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By Vadym Drozd, Yongzhou Sun, Shah Najiba, Jiuhua Chen, Andriy Durygin

"Phase transitions of the potential hydrogen storage compound, ammonia borane (NH3.BH3), was investigated using Raman spectroscopy and a diamond anvil cell at high pressures up to 9.5 GPa and low temperatures down to 90K. At room temperature, ammonia borane has three phase transitions in this pressure range. Upon cooling, four new phases were discovered through changes in characteristic Raman spectra. This result provides information about the stability of new bonding characteristics of this potential hydrogen storage material at low temperature and high pressure region.IntroductionDevelopment of hydrogen technology requires the safe, efficient and environmental friendly materials for hydrogen storage and hydrides have attracted much attention as hydrogen storage media. Among chemical hydrides, ammonia borane (BH3NH3) stands out due to its high gravimetric and volumetric hydrogen density ' "". Despite high hydrogen content, this compound is very stable. It releases hydrogen in several steps by thermal decomposition in the temperature range of 100°C to 500°C. Direct thermal decomposition also causes toxic borazine emission. Recent research interests on ammonia borane include destabilizing this compound to lower the dehydrogenation temperature with an enhanced hydrogen release rate using different techniques, e.g. the nanoscaffolds'', ionic liquids"" and acid'"" or transition metal catalysts' ""'. As a molecule of ammonia borane consists of protonic (NH) and hydritic (BH) hydrogens bonded by the polarized dative bond, thermal or catalyzed decomposition requires breaking of N-H and B-H bonding. Still now, the detailed information about the bonding characteristics of ammonia borane is not sufficient to understand details about its phases and structures. The development of methods to enhance hydrogen discharge rate from ammonia borane requires a detailed study about the structural and dynamical properties that control the stability and the intermolecular interactions of this material. This study is motivated to investigate the stability of the existing phases and also to explore the existence of any new phases at different temperatures and pressures which may have enhanced hydrogen release and uptake properties."

Jan 1, 2012

By Desmond Cook, Cynthia P. Dogan, Dale Govier, Gary Korth, James C. Rawers

"The microstructural and mechanical properties of iron powders processed in an attrition mill are highly dependent upon the processing environment. Extended high-energy ball milling in argon resulted in nanocrystalline bcc-Fe microstructure, while processing in nitrogen or alloying with carbon resulted in both nanocrystalline bcc-Fe and bct-Fe microstructures. In this U.S. Bureau of Mines study, both X-ray diffraction and Mössbauer analysis were used to show that the infused carbon and nitrogen concentrations were predominantly on the grain boundaries. Explosive consolidation resulted in a fully dense product with microstructure similar to the microstructure of the mechanically processed powder. Hardness values of the compacts correlated highly with grain size, independent of the processing conditions.IntroductionNanocrystalline materials have been theorized and shown to have unique properties that make them interesting for material scientists and promising for material engineering applications. Several conferences have been devoted solely to the techniques of preparing nanostructured materials have been held(l,2,3.). To date, most techniques used to generate nanocrystalline materials produce only a few grams of particles(1). High-energy ball-milling, however, is an efficient and effective technique that can produce substantial quantities of nanocrystalline materials with homogenous chemical composition that cannot be produced by conventional processing techniques(3).Applications and material evaluations of nanocrystalline materials require several grams of solid samples. Because nanocrystalline microstructures' are thermodynamically unstable, producing consolidated macro structures of nanocrystalline material has proved to be very difficult(2,3). In particular, retention of the nanocrystalline microstructure during consolidation of nanocrystalline particles has proven to be a problem. In contrast to many consolidation techniques that require elevated temperatures, explosive compaction uses a shock wave for consolidation( 4,5)."

