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By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By A. Gibson

Most methods for the treatment of scrap printed circuit boards do not reclaim the components in working order as the boards are either fed to a copper smelter, to recover the valuable elements, or, simply landfilled. This work reports the dissolution of the solder in fluoroboric acid containing Ti4+ ions which was particularly selective for solder, allowing the components to be recovered. The solder was subsequently electrowon from the leachant. The boards were then shredded and the copper dissolved in ammonium sulfate and, then treated via solvent extraction to give an electrolyte suitable for electrowinning. The remainder of the metals were dissolved aqua regia, silver remained unattacked by the aqua regia, palladium precipitated as Pd(NH4)Cl6 in the presence of zinc and nickel, the gold was removed by solvent extraction and precipitated as nanoparticles. The aqua regia was then diluted and the zinc and nickel separated by solvent extraction.

Jan 1, 2009

By Chen Dong, Yuanling Gao, Jilai Xue, Jun Zhu, Luxing Feng

"Porous Ni-Ti alloy has many applications in a wide range of engineering areas. The porous NiTi alloys were prepared from Ti and Ni powders in sintering process under argon atmosphere. The major chemical compositions of the sintered Ni-Ti body were Ni Ti, Nh Ti4O and Nh Ti, respectively, the internal pore structures were characterized by image analysis technique, which were dependent on various processing parameters such as sintering temperature, amount of poreforming agent, forming pressure, etc. The results show that the porous alloy samples had the characteristics of uniform pore and high open porosity; pore-forming agent and sintering temperature are important factors in porous; pressure affected the sintered products' pore, by affecting the combination of alloy powder with pore-forming agent.IntroductionPorous Ni-Ti alloy materials exhibit not only excellent shape-memory and superelasticity, high yield strength and ductility, good corrosion resistance and biocompatibility, but also have low density, low stiffness, and high energy absorption rate due to their porous structures [1]. In recent years, these porous Ni-Ti alloys have found applications in a wide range of engineering areas, such as bone implants [2-4], impedance-matching connectors [5], energy-absorbing structures [6,7], separators [8] and actuators [9], etc.Pore characteristics can play very important role in determining of the performance of porous NiTi alloys. For example, when the alloys are used to repair or replace hard tissue implant material, the pore shape and size not only determine their mechanical properties, but also have great effect on the fluid transmission of human body. The pore characteristics can also influence the stressstrain behavior of the porous Ni-Ti alloy and, thus, strongly affect their mechanical properties, superelasticity, and fracture mechanisms [10].In this study, the Ni-Ti alloys with high porosity were prepared in a powder sintering process under argon gas. The pore characteristics were investigated using SEM, XRD and image analysis techniques, especially in association with the content of pore-forming agent, sintering temperature and compacting pressure."

Jan 1, 2011

By Kafui Nyavor

Acid mine drainage (AMD) is presently the biggest single environmental problem facing the mining industry. New and expanding metal mines in most parts of the world have to demonstrate their ability to contain this problem to obtain operating permits. Conventional methods of controlling acid mine drainage have primarily been limited to collecting the drainage and neutralizing with alkaline materials which do not provide a permanent solution to the AMD problem. Since acid mine drainage results from the oxidation of sulfides in the presence of oxygen, water and iron-oxidizing bacteria, controlling any of these three factors contributing to pyrite oxidation provides a potential at-source remedy for reducing or preventing acid mine drainage formation. Physical properties such as hydrophobicity also play an important role in the attachment of bacteria, adsorption of oxygen, water, and other ions that subsequently lead to the oxidation of pyrite. In this communication, the suppression of pyrite oxidation by treatment with fatty acid amines (FAA) was investigated. The FAA treated pyrite samples were tested at various conditions of temperature and pressure. At an elevated oxygen pressure of 500 psi and a temperature of 600 C, less than 0.2% oxidation was obtained for the FAA treated pyrite samples, while over 1.2% oxidation was obtained for the untreated samples in 10 hours of oxidation time. Accelerated column oxidation tests at ambient condition showed that FAA mated samples reduced pyrite oxidation by at least 75% in 81 days.

