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By T. C. Goel, A. Venna, R. G. Mendiratta

"Processing of ferrites has gained tremendous importance in recent times to meet the high performance demands on ferrites in keeping with the fast emerging· technologies. The quality of ferrite powders has strong influence on ·the performance of final device. Fabrication· of high performing ferrite components requires starting ferrite powders of precise stoichiometry, purity and microstructure. It is difficult to obtain these attributes by the conventional ceramic method. The key to obtaining quality powders lies in the· solution techniques. With this in view soft ferrites have been prepared by a wet chemical process, known as the citrate precursor method, which involves the formation of citrate complexes of the constituent cations. The advantages of this process are the ease of preparation and close control of composition, homogeneity, purity and particle size. Electrical and magnetic measurements on lithium ferrites have shown resistivity higher by more than two orders of magnitude compared to that observed for samples prepared by the conventional ceramic method, and low magnetic losses, making the ferrites specially suitable for high frequency applications.IntroductionProperties of ferrites are known to be sensitive to .their processing technique. A small deviation in the compositional stoichiometry of the ferrite affects its properties greatly. Soft ferrites such as Ni-Zn, Mn-Zn and Mg-Mn. are well known ferrites covering wide-ranging applications [1,2]. Lithiiim ferrites have also assumed technological importance for microwave applications and are potential substitutes for the expensive garnets [3]. Lithium ferrites are often doped with zinc to tailor the saturation magnetization required at high frequencies. Lithium and lithium-zinc ferrites, however, present difficulty to processing due to the volatile nature of both the cation components, namely Li and Zn. These ions are volatile at temperatures > 1000°C which makes their processing difficult. One of the main considerations of high frequency performance of ferrites is the high eddy current losses which prevent the interaction of the magnetic field with the ferrite component and hence impair device performance. These losses can be reduced by having a material of high resistivity. Electrical conductivity in lithium ferrite has been attributed to electron hopping [4] between the two vaience states of iron, Fe2+ <=> Fe3+, on octahedral sites. Maintaining the + 3 valence state of otahedral- Fe ions is thus a prerequisite for achieving high resistivity. The resistivity of ferrites is normally found to be low when processed by the conventional solid-state or the ceramic method [5]. This is attributed to (a) extensive ball-milling employed in the method to mix the component oxides results in non-stoichiometric compositions due to introduction of additional Fe ions on abrasion of steel balls during milling, (b) high processing temperatures involved which result in significant volatilization of Li and Zn ions creating thereby oxygen non-stoichiometry which results in reduction of Fe3 + to Fe2 +, (c) large and non-uniform grain sizes. In the present work, preparation of Li and Li-Zn ferrites by a non-conventional method known as a citrate precursor method [6, 7] which requires lower processing temperatures and duration is reported. The method gives stoichiometric compositions on account of homogeneous atomic-scale mixing of the constituent cations via the formation of metal-citrate complexes mixed in solution state. The method is also capable of giving small grain size which aids the oxidation ofFe2+ ions."

Jan 1, 2000

By Mathilde Guilpain

A wide variety of plants are able to extract nickel (Ni) from soils and accumulate this metal in their foliage. Hydrometallurgical processes have been developed to recover Ni in the form of metal or salts, starting from the plant A. murale. They include: (1) a combustion step, to obtain ash containing 15–20% Ni; (2) a leaching step; and (3) purification. That whole flowsheet has been thoroughly investigated, and the processes scaled up to the pilot scale. Another strategy is presented here, consisting of recovering Ni without burning the plant. Ni can be extracted from the dry plant by water leaching, but the leachate is a multi-element solution from which Ni has to be separated. Selective precipitation of Ni hydroxide is not possible since Ni is bound to organic ligands. In this work, the plant leachate is processed by adsorption on the chelating resin DOWEXTM M4195. The results showed that Ni was selectively retained whereas the other main cations were not. Nickel could be recovered at the elution step. This methodology needs to be further investigated but these initial results are very encouraging and open the possibility of Ni recovery by agromining.

By Jing-she Li, Hai-yan Tang, Cheng-song Liu, Wei Liu

"In order to effectively utilize cheap and low quality iron ores, a hematite ore in a certain steel plant in Xinjiang was researched on to obtain ""iron increase and silicon reduction"" by ore dressing operation experiment and the performance indexes of the hematite ore were optimized. Based on the fundamental characteristics and high-temperature properties of the concentrate after ore dressing and other five kinds of iron ores which were co=only used in this steel plant, ore matching principles were proposed and a sintering ore blending optimization model was established. Finally, sinter pot test was carried out to verify the validity and practicability of the sintering ore blending optimization model which was aimed at giving consideration to the sintering indexes and the cost.IntroductionIn recent years, the price of imported iron ore with high quality is always at a high level, while iron ore self-sufficient rate in China is less than 50%. Enormous market demand and high dependence of domestic enterprises on imported iron ore makes the price of it hardly return to rational. In order to get rid of the situation of long-term meager profit and even deficit, more and more iron and steel enterprises in China transit their focus of reducing production cost to the utilization and development of relatively cheap but low-grade iron ore resources at home[l-4l_ However, besides the disadvantages of low iron grade, high content of impurities and complex embedded properties, the high-temperature properties of iron ore often go beyond the suitable ranges for producing sinter with high quality. Thus directly utilization of this kind of iron ore without ore dressing process would probably affect the metallurgical performance and indexes of sinter ore.Previous research and production practice have shown that traditional iron ore matching in sintering mainly focus on the reasonable collocation of properties of iron ores with low quality and high quality, but pay less attention to ore dressing process of low quality iron ores and matching them with high quality iron ores. Actually, compare with directly utilization, iron ores with low quality after ore dressing have higher suitability for matching with high quality ones which is beneficial to reduce the consumption of iron ores with high quality and control the production cost of sintering [5-s1."

