional ingot techniques; and grain refinement.Using XD~ technology it is possible to simultaneously introduce a number of different reinforcements in a given matrix, thus allowing for designing the microstructure to meet a specific material need. Thus, XD1l'1 technology is a very useful technique for achieving ""designer"" or ""engineered"" microstructures. XD TM technology has been applied to a number of systems including AI, NiAI, TiAI and Cu. Materials property and processing benefits will be discussed."

Jan 1, 1988

By Maribel L- Saucedo-Muñoz, Toshiyuki Hashida, Victor M. Lopez-Hirata, Shin-Ichi Komazaki

"Small-punch tests were conducted at 4, 77 and 293 K on three types of austenitic stainless steels JNl, JJl and JK2, which were solution treated, water-quenched and then aged at 923, 973, 1023 and 1073 K for 5 h. Small-punch test energy was employed for the evaluation of the aginginduced embrittlement behavior in these materials. Fracture surface of small punch test specimen for the solution treated steels exhibited a ductile fracture, showing the highest SP test energy values. The presence of intergranular brittle fracture was observed in aged specimens. Smallpunch test energy decreased significantly as the aging process progressed. The highest and lowest decrease in small-punch test energy with aging temperature occurred in JNl and JK2 steels, respectively. The decrease in small-punch test energy showed to examine appropriately the aging-induced embrittlement in these materials. The difference in aging-induced embrittlement behavior for these steels was explained based on the volume fraction of intergranular precipitates in aged samples.IntroductionA high level combination of strength and toughness is required for cryogenic structural materials used in the superconducting magnets of fusion nuclear reactor. This requirement is beyond the capability of conventional austenitic stainless steels [1]. The Japan Atomic Energy Research Institute (JAERI) developed new cryogenic JNl, JJl and JK2 austenitic stainless steels. The structure of superconducting magnets is supposed to be constructed by welding thick plates of this kind of steels. Thus, most of the components are exposed to thermal cycles. The slow cooling may cause microstructure changes in both the base material and weld zone. These changes may also decrease the fracture toughness of these materials at cryogenic temperatures. Therefore, it is important to study the effect of thermal aging on fracture toughness behavior for these steels. Konosu et al. [2] carried out a study of the effect of thermal aging on the mechanical properties for JNl steel using tension and fatigue tests. Kwon et al. [3] evaluated the deterioration in fracture toughness at cryogenic temperatures for the isothermally aged JNl steel by means of the Small-Punch (SP) test. No other reports were found about the cryogenic fracture toughness behavior for this kind of steels. To evaluate the cryogenic fracture behavior, the elastic-plastic Jrc value is a good alternative [4,5]; nevertheless, the standard required specimen size makes it difficult to be used for the fracture toughness evaluation in small zones."

Jan 1, 2011

By Eustathios S. Kikkinides

This work presents an integrated approach for the optimal design and control of hydrogen storage beds. A detailed 2-D mathematical model is developed for metal hydride beds and validated against experimental and theoretical literature results. Based on recent advances in dynamic optimization, the model is used to find the optimal process design and operating strategy in order to minimize the storing time, while satisfying, a number of operating constraints (such as pressure drop limitations, cooling fluid availability and maximum tank temperature). Trade-offs between various objectives, alternative design options and optimal cooling control policies are revealed illustrating the potential of the approach. In a further step the model is used to exploit the benefits between material and process design. Systematic simulation and optimization studies are performed at two different length scales (tank and adsorbent pore level) for carbon based materials. The macroscopic approach determines the optimal values of the sorption parameters while, based on these results molecular simulation techniques are employed to determine the pore size distribution of the adsorbents.

