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By Kim Fagerlund

A novel apparatus for studying refractory infiltration and dissolution/degradation under a temperature gradient was developed. To supersede conventional isothermal refractory testing, a new temperature gradient technique, based on a crucible equipped with a cooling element, has been developed to provide practical information on the penetration and dissolution of refractory materials under cooled conditions. This technique was adopted and applied to several refractory-slag systems. Commercially available magnesia chrome refractory bricks against a copper-containing calcium ferrite type of slag were tested and compared using both a conventional crucible test and the new temperature gradient method. The experiments were conducted at 1300-1420°C under a controlled atmosphere of nitrogen or air. It was noticed that the type of porosity has a significant effect on infiltration of magnesia chrome refractories. Furthemore, the copper-containing calcium ferrite slag caused a severe slag attack and refractory failure in some cases, due to its fluidity and corrosive nature.

Jan 1, 2002

By C. A. Landolt

Inco pioneered the use of tonnage oxygen in non ferrous metallurgy when it commissioned the first .industrial oxygen flash smelting process for the treatment of copper concentrates in the early fifties. This technological innovation was followed by other applications of technical oxygen. Inco is currently implementing a Sulfur Dioxide Abatement Program designed to reduce S02 emissions from the smelter by 60% in 1994. The new flowsheet includes new equipment for the oxygen flash smelting of Cu-Ni concentrates and for flash conversion of chalcocite. Oxygen smelting and converting technology will lead to a substantial decrease in use of fossil fuels and to generation of high strength S02 off gases suitable for efficient fixation in a new acid plant.

Jan 1, 1992

By K. Kashiwaya, N. Hiroyoshi, H. Furuya, N. Sumiya, M. Tsunekawa, M. Ito

"The number of hybrid vehicles is increasing and this is causeing an increase in waste nickelmetal hydride batteries. The cathode activating agent of batteries is made of nickel hydroxide and the anode activating agent is an alloy of nickel and rare earth elements. Conventional rotary kiln methods cannot recover the rare earth elements, and hydrometallurgical treatment of crushed product consumes large volumes of agent. The physical separation of the anode alloy from the cathode hydroxide would make it possible to reuse the alloy. The authors have reported separation of anode and cathode components in the large size fractions using a newly developed dry magnetic separation method. Wet magnetic separation has been applied to the powder fraction and about 90% anode purity was achieved. This paper reviews experimental results from previous publications and proposes an integrated treatment process for crushed nickel-metal hydride batteries.IntroductionEnvironmentally-conscious clean energy vehicles have attracted much attention in developed countries and particularly hybrid vehicles are increasingly mass-produced as low emission vehicles. Hybrid vehicles have both a gasoline engine and an electric motor to save on gasoline usage and a nickel-metal hydride battery is used to store electric energy. The battery contains Nihydroxide and Co as the cathode activating agent and an alloy of Ni and mischmetal (mM), a rare-earth element mixture consisting of La, Ce, and Nd, as the anode hydrogen adsorption component. In conventional recycling, the Ni and Fe are recovered with a rotary kiln-electric melting process and the Co and mM go to the slag component [1] and hydrometallurgical treatment of crushed product consumes large volumes of agent. Japan Oil, Gas and Metals National Corporation have proposed a low energy and low cost recycling treatment process combining the physical and chemical treatments and the authors are investigating the physical treatment process."

Jan 1, 2008

By Vladyslav M. Sokolov

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

Jan 1, 2006

By Takahiko Okura

"It is said that the energy and resources crisis will come before long because the lifetime of known deposits of crude oil and common metals such as Pb, Zn, Cu is estimated to be less than 50 years. Establishing the sustainable society by means of resources-recycling has become an absolute necessity.The non-ferrous metals industry in Japan has been involved in the resource- recycling business for many years, along with the introduction and enforcement of various legislations to preserve the environment and natural resources. Including process-linkage during various manufacturing activities, the non-ferrous metals industry, the iron-making and cement industries are treating considerable amounts of recycled materials and wastes, in an environmentally-sound and economic manner.The Mining and Materials Processing Institute of Japan has submitted “The present and issues in Japanese non-ferrous metals and recycling industries.”The topic of the paper is to highlight the actual conditions within the resources-recycling structures and the present issues.IntroductionGlobalization has been changing the world, introducing the spike of energy and metals price. In addition, the preservation of the environment has also been strongly facing the crisis and many people have been aggrieved by both shortage and the increment in the price of the meals.In the world of metals, even though their reserves are coming depleted, the production rates are increasing, and then the industry has to enhance their productivity under stricter environmental regulations. The Japanese industry experimented the same scenario some 40 years ago, facing big pollution problems, but concurred them and enhanced the technology to overcome the more severe regulations. It will be fruitful to present the current situation in the Japanese industry for the world. The present issues are also presented."