Jan 1, 1994

By Donna L. Bodine

The ability of oxidized Upper Freeport bituminous coal to adsorb Cu2+, Cd2+ and Mn(VII) from very dilute aqueous solutions has been studied. Low-rank coal is known to adsorb heavy metal ions from dilute, aqueous solutions, probably by ion exchange and/or chelation by acidic functional groups on the coal surface. However, it would be advantageous to use higher rank coals for water treatment. Coal samples were oxidized thermally or by 30% H202 to increase the surface concentration of phenolic and carboxylic groups, then portions were shaken with Cu2+ and Cd2+ solutions. Acidic KMnO4 was also used to oxidize coal, with concurrent sorption of the resulting Mn(IV) and Mn(ll). The effect of oxidation treatment, metal ion concentration, and solution pH on metal uptake kinetics was investigated. Potential applications for treating effluents, especially those containing oxidizing ions, are discussed, along with possible flowsheet options.

Jan 1, 1995

By Jean-Pierre Birat, Ana-Maria Iosif, Denis Ablitzer, Olivier Mirgaux

"Integrating environmental considerations into the product traditional process design is now the major challenge for steel industry. Life Cycle Assessment (LCA) is nowadays considered as an appropriate method for assessing environmental impact and selecting new technologies to reduce CO2 emissions for steel industry.In this paper we propose a new methodological concept which combines LCA thinking with process simulation software in order to carry out the life cycle inventory of classical steelmaking process.Using Aspen PlusTM software, a physicochemical model has been developed for the integrated steelmaking route. This model gives the possibility to carry out life cycle inventories for different operational practices in order to optimise the use of energy, to calculate CO2 and other emissions and to control the mass and the heat balances of processes.It is also shown that such approach can be used to design and assess new technologies for steelmaking without large industrial application.IntroductionDuring recent years, it was recognised that CO2 emissions are the major factor of the global warming effect. In order to meet Kyoto requirements, the steel industry is embracing the challenge of sustainable development by improving its competitiveness and economic success while reducing its environmental impacts. Integrating environmental considerations into the traditional product design process, for powerful eco-efficiency, is now one of the major priorities for steelmakers.The European Steel Industry has measured up to this challenge by creating ULCOS (Ultra Low CO2 Steelmaking) consortium that has taken up the mission to develop breakthrough steelmaking process with the potential to reduce CO2 emissions (Eurofer, 2005). In order to develop technologies to reduce emissions, it is necessary to assess the environmental impact of the classical steelmaking route (coke plant, sinter plant, blast furnace, basic oxygen furnace, continuous casting and hot rolling)."

Jan 1, 2009

By M. M. Kim

As-electrogalvanized coatings of pure Zn, Zn-11% Fe, and Zn-18% Fe coatings were characterized in terms of initial crystal structure and surface morphology. Samples were then subjected to heat treatments simulating the paint bake cycle of automobile manufacturers. Surface morphology changes were correlated with the process variables, and crystallo.graphic changes were interpreted by mapping heat treatment routes on the Fe-Zn phase diagram. The morphology of pure zinc electrogalvanized coatings with heat treatment from platelets to smeared platelets. The zn-11% Fe coating changes with heat treatment from tetrahedral nodules to a mixture of round and tetrahedral nodules, with the Zn-:18% Fe coating always having round nodules. Regarding crystal structure, a critical transformation time can be defined at any selected temperature, below which the crystal structure does not change. This temperature is related to iron content.

Jan 1, 1990

By Varuzan Kevorkijan

A new method for faster production of functionally graded metal-ceramic laminates is based on reactive pressureless counterflow infiltration/penetration of a ceramic substrate with two different metallic infiltrants. The porous or dense ceramic preform is pressurelessly infiltrated or penetrated from one side by the first metallic infiltrant to the desired cross section of the preform, producing the top layer made up of the solidified infiltrant and the underlayer consisting of reactive infiltrated preform. The partly infiltrated perform is then completely infiltrated starting from the other side by the second metallic infiltrant, in this way fabricating the internal layer, consisting of the ceramic perform infiltrated with the second infiltrant and the bottom layer formed by the solidified second infiltrant. Systems already investigated include carbide, nitride and boride ceramic performs infiltrated with aluminum and magnesium alloys.