Jan 1, 2006

By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

Today’s world relies upon advanced green technologies that are made of critical elements with unique properties. Examples include rare earth elements (REEs) that are critical in the manufacturing of wind turbines and electric/hybrid vehicle batteries, key components of a greener future that face supply uncertainty and near zero recycling. To tackle their supply challenges, activities have begun for urban mining from waste electrical and electronic equipment (WEEE) that contain considerable amount of REEs, but their current level of recycling is less than 1%. Current recycling practices use either pyrometallurgy, which is energy intensive, or hydrometallurgy that utilizes large volumes of acids and solvents and generates large volumes of hazardous waste. In this study, we developed a novel and sustainable process to recycle REEs from WEEE, NiMH batteries in particular. The developed process relies on supercritical fluid extraction (SCFE) utilizing CO2 as the solvent, which is abundant, safe, cost effective, and inert. The effect of seven operating parameters, namely temperature, pressure, residence time, sample to chelating agent ratio, agitation rate, complex formulation, and methanol addition on REE extraction efficiency was investigated, and optimum operating conditions were determined. This work is the first to utilize a very efficient and safe process that runs at low temperature to extract metals from postconsumer products with minimum hazardous waste generation, while offering about 90% leaching efficiency for REEs. We expect our process to find widespread applicability in urban mining of REEs using green chemistry.

By Guanghui Li

In the paper, the recovery technology of gallium from zinc-leaching residue by cold-bonded coal-based direct reduction process following magnetic separation was developed. The results show that the scattered metal Ga can be concentrated obviously after the reduction of zinc-leaching residue briquette and magnetic separation of reduced product. At the same time, the volatilization of Zn in the residue is enhanced during the reduction. When the residue, bear¬ing 18.60% Zu.21.18% Fe and 527 g/t Ga, was reduced with coal at 1100°C for 150 min, the results of Zn volatilization of 9842% and Ga recovery of 89. 10% were obtained in reduction. After magnetic separation of the reduced product, the concentration of Ga in sponge iron is 2164 g/t, and the separation recovery of Ga reaches 92.42%. The enriched mechanism of Ga during reduction -separation process was studied by using electron microscope, scanning elec¬tron microscope, energy spectrum and mineralogical analysis. The investigations show that there is no formation of independent phase of Ga during reduction process. The Ga occurs mainly in metallic iron phase (the concentration of Ga in metallic iron phase is 0.04%-0,4%), in addition, there exists a little Ga in poorly crystalline sulphide (o.08%-0./5Y& Ow). But Go does not exist in most of glass and silicate phase. The affinity of Ga for metallic iron is the enrichment basis of Go in reduction, and it is also in favor of recovering Go during magnetic separation. Key Words: Gallium Zinc-leaching Residue Cold- Bonded Direct Reduction

Jan 1, 2003

By Ilkka V. Kojo

This paper gives an overview of the primary copper smelting business during the years of flash Smelting in the light of various projects taking into account the sustainability of copper production. Also the future challenges of copper smelting are addressed with special emphasis on the environment. Flash Smelting connected with either Peirce-Smith converting or Flash Converting offers the most economical and environmentally friendly alternatives for the smelting of normal and lean copper concentrates. For rich copper concentrates the feasibility of Outokumpu Direct Blister Flash smelting is, understandably, beyond compare. When the total investment costs for building a smelter and acid plant are considered, it is clear that Flash Smelting is the more feasible option compared to bath smelting. Reduction of equipment and operating cost is further achieved by the LUREC-process developed by Outokumpu Technology for operating plants with SO2-contents up to 25 % by volume. As an example the Kennecott-Outokumpu Flash Converting Furnace (FCF) has been in operation at Kennecott Utah Copper for 10 years and has achieved excellent results both environmentally and production vice. The FCF treats the entire output of the Kennecott Flash Smelting Furnace and has excess converting capacity. Furnace life, initially projected at two to three years, is now projected to be more than 5 years. It is likely the life will be essentially the same as a well-operated Flash Smelting furnace.