Jan 1, 2008

Sodium is added to aluminum-silicon eutectic alloys to modify the structure. The ideal amount is about 100 ppm but due to the fact that sodium is lighter than aluminum and can float to the surface where it bums, oxidizes ad volatilizes, a far greater amount is usually added. Furthermore, as the sodium is continually lost from the alloy the optimum amount is only present for a limited time. The net result is a process which is hard to control, produces fumes and a considerable amount of dross. It is shown that by electrochemically titrating sodium through a tube of sodium beta alumina electrolyte that the sodium can be added continuously in a controlled way. As the sodium is added to the bulk of the aluminum, there is no sodium on the surface of the alloy so that little surface oxidation occurs, and no fumes and dross are produced. This leads to an improved product and working conditions.

Jan 1, 1995

By Asok Kumar Das

"In steel making ferroalloys occupies a commanding role for production of varied quality of steel. Ferroalloys enable alloying elements such as chromium, silicon, manganese, vanadium etc to be safely and economically introduced into metallurgical processes thus giving certain desirable properties of the alloyed metal. Their importance grew with the progress of the steel metallurgy which implied more diversified alloying elements, in better controlled quantities, in purer steel. The ferroalloy industry became a key supplier to the steel industry. Production of ferroalloys generally involves the use of Electric Arc furnace(EAF) into which raw materials(e.g. various metal ores, quartz, coke, lime etc ) with relatively fluctuating physical compositions are loaded. Due to this, one of the major environmental impacts of producing ferroalloys is the emission of dust and fume from the smelting process. INTRODUCTIONFerro Alloys are essential ingredients used for refining, de-oxidation, desulphurization and alloying addition in the production of different types of steel and hence Ferro Alloy industry forms a back bone of iron and steel in the world. Indian ferro alloy industry is more than 45 years old. It produces most of the bulk ferro alloys and a large number of special ferro alloys. The present installed capacity of the Indian ferro alloy industry is sufficient to meet the requirement of existing level of indigenous steel production of about 46 million tonnes. Revised National Steel Policy – 2008 envisages production of more than 100 million tonnes of steel by the year 2011-12, at proportionate annual growth rate per annum. The focus of the policy is to achieve global competitiveness not only in terms of cost, quality and product-mix but also in terms of global benchmarks of efficiency and productivity. In order to achieve the objectives of National Steel Policy and also to meet the requirement of ferro alloys, the Indian Ferro Alloy Industry has to gear up in terms of enhancement in production capacity, sourcing of raw materials, up gradation of technology, improvement in productivity, automation / mechanization, customer satisfaction etc."

Jan 1, 2008

By J. E. Murphy

Neodymium was electrowon into a Mg-Cd molten cathode at 650 °C from NdC1,-KC1 electrolyte. With the chloride system, neodymium was deposited into the molten alloy cathode until the neodymium concentration reached 20 wt pct. The alloy was then vacuum melted to remove the Mg and Cd. The current efficiency exceeded 80 pct under optimum conditions and the purity of the metal was 99.9 pct after vacuum melting. As an alternative approach, neodymium was electrowon at 1,030 °C from Nd,O, dissolved in a molten fluoride eleotrolyte. With the oxide-fluoride electrolyte, the metal was electrowon in a molten state with current efficiencies up to 60 pct. The purity of the metal was 99.8 pct with oxygen and carbon as major impurities. A number of problems were encountered including anode effect, low oxide solubility in the electrolyte, high neodymium metal solubility in the electrolyte, and reactivity of the metal with the cell materials. Approaches to improved cell, operation and prospects for commercial adoption of the electrolytic production of neodymium metal are discussed.