Jan 1, 1994

By Kosei Morita, Osamu Nakano, Katsuhiko Nagai, Kazuhiro Mori

"The Sumitomo Toyo Smelter and Refinery commenced its operation in 1971 with three Peirce- Smith (PS) converters. “2 hot – 1 blowing” operation was practiced, that is one of two available converters was blowing and the other was standby in a hot state while the third converter was under repair. After several improvements, the stack time ratio reached around 90%; and processing 5 batches a day became possible.As a result of the expansion program of the Toyo smelter and refinery that started in 2001, the converter operation pattern was shifted from “2 hot – 1 blowing” to “2 hot – 2 blowing” with the installation of second converter blowers and an additional ladle crane.In 2005 a, the fourth converter was installed and “3 hot – 2 blowing” operation began. Also, with improvements experienced in the anode furnaces and the anode-casting wheel operation, today, the number of cycles has been increased up to more than 8.5 a day.The treatment techniques of fugitive gas containing sulfur dioxide from converter furnaces have been gradually reinforced, and the fixation rate of treated sulfur is currently being maintained at more than 99.9%. This paper introduces the operations described above, and the improvements in environmental management techniques for the Toyo PS converter operation."

Jan 1, 2009

By Boris Arlyuk

The system of short term forecast of metal prices at LME is based on correlation between prices within the quarter forward and at the first place by economic parameters at the West, determining the consumption of metals. Such economic parameters are presented by data of indexes of Western World industrial production (WW IP), official data of IP and Dow Jones indexes at USA. For price forecast within the quarter forward (one day ahead, 3 day -65 days MA forward prices) are significant the changes of actual prices (official and close) at the past and the parameters of daily trade at LME at the past (futures turnover, open interest, LME stocks). It is developed subsystem of price forecast within the quarter forward based on analytical approach determining the relations between the participants of the market. It gives the opportunity to reduce the number of empirical coefficients at the model and receive good accuracy of forecast the MA prices and its direction at the future. Very important part of short term forecast is subsystem determining analytically the probability that the price forecasted for the next trading day will be the maximum or minimum daily price within the quarter forward. The thresholds probabilities are defined by identification the model at the past by maximal commercial efficiency. Such system was tested at the past at period since 2000 till 2005 and gives very high commercial results at operations on 1M forwards and hedging the sales of nonferrous metals traded at LME (primary aluminium, light alloys, nickel, copper, zinc, lead and tin).

Jan 1, 2006

By Joseph Sofra

It has become increasingly evident that sustainable metals production in the 21st century requires producers to balance the needs of cost effective, high value production with that of responsible plant operation. This is becoming more difficult as lower grade and more complex feed materials, including recycled scrap and residues, are being processed to reduce production costs and decrease exposure to primary metal market fluctuations. One particular facet of the metals industry facing these challenges in the 21st century are copper producers, The recent steady decline in the copper price has seen the industry cut expenditure, tighten control on income streams and focus on high returns on capital investment. For these reasons copper producers are looking towards flexible technologies that can deliver high value products, with minimal environmental impact at low capital and low sustainable operating costs. Ausmelt's Top Submerged Lancing (TSL) technology for copper production is a low cost, proven technology for the processing of both primary and secondary copper materials. Both the smelting and converting operations introduce significant advantages in environmental performance, improved process efficiencies and high rates of metal recovery, Ausmelt has made significant gains in the past 4 years in establishing a strong market position for its copper technology, New installations in China, South Africa and India as well as existing operations in Zimbabwe and China have demonstrated its effectiveness. This paper reviews the application of Ausmelt Technology for both smelting and converting of primary and secondary sources, It discusses Ausmelt's design and implementation philosophy, and how this philosophy meshes with the needs of the end user.