Jan 1, 2003

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By Kazuki Morita

A new route to produce solar grade silicon (SOG-Si 6N) from metallurgical grade (MG-Si 98%) has been developed in Japan, which may satisfy the increasing demand for solar cells in the near future. Since some elements such as P and B have very large segregation coefficients, solidification refining is not effective for their removal and costly processes, such as electron beam vacuum melting and oxidation plasma refining, are required. According to our previous results which showed the effectiveness of leaching procedure with Ca addition for Fe and Ti removal, possibility of P and B removal by acid leaching was focused expecting that their affinities for Ca in molten silicon might be considerable. Hence, the effects of Ca addition on the thennodynamic properties of P and B in molten silicon alloys have been investigated for overall control and optimization of the SOG-Si production process in the present study. The interaction parameters between Ca and P, and Ca and B were determined by chemical equilibration techniques at 1723 K. Although the interaction parameter between Ca and B was slightly negative, that between Ca and P showed a large negative value. Also, the results for the leaching test with various amount of Ca addition revealed that the removal fractions of both elements, especially P, drastically increased with increase in the Ca content, which showed very good agreement with the prediction from the interaction parameters derived in the present work. The present results suggest that the preliminary leaching procedure can reduce the processing time and energy for SOG-Si refining. Keywords: Silicon, Solar Cell, Refining, Acid Leaching, Thennodynamics. Interaction, Phosphorus, Boron, Calcium

Jan 1, 2003

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reprodueible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CuzS-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in CuzS-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at 1200°C; (iii) Phase equilibria and thennodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thennodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By A. R. Udupa

The reduction roasting behavior of chalcopyrite has been investigated using various combinations of a desulfurizing agent, i.e., CaO or Na2CO3, and a reductant, i.e., CO, H2 or C. Using these, combinations the sulfur is removed from the mineral as CaS or Na2S rather than SO2 as is the case with conventional copper smelting and converting. The laboratory reduction ex¬periments were conducted using thermogravimetric analysis (TGA) and boat tests of mixed combinations of fine particulate reactants subjected to a continuous gas stream. The degrees of metallization were determined by both weight loss and chemical analysis methods and the products examined using optical and scanning electron microscopy and electron probe microanalysis. The percent reduction after one hour at 900°C ranged from 60% to 94%. From these data It was possible to provide postulations as to the controlling reduction mechanisms.

Jan 1, 1983

By J. F. White

An experimental study was undertaken to evaluate the feasibility of a selective chloridizing roasting pre?treatment process for the elimination of impurities from zinc feed?stocks prior to recovering zinc by conventional unit operations. In this investigation, a number of chemistries that might serve as a basis for such a pre? treatment process were examined. A variety of chloridizing agents were admixed with EAF dust to promote the selective removal of lead and cadmium by the formation of volatile metal chlorides, he results of the experimentation firmly establish that selective chloridizing roasting is a technically feasible means of eliminating lead and cadmium from EAF dust. Excellent extraction efficiencies were accomplished with a number of chloride additives; as high as 98 percent lead extraction and 88 percent cadmium extraction were attained with minimal zinc losses, Continuous pilot?scale tests reinforced the trends established by laboratory?scale experimentation, Attempts of chlorine elimination using pyrohydrolysis were less successful. The extent of chlorine elimination was found to be highly dependent upon EAF dust sample type and treatment temperature.