Jan 1, 1995

By Bo Yan, Jiaquan Zhang, Haibo Sun

"Based on the validation of steady-state isothermal mathematical model by a 0.4-scale water model for the single-strand slab casting tundish, the effect of varying pouring temperature on the flow, temperature field, and residence time distribution(RTD) of the liquid steel was studied by a transient hydrodynamic model. Due to the decreasing temperature of ladle stream over a casting period of 50 min, the direction of vortex flow at the downstream side of dam changes to clockwise from the anticlockwise at 4 min after the new teeming, and reverts to anticlockwise direction again at 43 min. Meanwhile, the melt flow state in the dam hole is also varying with time. For conventional isothermal water modeling, the RTD parameters obtained are much different as compared with the non-isothermal ones. For the flow control devices(FCD) design, however, the identical optimal scheme can be concluded from the point of view of isothermal modeling.IntroductionOriginally, tundish was adopted as a buffer and distributor to hold and allocate molten steel for sequence casting upon ladle exchange and to provide a desired steel flow rate to the mould below. With the increasing demand to strand quality, the tundish has become a critical metallurgical reactor to enhance inclusions removal, avoid reoxidation of molten steel, and prevent slag entrapment. The general trends to obtain these metallurgical effects are to optimize steel flow pattern and to extend the residence time of molten steel in the tundish through increasing the volume of tundish and/or using FCDs in the interior of the tundish."

Jan 1, 2012

By Lanre Oshinowo

The trend in process engineering is to design compact, more efficient processes, there is the paramount requirement to get the job done right the first time going from the drawing board to full-scale commercial operation. To accomplish this goal, there is also the need for tools beyond the traditional engineering toolkit to evaluate designs through virtual prototyping, thereby reducing the risks associated with making design decisions. One of the most important tools that has recently come to the forefront of process design and development is Computational Fluid Dynamics (CFD). CFD has been used at HATCH to address the key process parameters that drive the design of hydrometallurgical unit operations. This paper will detail the role of CFD at HATCH in achieving a superior level of confidence in the process design of autoclave circuits. Specifically, the optimum application of multiphase modeling including hydrodynamic, heat and mass transfer to hydrometallurgy operations, the impact of non-Newtonian slurry rheology on autoclave performance, and the challenges of optimizing the mixing of key reactants into slurries in autoclave reactors, is discussed.

Jan 1, 2003

By E. Almendras de Siegel

Pyrometallurgical processes have the thermodynamic capability of treating complex and dirty ores and concentrates to produce high purity metals and inert slags. Modem pyrometallurgical processes are environmentally sound and competitive with other processes. However, there is still a need for sensors and other practical tools that permit a rapid evaluation of the performance of these processes. In order to contribute to satisfying this fundamental requirement, the authors developed the IDENT.LA software that permits the automatic mineralogical analyses of inorganic materials, including the final and intermediate products of pyrometallurgical processes. The technique allows determining the grain size distribution of mineralized inclusions, the surface relations between metallic phases, and conducting modal analyses of the essential phases that are present in the samples. Three basic automatic operations are performed: creating a representative image of the sample; identifying the metallic and non-metallic phases; and measuring the features of the resulting image. The results are used to evaluate the performance of pyrometallurgical and other processes. In this paper, the authors discuss the application of the technique to a sample of slag from a slag cleaning process that uses a carbonaceous reductant. In this case, process performance impacts not only on the efficient reduction of the slag magnetite and on copper recovery but also on the quality of the process off-gas. The mineralogical analysis of the slag is a valuable tool in assessing process performance and in recommending changes of operating conditions.