Jan 1, 2003

By A. Mikula, S. Karlhuber

"Unique physical and mechanical properties made the Pb-Sn solders attractive for low temperature joining of electronic parts. But since lead in solder materials has become a great enviromental problem and health concern, lead will be slowly replaced by other materials in soft solders. Some of these materials which are currently under investigation are ternary tin alloys. Many different physical properties like wetting behavior, electrical and thermal conductivity and surface tension are measured on these alloys, but on the thennodynamic properties and the phase diagram of the alloys under discussion there is only little information available. We investigated the (Ag, Au, Cu)-Sn-Zn systems and determined the thermodynamic properties over the whole composition range by emf-measurements. From these measurements we also got some information on the liquidus. In the Sn-rich corner the phase diagrams are still under investigation.IntroductionSoldering is technically defined as the joining of two base materials, mostly metals or metal coated nonmetallic substrates, with a third metal. The melting temperature of the third metal or metal alloy should be well below those of the substrates. Solder alloys can be categorized in soft and hard solders. Soft solder alloys usually contain lead, tin, bismuth, indium or cadmium and hard solders gold, zinc, aluminium or silicon. The difference between soft and hard solders is the melting temperature of the soldering material. This temperature is around 350°C.An interesting brief history of solders is given by Vianco and Frear [1]. They report, that in 4000 B.C. solders were already used in Mesopotamia. From archaeoligical evidence those solders were gold-based hard solders.Tin-lead soft solders and their use are not easily found, because in course of time tin has been reduced to stannic acid, making the identification quite difficult. Well preserved soft solder artifacts were discovered in King Tut's tomb dating from 1350 B.C. In ancient time Pb-Sn solders were used primarily for the manufacture and repair of cooking utensils and metal tools. The Romans used lead-tin solders extensively in the construction of the aqueducts."

Jan 1, 1996

By Kathryn C. Sole

A novel solvent-extraction process for the refining of gold was recently commercialised, with the commissioning in May 1997 of a 24 t a-' refinery at Harmony Gold Mine in Virginia, South Africa. The MinataurTM Process (Mintek Alternative Technology for Au Refining) uses solvent-extraction technology to produce gold of 99.99% purity from the cathode sludge arising from a conventional carbon-in-pulp / electrowinning circuit. Implementation of this process introduces significant cost benefits compared with the conventional dore smelting / toll-refining route previously followed. This paper outlines the process, presents selected operating results obtained during the first few months of operation, and provides some details of the associated techno-economic advantages.

Jan 1, 1998

By Tian Tang, Sergio D. Felicelli

"The laser cladding is an important surface treatment for enhancing resistance against corrosion, abrasion, and wear. The focus of the present study is to develop a three dimensional finite element model to analyze the temperature history and thermal stress evolution during multi-pass laser cladding process on H13-H13 tool steel sample. A sequentially coupled thermal-stress analysis methodology was adopted in this study. The thermal model was firstly established to investigate the temperature history of the laser cladding process. Then the temperature history was used as input to mechanical model to calculate the thermal stress evolution during the process and the residual stress after the sample completely cooled down to room temperature. The influences of process parameters including the scanning speed and scanning strategies on temperature history, thermal stress evolution, and residual stress were investigated in details.IntroductionLaser cladding is an advanced material process technique, which is often used to improve mechanical properties or increase corrosion resistance, repair worn out parts, and fabricate metal matrix composites. In this process, the injected powder or wire feedstock material and a thin layer of substrate are melted and consolidated by use of a laser in order to coat part of a substrate or fabricate a near-net shape part.Numerous mathematical models have been established for analyzing the effects of process parameters, microstructure evolution, and thermo-mechanical behavior of laser cladding. Zhou et al. [1] established an analytical model to investigate the laser induction hybrid rapid cladding for Ni-based WC composite coatings. Huang et al. [2] also developed an analytical model to theoretically investigate the interaction between the laser beam and the powder stream of laser cladding process. A simple and realistic model of laser cladding was proposed by Picasso et al. [3]. The cladding layer is very sensitive to cracks due to the accumulation of residual stress, caused by non-uniform temperature changes, which have limited the wide application of laser cladding technique in industry. Recently, fmite element method has been increasingly used to simulate the laser cladding process [ 4-6]."