Jan 1, 2006

By Keizo Uematsu, Satoshi Tanaka, Nozomu Uchida, Anze Shui, Joaquin Lira, Cyril Lavelle, Midori Saito, Thierry Poirier

"Dispersed and flocculated alumina (non-spherical particles) slurries were prepared by pH controlling with HCL Spray-drying of these resulted in dimpled granules with a smooth surface and high density, and spherical granules with rough surface and low-density, respectively. Detailed characterization on granules and their compacts includes: SEM observation, density measuring (mercury porosimetry and Archimedes's Principle) and liquid immersion optical microscopy. Compaction of these granules originated a larger particles rearrangement in the samples made with the spherical granules than with the dimpled granules. This was verified through the orientation of alumina particles, which was pronounced in the compact made with the former granules.IntroductionOn immersing a ceramic powder in water, the surface usually acquires a charge by interaction with ionic species in solution. The charge is affected by pH and the electrolyte concentration of the water. 1 The dispersion in a slurry is achieved through the interaction of charges on the particle surface with the media. In the ceramic processing, especially in the process of casting, the dispersion of slurry has been one of the most important topics studied for many years. Recently the attention is paid on its role in the pressing. The granule characteristics are governed by the dispersion state of slurry. Takahashi et al2 , Tsubaki et al3 and Walker et al4 showed that the granules from dispersed slurry were dimpled and of high density, while granules from flocculated slurry were spherical and of low density. This variation in the granules characteristics should have a marked effect on the structure of compact.This paper presents the influence of the dispersion state of alumina slurry on the granules characteristics and also on the internal structure of compacts. Different dispersion states were elaborated by adjusting pH of the slurry. In this method, the particles are dispersed or flocculated only by the effect of surface charging, and thus some secondary effect such as the steric hindrance from an electrolyte dispersant is avoided. The characteristics of granules and compacts are examined with SEM, density measurements by mercury porosimetry and by Archimedes's Principle and liquid immersion optical microscopy. This novel microscopy provides various important information on packing structure of particles, such as their orientation. 5"

Jan 1, 2000

By Laurentiu Nastac

"The importance of investigating solute redistribution during the unidirectional solidification of multi-component alloys is broadly discussed in the literature. A previously developed analytical model that was experimentally validated for Al-Cu, Sn- Bi and Fe-Si dilute binary alloy systems is used in this article to study in detail the solute redistribution, the liquid/solid interface stability based on an extended transient constitutional undercooling criterion and the size of the initial transient region during the unidirectional solidification of Ti-6-4 and Ti-17 alloys. A comparison between Ti-6-4 and Ti-17 alloy systems with respect to interface stability and the size of the initial transient region is also provided. The effective partition coefficients of the alloying elements in these alloys were determined based on specially designed experimental measurements.IntroductionThe importance of investigating solute redistribution during alloy solidification is broadly discussed in the literature [1-5]. One of the relevant applications of this study would be the mathematical modeling of equiaxed and columnar solidification of multicomponent alloys. This includes the instability of the solid/liquid interface. There are several mass and heat transfer processes that involve the calculation of solute redistribution during directional solidification such as industrial directional solidification processes, continuous casting, remelting processes, Czochralski crystal growth technique, floating zone techniques, etc."

Jan 1, 2012

By Andrew Campbell, Michael Reed

"WorleyParsons has used Discrete Event Simulation methods in conjunction with more traditional process models to assess the performance of copper smelting operations. This work was performed to determine the plant capacities and suitability of proposed debottlenecking options including accounting for the planned and unplanned (breakdowns) shutdowns in the various parts of the plant and supply chain. This paper outlines the methods used along with demonstrating the benefits of selecting a feasible option and minimizing capital and operating costs.IntroductionTraditionally for de bottlenecking studies of smelters and other process plants, a mass balance is performed based on continuous operating rates and expected operating hours. Smelters have several points of failure that will restrict, if not take the entire plant offline. By using a more detailed model, validated against plant experience, bottlenecks can be demonstrated and strategies to remove them to increase plant availability and economic.The modeling simulates the plant performance in real time, and by performing enough simulation the expected long run performance of the plant can be estimated. The models have been built using ExtendSim which is a powerful Discrete Event Simulation software package that is ideally suited to the batch and semi-batch processes and events that occur within smelter operating environments. The value of performing this work is that the operational performance of the plant can be assessed ensuring production targets are met, without using excessive capital outlay."