Jan 1, 1999

By Gjergj Dodbiba, Toyohisa Fujita, Takahiro Kikuchi, I-Chen Wu

"In order to separate molybdenum (Mo) from the high-level radioactive liquid waste (HLLW), Pb-Fe based adsorbents were synthesized. The adsorbents were precipitated by adding sodium hydroxide in mixture of 1 mol/L lead nitrate and 1 mol/L ferric nitrate aqueous solutions. Each precipitate was then filtered, dried and ground to obtain a fine powder, which has been used as an adsorbent. Two main parameters were considered when synthesizing the adsorbents, i.e. the pH value at precipitation of adsorbent precursor and the calcination temperature of Pb-Fe based adsorbent. Moreover, the structures of the synthesized adsorbents were investigated by means of an X-ray diffractometer.The experimental results indicated that the calcination temperature of the Pb-Fe based adsorbent has a great influence on adsorption capacity of the adsorbent for Mo. It was found that when the Pb-Fe based adsorbent was calcinated at 500 oC, the sorbed concentration of Mo was the highest.1. IntroductionThe high-level radioactive liquid waste (HLLW), arising from the reprocessing of nuclear fuel are generally immobilized in an alkali borosilicate glass matrix. Broadly speaking, alkali borosilicate glasses are the matrix of choice for the immobilization of the HLLW, since they permit vitrification of waste stream of variable composition, [1]. Within this frame, the incorporation of molybdenum (Mo) is of particular interest in the vitrification of HLLW. Molybdenum is know to have a low solubility in borosilicate glass compositions and its presence in excess results in the phase separation of a complex yellow molten salt during vitrification, [1]. The formation of so-called “yellow phase” material during the vitrification process is undesirable since it leads to the accelerated corrosion of the inconel crucible liners. Furthermore, the “yellow phase”, which is reported to contain also other fission products, is soluble in aqueous solution providing a potential route for the leaching of radionuclides from the vitrified waste, should it come into contact with water, [1]."

Jan 1, 2008

By P. K. Narasimhargahavan

This paper discusses briefly the major reasons associated with the growth and its impact on the energy requirement and Environmental imbalance. A projection based on the present global Alumina and Al requirement indicate a substantial further growth of at least 30% over the next 10 years. It is indicated that the main factors which are likely to influence investments are the environmental factors such as the Climate Change and global response to the growing energy prices and sustainable development. Each of the developed / developing nations must find response to the GHG emissions which will encourage the Al Industry to make an effective contribution to global warming while preserving the international competitiveness of the industry - a challenging task. The efforts shall concentrate on improving energy efficiency in the industry possibly of the order of 25% over the next 10 to 20 years. The developments in this line are discussed.

Jan 1, 2010

By Christian Ludwig, Virginie Silberstein, Rizlan Bernier-Latmani, Simona Regenspurg

"Residues from waste incineration (bottom ashes) form large amounts of heavy metal-rich waste. Theoretically, heating and the addition of chloride to the ashes could remove these metals by formation of volatile metal chlorides. The remaining heavy metal-poor ashes could be used, for example, as cement additives. In the proposed process of our study we used bypass dust from the cement industry as chloride additives to the bottom ashes. We aim to determine experimentally the optimal conditions to remove heavy metals from ashes and to simulate this process by thermo- chemical modeling. In our experiment we investigate heavy metal flows by heating of differently composed mixtures of bottoms ash and bypass dust in dependence of different furnace temperatures (500-1200 °C). Furthermore, we investigate the reactivity (leaching characteristic) of the resulting product in order to predict if secondary residues can be landfilled in agreement to Swiss regulations for inert materials.IntroductionThe incineration of garbage is generally considered as the most environmentally friendly method for the reduction of municipal solid waste. This is because, compared to traditional storage of waste on landfills, incineration produces less greenhouse gases and destroys toxic organic compounds. The released exothermic energy can be recuperated and the residues from the combustion chamber (bottom ash) are strongly reduced in volume. However, they still form about 600 kt of waste per year in Switzerland, which needs to be landfilled. However, these residues could be potentially used as construction materials after mechanically recovering ferrous and non-ferrous metals. However, the resulting ashes (discharged dry or wet) still contain increased amount of heavy metals (exceeding state regulation) requiring them to be finally deposed on a hazardous waste site. A thermal treatment of these ashes could enable both, to separate and recuperate the remaining heavy metals and an inorganic heavy-metal poor material. The evaporation of metals depends on temperature and can be lowered by addition of chlorides, which would lower the boiling point of most metals by formation of metal chlorides (table 1). 745"

Jan 1, 2008

By Christian Ludwig, Virginie Silberstein, Rizlan Bernier-Latmani, Simona Regenspurg