Jan 1, 1996

By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By A. V. Tarasov

The proposed process is based on creating a controlled frothed layer of molten slag, in which fine particles of carbonaceous reductant and raw material to be processed are mixed with emulsified iron. Frothing of the slag layer without external blowing occurs as a result of intensive evolution of gaseous reduction products. The froth reaction process is maintained due to the heat of an electric arc in the slag layer. When the metal bath is heated by the arc to 1400- 1 500°C, the low temperature of the slag surface of about 1200-1 300°C is maintained due to low thermal conductivity of slag froth preventing heat loss. In order to maintain the required slag froth level and control the process temperature, air tuyeres are installed above the slag bath; blowing air serves also for oxidation of zinc in fumes and for its transportation. High adsorption and thermal insulating properties of slag froth ensure virtually complete elimination of dust and mist entrainment along with low heat losses. The main macrokinetic regularities of the carbon thermal reduction of zinc-containing slag melts have been studied under frothing conditions. The mechanism of formation of gas-slag emulsion has been identified under the conditions of reaction [C]+[O]=CO occurring locally at the slag-metal interface. It has been demonstrated that under the froth reduction conditions the zinc removal rate from the melt increases on the average by 3 to 5 times. Based on the physical and chemical data obtained, basic principles of the dezincing technology have been developed for different intermediate oxide iron-containing products produced in the process of ferrous and non-ferrous metals production.

Jan 1, 2002

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By George Owusu

A study has been carried out on the use of solvent extraction, instead of the traditional zinc dust cementation process, to remove copper from concentrated zinc sulphate leach solutions. In a series of experiments using plant solution containing 1.9 g/L Cu, 2 g/L Fe, 173 g/L Zn, 7.9 g/L H,SO,, 0.25 g/L Cd, 15 mg/L Co etc. and LIX 622 in SX-1, up to about 97-98 % of copper present in the zinc sulphate leach solution was extracted with negligible co-extractions of zinc, iron, cadmium, cobalt, etc. pH modification was not required for this reagent. The copper loaded organic was almost completely stripped using 150 g/L sulphuric acid. Investigations into the effect of any possible organiclextractant contamination on zinc electrowinning showed (if any) little effect on current efficiency if the organic contamination is less than 45 ppm; current efficiencies of 95-97 % were obtained. At organic contaminations higher than 45 ppm, the current efficiency dropped to about 92- 94 %. Visually, the organic-contaminated cathode sheets had rough surface morphology, becoming more intense with increasing organic concentration, compared to the non-contaminated cathode sheets.

Jan 1, 1998

By L. Sh. Tsemekhman

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

Jan 1, 2003

By Chunhua Liao, Chao Peng, Guangsheng Huo

To get the separation of tungsten and molybdenum, we adjusted the pH of the solution to 7, at which tungstate (WO4 2-) will be polymerized into HW6O21 5-, while molybdate will still exist in the form of MoO4 2-. Two strongly basic anion exchange resins (D201, D213) were experimented for the separation of tungsten and molybdenum. The results of condition experiments indicate that D213 resin performs better in the treatment of lower concentration solution A (WO3 10g/L, Mo 4.12g/L) with a separation factor as high as 10.64. While D201 resin is more suitable for the high concentration solution B (WO3 70g/L, Mo 28.97g/L) with a separation factor of 6.9. The results of column testing performed on D213 resin show that the solution after loading process with a mass ratio of Mo/WO3 = 50 and the desorption solution with a mass ratio of WO3/Mo = 27 can be obtained

Jan 1, 2014

By Yousef Mohassab, Manoranjan Misra, Monalisa Panda, Eman Wahbah

This work studies the removal of arsenic (V), arsenate, and arsenic (III), arsenite, from aqueous solution using calcined Quintinite-3T. The two adsorbents Quintinite-3T was prepared, calcined at different temperatures, and characterized by XRD, BET, and SEM. The surface area of the calcined Quintinite-3T was 193.4 m2/g. The particles size ranged from 12 to 56 nm for the uncalcined Quintinite-3T and from 24 to 42 nm for the calcined Quintinite-3T. Kinetic analysis, adsorption isotherm, and factors affecting the adsorption were investigated. Calcined Quintinite- 3T retained As(v) and did not release it back to water even after an entire month.

Jan 1, 2016

By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus, The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn3O4) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6,7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn)04 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10.5 m2/s range. The pore size was mainly between 0.1 and 10 um,

Jan 1, 2003