Jan 1, 2014

By Xiao Y. Yan

A fused salt electrochemical process was investigated for the synthesis of non-oxide ceramic powders directly from metal oxides, boric oxide, and carbon powders by electro-deoxidation. Sintered pellets of the mixed powders were designed to act as a composite cathode in the electrolytic cell. Electrolysis was carried out in molten CaCl2-NaCl eutectic at 3.1 V and at 600-900 ºC under argon. The favoured cathodic reaction was the removal of the oxygen from the oxides to produce metal atoms that reacted with either the reduced boron atoms, forming a metal boride, or the carbon initially present in the sintered pellets to produce a metal carbide. The technical viability of the process was demonstrated by the electro-deoxidation of sintered pellets of TiO2/B2O3 and TiO2/C to produce TiB2 and TiC, respectively. Compared to existing carbothermic reduction process, this new electrochemical process may be less energy intensive and may lead to lower production costs. I

Jan 1, 2008

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By John W. Graydon

Incineration is an attractive alternative to the disposal of MSW in landfill sites. However, the process of incineration generates fly ash which contains significant levels of leachable heavy metals - particularly cadmium, lead, and zinc - and it is essential to manage this fly ash in an environmentally sound manner. The compositions, phases, textures, morphologies and size of fly ash particles have been studied by light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how fly ash is formed during incineration, in understanding the leaching behavior of untreated fly ash if it is disposed of in a landfill and, most importantly, in guiding the development of the best treatment strategies for fly asti to mitigate its environmental impact.

Jan 1, 1992

By R. Kola

Since more than 15 years the Waelz process at "Berzelius" in Duisburg has proved suitable for reprocessing the zinc and lead containing dust and .sludge which inevitably occur in making steel in EAF-plants. The produced Waelz-oxide is agglomerated in a hot-briquetting plant and charged to an Imperial Smelting Shaft Furnace to recover the valuable elements in form of metallic zinc and lead. In view of the actual importance of the dumping problems of the EAF wastes a description of the "Berzelius" treatment route is given but also the situation in Western Europe is illustrated. Dust from stainless steel production is successfully treated in the Scan Dust Plasma Process in order to recycle Chromium and Nickel, while the resulting Zinc-Dust is treated via the Waelz-ISF-Route. For treatment of low Zinc-containing dust, sludge and fines from integrated steelworks, pilot scale tests have been carried out successfully in the Circulating Fluid Bed in order to recover metalized iron and .zinc/lead fume. A 30,000 tpy Demonstration Plant is planned?.

Jan 1, 1990

By Jinxing Ji

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.

Jan 1, 1995

By K. J. Murphy, A. R. Smith, A. P. Odorski

"The need for large quantities of oxygen for use in metallurgical processes was a major driving force in the commercialization of tonnage air separation plants. Oxygen, nitrogen and argon impact the quality, energy efficiency and environmental aspects of metals production. Cryogenic air separation processes have been used to supply most industrial requirements, however, newer technologies are available or under development to meet the needs of today's and tomorrow's metallurgical processes. This paper reviews the technical features and state of development of adsorption, chemical, cryogenic and membrane technologies. The technologies are compared in terms of plant size, oxygen purity and pressure, nitrogen and argon co-production, product use pattern and back-up requirements. Computer control systems are described that optimize operation over varying load patterns and ambient conditions; substantially lowering energy consumption. IntroductionOxygen production totalled 390 billion cubic feet in 1987. Although current production is lower than the peak of 455 billion cubic feet reached in 1979, oxygen remains the fifth leading chemical product manufactured in the u.s. (1) Metals manufacturing and fabrication accounts for sixty percent of the oxygen consumed in the u.s. Oxygen use in the steel industry consists of air enrichment for conversion of iron ore, purification of the iron in basic oxygen or other furnaces, and for cutting and welding the finished steel product. Nonferrous ores are smelted in oxygen enriched atmospheres to reduce energy consumption and increase capture of sulfur compounds to meet environmental requirements. In the future oxygen usage is expected to become even more important in metals production as energy costs increase, environmental standards become more stringent, and as new coal based processes become commercialized. Oxygen usage per ton of metal in the new direct reduction processes can be up to ten times higher than traditional steel making."

Jan 1, 1988

By Joseph C. Milbourne

Tetra Technologies CCIX? (continuous countercurrent ion exchange) system has been involved in a wide range of uranium concentration, separation and purification applications over the past 40 years. Uranium ion exchange applications have ranged from the treatment of copper heap leach solution containing 5 parts per million of uranium to the treatment of high strength sulfuric acid solutions containing several thousand parts per million of uranium. The flexibility and the countercurrent mode of operation and other unique features of the CCIX? have resulted in successful uranium recovery from these solutions and many others.