"Residues from waste incineration (bottom ashes) form large amounts of heavy metal-rich waste. Theoretically, heating and the addition of chloride to the ashes could remove these metals by formation of volatile metal chlorides. The remaining heavy metal-poor ashes could be used, for example, as cement additives. In the proposed process of our study we used bypass dust from the cement industry as chloride additives to the bottom ashes. We aim to determine experimentally the optimal conditions to remove heavy metals from ashes and to simulate this process by thermo- chemical modeling. In our experiment we investigate heavy metal flows by heating of differently composed mixtures of bottoms ash and bypass dust in dependence of different furnace temperatures (500-1200 °C). Furthermore, we investigate the reactivity (leaching characteristic) of the resulting product in order to predict if secondary residues can be landfilled in agreement to Swiss regulations for inert materials.IntroductionThe incineration of garbage is generally considered as the most environmentally friendly method for the reduction of municipal solid waste. This is because, compared to traditional storage of waste on landfills, incineration produces less greenhouse gases and destroys toxic organic compounds. The released exothermic energy can be recuperated and the residues from the combustion chamber (bottom ash) are strongly reduced in volume. However, they still form about 600 kt of waste per year in Switzerland, which needs to be landfilled. However, these residues could be potentially used as construction materials after mechanically recovering ferrous and non-ferrous metals. However, the resulting ashes (discharged dry or wet) still contain increased amount of heavy metals (exceeding state regulation) requiring them to be finally deposed on a hazardous waste site. A thermal treatment of these ashes could enable both, to separate and recuperate the remaining heavy metals and an inorganic heavy-metal poor material. The evaporation of metals depends on temperature and can be lowered by addition of chlorides, which would lower the boiling point of most metals by formation of metal chlorides (table 1)."

Jan 1, 2008

By P. S. Arthur

The ISASMELT? process is a submerged lance smelting technology operating in smelters in Australia, the USA, Belgium, India, Germany, Malaysia and China. Further plants are under construction in Peru and Zambia. Following the invention of the Sirosmelt lance technology Mount Isa Mines recognised the commercial potential in the novel top blown bath smelting process and embarked on a development program that has lasted more than 25 years. After successful operation of pilot plants and demonstration plants producing copper and lead, Mount Isa Mines decided to license the technology to external companies. Since the purchase of Mount Isa Mines by Xstrata in 2003, Xstrata Technology has assumed responsibility for transferring the technology to ISASMELT? licensees. In the 15 years since the first commercial furnaces started operation plants have been constructed (or are under construction) with a combined annual smelting capacity of more than six million tonnes of concentrates or secondary raw materials. Process development continues on the commercial scale plants at Mount Isa and elsewhere. Many of the improvements implemented by plant operators have been passed on to, and adopted by, other licensees. Exchange of ideas and technical improvements occurs through ad hoc visits to fellow licensee sites and through regular licensee workshops arranged by Xstrata Technology. This paper updates the reader on the status of various ISASMELT? plants either operating or under construction. It highlights the important role that the technology provider?s operational experience plays in ensuring that new smelting plants ramp up quickly to nameplate capacity.

Jan 1, 2006

By James Wang

In July 2003, The Office of Hydrogen, Fuel Cells and Infrastructure Technologies of the Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy solicited Grand Challenge Proposals to establish three Centers of Excellence in hydrogen storage developments for reversible metal hydrides, non-reversible chemical hydrides and carbon storage materials, respectively. The program mission is to research and develop cost-effective, on-board hydrogen storage systems that enable a minimum range of 300 miles within the weight and volume constraints of the vehicle. Currently, no hydrogen storage technology available can meet the DOE cost and performance targets. In April 2004, Sandia National Laboratories was selected by DOE to lead the Metal Hydride Center of Excellence with partners from 5 other national laboratories. We will present the organization and recent accomplishments of the Metal Hydride Center which is confident to accomplish DOE/FreedomCAR and Fuels Partnership objectives for 2010 in hydrogen storage for vehicular transportation applications.