Jan 1, 2014

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"&apos;) was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

By Masayoshi Matswnoto

The Kosaka Smelter and Refinery produces copper and lead, and has a history of more than 100 years as a metallurgical department of Dowa?s Kosaka Mine. The Smelter treats complex sulfide concentrates which are difficult to smelt. Valuable metals are recovered using various processes developed by Kosaka Smelter and Refinery. Effluent waters from the smelter contain large quantities of heavy metals. This paper describes how Kosaka Smelter and Refinery recovers valuable metals from various effluent waters and handles overall waste waters in order to meet strict environmental standards.

Jan 1, 1993

By Xiaojie Gao, Jingshe Li, Chengsong Liu, Haiyan Tang

In order to clarify the reaction between MnO-SiO2 oxides with low FeO content and Fe-Mn-Si alloy, two diffusion couples were produced by the new method using confocal scanning laser microscopy (CSLM). The interface of the alloy and oxide, content of Mn and Si in the alloy near the interface, size distribution and composition of the particles which precipitated in the alloy were observed and analyzed using the electron probe microanalysis (EPMA). Results show that though the FeO content in the oxides decrease to 1% which is lower than the equilibrium with the molten steel at 1873K, the diffusion of oxygen from oxide to alloy still exists during the heat treatment at 1473K and causes shorter Particle Precipitated Zone (PPZ) and Manganese Depleted Zone (MDZ) normally for the reduction of diffusion flux of oxygen.

Jan 1, 2015

By Markus Aspiala, Fiseha Tesfaye, Pekka Taskinen

In this paper, the standard thermodynamic properties of Ag3Sb and Ag6Sb intermetallic compounds have been studied by the solid state EMF-method, using Ag+ ion conducting β- alumina and AgI. The intermetallic compounds were synthesized from pure substances in evacuated silica ampoules and their formation were confirmed by the SEM-EDS analyses. The EMF measurements were made on electrochemical cells of the type [Ag | β-alumina | Ag-Sb] and [Ag | AgI | Ag-Sb]. The usage of β-alumina electrolyte, in this study, enabled thermodynamic measurements of the Ag-Sb-intermetallic compounds above 710 K, hitherto unreported. Based on the new experimental data, thermodynamic properties of the Ag-Sb-intermetallic compounds have been determined. The obtained experimental values have been compared with the available literature data.

Jan 1, 2015

By cheng Peng-fei, TANG Hai-yan, guo Xiao-chen, LI Jing-she, Liang Yong-cang, Zhao Baojun

The origin and evolution of non-metallic inclusions for Al-killed casing steel during EAF-LFVD- CC process were studied by industrial tracer experiments. The formations of Al2O3 and MgO·Al2O3 micro- and macro-inclusions from ladle slag were analyzed by theoretical calculations. The results show that micro-inclusions were formed during deoxidation and temperature decreasing in the process of casting, most of the macro-inclusions come from entrapped ladle and mold slags. In addition, most of the Al2O3 formed were modified into 12CaO·7Al2O3 and 3CaO·Al2O3 inclusions which are liquid at steelmaking temperature. MnS cannot be fully modified to CaS and it was only wrapped outside the alumina or calcium aluminate in the form of (Ca,Mn)S with the amount of Ca-Si wire fed during the test.

Jan 1, 2016

By Manju Gurung, Birendra Babu Adhikari, Keisuke Ohto, Hidetaka Kawakita, Katsutoshi Inoue, Shafiq Alam

Novel bio-adsorbent gel was prepared by immobilizing functional groups of glycidyltrimethyl ammonium chloride, a kind of quaternary ammonium chloride, onto polymer matrices of persimmon extract for the recovery of precious metals such as palladium(II) and platinum(IV) from chloride media. It was found that this adsorption gel exhibits high selectivity to gold(III), palladium(II) and platinum(IV) over base metals such as copper(II) and iron(III) while crude persimmon extract, the feed material, exhibits high selectivity only for gold(III). From the adsorption isotherms study, the maximum adsorption capacities for gold(III), palladium(II) and platinum(IV) were evaluated as 3.30, 1.67 and 1.00 mol/kg, respectively. Those for palladium(II) and platinum(IV) are higher than those of simple quaternary ammonium chloride type of chemically modified persimmon tannin gel and commercially available anion exchange resin.