Jan 1, 1995

By Rubén Alvarado

The markets and environmental protection rules are more and more exacting, both of which have determined that copper smelters should look for technological development and global management to ensure their viability and competitivity in the short and long term. The main facilities of the present and future Smelting-Converting Process at Codelco's Caletones Smelter, is based on Teniente Converter reactors with a high operational availability that have reached concentrate processing capacities near 2,000 tpd. These reactors are in operation in most of the smelters in Chile as well as in Zambia, Peru, Mexico and, in ?the near future, in Thailand. Since 1993, the Smelting-Converting process of the Caletones Smelter of Codelco-Chile has been based on one Reverberatory furnace, two Teniente Converters and four Peirce-Smith Converters. These facilities, together with the operation of two Fluidized Bed Dryers, three Slag Cleaning Furnaces, and two Oxygen Plants have allowed the smelter to reach concentrate smelting capacities and copper productions of 1,215 kt/year and 360 kt/year, respectively. This transitional operating scheme, combining together traditional and advanced technological equipment, needs further modernization to successfully face the modern world challenges, especially with relation to the environmental commitment, production costs and wide satisfaction of customers. For this reason, for the period 1997-2000, a Modernization Plan has been worked out. This plan considers an increase of the present throughput, which will permit a significant increase in productivity, as well as finding a definitive solution for meeting the environmental regulations. Among these projects, we can point out the definitive shut down of the Reverberatory Furnace, which is a contaminating piece of equipment of low energetic efficiency. Additionally, it considers the installation of two new Slag Cleaning Furnaces, one additional Oxygen Plant, and the incorporation of two new Sulphuric Acid Plants with a production capacity of 4,500 T/D, that will recover over 92% of the sulphur content, of process off-gases.

Jan 1, 1998

By David Dreisinger

The cyanidation of copper containing gold ores results in the co-dissolution of copper along with gold. Copper dissolution results in elevated cyanide consumption that may make the treatment of the gold ore uneconomic. Copper-cyanide species in gold mill effluents may increase the environmental toxicity of the gold mill solutions. The objective of this study was to examine the use of solvent extraction to recover the copper cyanide species from gold mill effluents. Solvent extraction with Cognis (formerly Henkel) reagents LIX 79 and LIX 7950 was studied. Excellent extraction of copper and cyanide was achieved using pH control in extraction. Copper and cyanide may be stripped from the reagents using basic eluants. Various routes for copper and cyanide recovery from the strip solution were studied. Excellent results were obtained using electrowinning in both divided (Nation membrane) and undivided cells. Cyanide recovery was obtained by AVR treatment of a bleed stream from electrowinning. Full results of solvent extraction, copper and cyanide recovery are reported.

Jan 1, 1998

By L. Lü, M. O. Lai

"Mechanical alloying is a dry, high energy ball milling process which has been used to synthesize metallic powders in the solid state. The present study use this technique to synthesize Cu-base shape memory alloy powder from commercial Cu70Zn30, Cu86Zn14 and element AI powders. The evolution and formation of shape memory alloy powder were monitored using X-ray diffraction and microscopy. It was observed that shape memory alloy powder started to form after 1.8 ks of mechanical alloying. ? phase was clearly detected after 3.6 ks of mechanical alloying. The intensity of X-ray diffraction of the y phase increased when mechanical alloying duration was prolonged indicating an increase in the amount of y phase. Microstructure observation showed different stages of formation of alloyed powders: welding between powders and formation of layered structure, deformation and fracturing of layered structure, and finally the formation of alloyed powders.IntroductionMechanical alloying (MA) is a process used for producing powders with controlled and extremely fine microstructure. It was original developed in 1966 (1) to produce aNi-based superalloy combining oxide dispersion strengthening with gamma prime precipitation hardening. In recent years this technique has been used in producing a wide range of materials including intermetallic compounds (2, 3), amorphous materials (4-6) and other materials (7-9). In MA, a blend of powders is subjected to highly energetic compressive collision. The powder panicles are welded and fractured during ball milling. Therefore, it is essential that at least one of powders should be ductile to act as combiner. It has however been found that brittle components without soft element can also be mechanically alloyed (10), even ceramic powders (11).The present work aims to study the mechanism of formation of shape memory alloy powder during MA."

Jan 1, 1994