Jan 1, 2013

By J. Vander Linden, R. De Ketelaere, M. Verhaege

In this paper, results are presented concerning the search to implement Supported Liquid Membrane (SLM) technology for the recovery of copper from electroplating effluents. Acid copper electroplating rinse solutions or effluents resulting from the post-treatment of, for example, cyanide-containing copper electroplating baths all contain copper (2+) in the lower concentration levels. A thorough study of the influence of the individual parameters and of their combined impact on mass transfer in small scale laboratory SLM modules has been performed, enabling to set forward the appropriate operating conditions for a pilot plant installation. The pilot plant, containing two SLM modules. of 18 m2 of surface area, has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that this installation is able to treat 40 l/h of acid copper sulphate rinse solutions· containing 500 ppm of copper. The final copper concentration in the effluent can be reduced to a few ppm while copper metal is recovered by electrolysis of the concentrate. This technology is also applicable to the treatment of solutions with low copper content of origins other than plating shops, such as tailings from copper plants or mine waters.

Jan 1, 2000

By Bing Li, Miao Shen, Qiang Wang, Yuqi Chen

Electrochemical methods including cyclic voltammograms, square wave voltammograms, chronopotentiometry are applied to characterize the reduction potentials of Na+ and Li+ ions in LiCl-KCl melts. According to theoretical calculation, the reduction potential for Na+ is slightly more negative than Li+ in NaCl-LiCl-KCl melts at 450℃. However, by electrochemical measurements, the reduction potential of Na+ is slightly more positive than Li+ in the above melt and the potential difference between Na+ and Li+ reaches 0.16-0.2V on an inert W electrode in 1.0-2.0 wt% NaCl-LiCl-KCl melts. An active Pb electrode is used to improve the removal rate of Na+ from LiCl-KCl melts. The reduction potentials for both Na+ ions and Li+ ions on a Pb electrode shift to more positive values and the reduction currents become larger. After 6h electrolysis on a Pb electrode at -3.0V, the practical removal efficiency of Na+ ions reaches 90.12% and the reduced products contain metallic Na and Li with a Na/Li mass ratio of 4.25/1.

Jan 1, 2015

By Shichao Zhao, Ke Xie, Qijie Zhai, Wenbin Xia, Yuanyi Guo, Changjiang Song

"This paper investigated the structure evolution and phase formation ofFe-(11,13,15wt.%)Mn alloy under near-rapid solidification conditions. It is found that the area ratio of equiaxed zone in the Fe-13Mn alloy is the largest. And the primary dendrite arm spacing of Fe-(11,13,15wt.%)Mn alloy increased clearly with increasing distance from the surface. The volume percentage of HCP phase increased with increasing manganese content in the range from 11 pct to 15pct.IntroductionThe developing trend of automobile is the energy conservation, enviromnent protection, light weight, and high security. So the material would be required to the higher strength, higher plasticity and more likely to processing of automotive steel. Fe-Mn based alloys is considered as a potential material to the third generation automobile steel for its high damping performance [1], good mechanical properties [2-3], and high young's modulus [4]. And it is important that metastable HCP phases of Fe-Mn based alloys, which attracts technological interest for theoretical and experimental research [5-6].Metastable materials have been extensively used in the area of iron steels. Among various fabrication methods for high performance materials, rapid solidification is one of most popular ways to produce advanced materials by obtaining metastable phases. The solidification of metals in metastable phases provides access to an extended range of materials properties with novel properties [7]. Thus, in this work, Fe-Mn alloy metastable materials prepared by near rapid solidification is studied."