Jan 1, 2006

By Chu Yong Cheng

Synergists can be used in solvent extraction to improve the selectivity of extractants for metals. Research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy / CSIRO Minerals has shown that the pH isotherm of nickel with Versatic 10 was significantly lowered by the addition of the synergist Acorga CLX50. The paper discusses how this synergistic shift can be used to alleviate a gypsum formation problem at Bulong nickel laterite operation in Western Australia. Metal pH isotherms were obtained with Versatic 10 and synergist CLX50 using synthetic leach solutions. In terms of pH50, the extraction order of the metals with 0.5 M Versatic 10 alone was Cu > Zn > Ni > Co > Mn > Ca > Mg, whilst the extraction order with Versatic 10 and 20% by volume CLX50 was Cu > Ni Zn > Co > Mn > Ca > Mg with the pH50 (Mn-Co) significantlyincreased. This is significant because the isotherms of valuable metals Ni, Cu, Co and Zn shift more towards low pH than those of the waste metals Mn, Mg and Ca, resulting in a possible good separation of Ni, Cu, Co and Zn from Mn, Mg and Ca. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel plants make these processes complicated and costly in capital and operation. The research work carried by the SX groupat the AJ Parker Centre has led to the development of direct SX (DSX) processes to recover nickel and cobalt from leach solutions using synergistic organic systems. Semi-continuous tests with a BHP Billiton pilot plant leach solution showed that Ni and Co together with Zn and Cu were separated from the major impurities, Mn, Mg, Ca, and Cl, in the first SX circuit. The co-extracted impurities were easily scrubbed. After stripping, Ni and Co together with Zn and Cu were concentrated, resulting in a much smaller second SX circuit in the down stream processes.

Jan 1, 2003

By A. Kapilashrami

Slag foaming proves to be both blessing and curse for the process productivity, depending on where in the process it occurs. In pyrometallurgical processes, slag foaming is often a result of chemical reactions taking place in the slag. As the slag composition and reaction rates are changing, foaming occurs under dynamic conditions. In the present work, slag foaming was studied with XRF. The foam displayed a fluctuating behaviour, unaccountable by existing models. The concept of foaming index was found not to be satisfactory in describing the foam, resulting in the need for alternative theories. The rate of fluctuations was seen to be related to the difference between rate of gas generation and rate of gas escape from the system (Ug-Ue) as well as the bubble sizes. Thus, model development of dynamic foaming phenomenon has to take the effective chemical reaction rate as well as the bubble sizes into consideration. The first step in obtaining foam is to form bubbles. In the present work, gas bubbles were generated through chemical reaction at interface between two immiscible liquids and the bubble formation was studied optically. The gas bubble size was seen to be uninfluenced by the reaction rate. However, bubble formation was seen to take place in one of the phases and since the bubbles consequently traversed the interface under the influence of buoyancy, the viscosity of the first phase was found to influence the final bubble size where increased viscosity would yield a larger bubble size.

Jan 1, 2006

By Tabbetha A. Dobbins

We report studies concerning the time frame for catalytic reactions between NaAlH4 (sodium alanate) and TiCl3 during high energy milling. Spectral features in x-ray absorption spectra were analyzed for samples milled for various times (0 minutes, 1 minute, 5 minutes, 25 minutes, and 125 minutes). A structural transition from Ti3+ to Ti0 is observed within the first 5 minutes of milling. The Ti0 structure persists for samples milled for times longer than 5 minutes?even after those samples underwent a subsequent single hydrogen desorption/absorption cycle. Samples milled for less than 5 minutes retain Ti3+. For samples milled for 1 minute, the Ti-K edge position shifts from Ti3+ to Ti0 after a single desorption/absorption cycle. However, the first coordination sphere around the Ti0 absorber occurs at longer distances for 1 minute milled sample. These results hint at the formation of Ti0 pure metallic clusters upon desorption/adsorption cycling of 1 minute milled sample. Previously reported x-ray absorption spectroscopy studies have demonstrated the structural transition from Ti3+ (in TiCl3) to Ti0(determined to be TiAl3 found at the surface of the alanate powder). Aluminum deficiency on the NaAlH4 lattice is responsible for controlling hydrogen absorption capacity. These time-resolved spectroscopy studies suggest the possibility for controlling aluminum deficiency, while still maintaining titanium activation of the alanate powder, by manipulating the coordination environment of the titanium dopant during the first five minutes of high energy milling. Specifically, a possible approach to mitigating aluminum deficiency during doping would be to introduce an alternative species to which the to Ti3+ catalyst would form a metallic bond after the TiCl3 has attached at the surface of the sodium alanate powder and before the Ti3+ forms the TiAl3 intermetallic species.

Jan 1, 2006