Jan 1, 2013

By Mehdi Asadi, Heinz Palkowski

"In recent years, the increased demand for advanced high-strength steels (AHSS) mainly had been driven by the need of the automotive industry to reduce weight and to improve safety. Beside good ductility and high strength, those steels have a high bake hardening (BH) effect, giving additional contribution to the strength of structural parts, subjected to the paint baking process. In this paper we concentrate results gained for hot rolled dual phase (DP) steels.For the simulation of changing process conditions within the final hot rolling the specimens were hot deformed using different schedules of temperatures and reductions, selected according to the non-recrystallization temperature (TnRX). It was possible to refine the DP steel structure by control-ling the deformation temperature and the amount of strain below TnRX during the thermo-mechanical controlled processing (TMCP). This structure refinement resulted in an improvement of the strength and BH behaviour. A wide spectrum of mechanical properties could be obtained depending on the different hot deformation schedules. The best strength and BH levels were recorded for the deformation below TnRX at the highest amount of strain.IntroductionDP steels are characterized by a good formability, high strength and a good compromise between strength and ductility [1]. Moreover, the DP steels exhibit a continuous yielding behaviour, low yield point and a high strain-hardening coefficient [2]. Furthermore, the DP steels often show a large potential for bake hardening (BH). BH refers to the increase in yield strength as a result of the paint baking treatment of the shaped auto-body parts. The primary mechanism that causes the additional strengthening is the immobilization of dislocations by the segregation of interstitial atoms, known as classical static strain aging [3]. The increase of strength thus achieved allows a further reduction of sheet thickness and improves the crash safety and the dent resistance. The BH of special steel qualities is technically used in DP, where e.g. the increase in strength is realized in the final heat treatment [4]. Previous own investigations [5-6] stated that the BH effect of DP is much stronger than that one for conventional BH steels."

Jan 1, 2012

By Rajesh K. Mishra

In secondary precious metals refining, the feed to the plant itself is a waste generated in manufacturing processes. Constant changes in manufacturing processes produce ever changing feed materials to the secondary PGM (platinum Group Metals) refineries. After extracting the precious metals, secondary wastes are generated. The discharge of effluent is dictated by both the PGM losses in wastes and the regulatory mandates. This paper will discuss some. of the conventional as well as some newer approaches to face both the challenges.

Jan 1, 1995

By Masao Miyake, Eiichiro Matsubara, Tetsuji Hirato, Yasuhiro Awakura

"Zn-Cr alloy coating with around 15 wt% Cr has been found to have much higher chemical corrosion-resistance to steel than conventional zinc plating, while· its structure has not been clarified. The Zn-Cr alloy plating is performed at high current densities around 1 A cm-2 and for 10 to 20 sec using acidic aqueous sulfate solutions with some additives in the iron-steel industry. Due to the high current densities, it seems reasonable to consider that the Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings have a non-equilibrium phase and have a structure change in the .direction of thickness. In this research, the crystal structure of the Zn-Cr alloy coating electrodeposited at high current densities and change of the structure in the direction of thickness were examined by X-ray diffraction. The coatings containing under 20 and 35-40 wt% Cr had hcp and bee structure, respectively, while the coatings containing 20-35 wt% Cr comprised two phases with the hcp and the bee structure. The structure of the coating varied in the direction of thickness; both the hcp and bcc phases coexisted in the vicinity of the substrate, while the hcp phase became predominant with increasing distance from the substrate.IntroductionRecently it has been reported that Zn-Cr alloy coating containing around 15 wt% Cr has much higher corrosion-resistance to steel than conventional zinc plating.1-3) The corrosion-resistanc·e of Zn-Cr alloy plated steel sheet with a plating amount of 20 g m·2 is, for example, superior to that of Zn plated steel with a plating amount in the range 60 to 90 g m·2 , which is widely used for automotive bodies today.4l The Zn-Cr alloy plating is obtained by electrodeposition at current densities over 0.5 A cm·2 from a sulfate solution containing zinc and trivalent chromium ions and some additives.5•6) The deposition current densities mentioned above are much higher than those for usual electroplating processes, e.g., Zn, Cu and Ni plating, carried out about 0.05 A cm·2 • Therefore, the time required for plating is very short; around 10-20 sec. Due to the high current densities, it seems reasonable to consider that the· Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings do not have a phase expected from equilibrium diagrams; no phase diagram of the Zn-Cr system with a full composition range has been available. 7). In other words, the alloy phase plated would be a non-equilibrium phase with unknown structures."

Jan 1, 2000