Jan 1, 2016

By Zhengjie Chen, Wenhui Ma, Jijun Wu, Kuixian Wei

The gasification reactivity of PC (petroleum coke), strengthened by addition of different potassium carbonate proportions using different grinding medium, was investigated by using thermogravimetric analysis (TGA). Results showed that the gasification reactivity of PC not only increased with the increase of catalyst-loaded, but also showed the effective improvement by anhydrous alcohol. The PC was mixed with potassium carbonate [K2CO3] catalyst at 0.5%, 0.8%, 1.0% and 1.5%, and then ground wet with distilled water. The CO2-gasification rate of PC was only 77.35%, 80.55%, 84.07% and 85.88% under the gasification temperature 1100 °C and holding time 120 min, at different K2CO3 respectively. However, when the PC was ground in anhydrous alcohol at the same condition of catalyst-loading, the gasification rate of PC reached 95.43%, 96.63%, 95.50% and 95.61% at the holding time of 108 min, 101 min, 74 min and 35 min, respectively. It was shown by FTIR, SEM and EDX determinations that the anhydrous alcohol used as the grinding medium can further improve the gasification reactivity of PC when compared with the distilled water.

Jan 1, 2016

By Yuanbo Zhang, Zhixiong You, Li Qin, Guanghui Li, Tao Jiang

Low-grade manganese oxide ore is generally characterized by high iron content. In this work, sulfidation roasting of an iron-rich manganese oxide ore with elemental sulfur was characterized. The experimental results indicated that manganese dioxide can be selectively reduced over iron oxide by using elemental sulfur. The manganese phases in roasted product included low-valence manganese oxide, manganese sulfide and manganese sulfate, while those of iron mainly depended on the sulfur addition. Iron oxide would only be reduced or sulfidized at larger sulfur additions. The effect of roasting temperature and S/Mn mole ratio on the phase transformations was also investigated; extractions of Mn/Fe by sulfuric acid were evaluated. An extraction of Mn greater than 95% was obtained while that of Fe was controlled less than 10% under the optimal conditions.

Jan 1, 2016

By Xinlei Jia, Wenming Guo, Yanling Zhang

A large amount of stainless steel dust rich in Fe, Cr, and Ni has been being generated in China. Smelting treatment is accepted as a practical method for the recovery/reutilization of these second resources, during which Fe, Cr, and Ni is reduced into one metal phase and then separated from the residue slag. Based on the typical compositions of stainless steel dust, the residual slag can be termed as CaO-SiO2-MgO-Al2O3 system. In this paper, the activity coefficients of Cr in Fe-Cr-Ni-C (-Si/Al) melt and the properties of CaO-SiO2-MgO-Al2O3- 1%CrO system thermodynamically approached. Then, in laboratory experiments, the recovery ratios of Cr and its distribution behaviors between Fe-Cr-Ni-C melt and CaO-SiO2-MgO-Al2O3 slag system were examined.

Jan 1, 2015

By Jesús Contreras

Since the commencement of its activities in Huelva in 1970, Atlantic Copper has maintained a course of action that has been more demanding than the successive environmental legislations current at different times. As its primary objective it has sought compatibility between the protection of the environment and both its industrial activity and the social and economic development of the area in which its Metallurgical Complex is located. For this reason, since the seventies it has maintained a continuous programme of investments which have allowed it to attain its present environmental situation. As a consequence of the Environmental Policy of Atlantic Copper, in April 1998 it obtained certification for its Integrated System of Environmental Management (SIGMA) according to international standard IS0-14001, and under European Community Regulation 1836/93 (replaced by the 76112001) for the Eco-Management and Eco-Audit System (EMAS). The SIGMA formalises the environmental management practices of Atlantic Copper and engages it to have available a system that can be fully audited. Atlantic Copper was the first European Company in the non-ferrous metallurgical sector to obtain both the UNE-EN-ISO 14001 certification and the EMAS registration. The present paper reviews the actions by Atlantic Copper in environmental matters that have allowed it to achieve its present position. It also describes the coming stages of improvement planned and the modifications to be carried out in the near future, in particular the criteria for the selection of technologies on the basis of the concept of BAT (Best Available Techniques) introduced by the European Union, and always guided by the final objective of converting Atlantic Copper into a reference within the sector, comparable to the best designed and operated installations in the world.

Jan 1, 2003

By Batric Pesic

Gold dissolution with bromine was studied by using the rotating disc technique. Geobram TM 3400 was used as a source of bromine. The parameters studied were: rotating speed, Geobrom 3400 concentration, pH, temperature, sulfuric and hydrochloric acid concentration, and the concentration of various cations (copper, iron, zinc, aluminum, manganese, potassium and sodium) and anions (chloride, bromide, sulfate, nitrate, and iodide) According to the Levich plot and activation energy, gold dissolution was controlled by a chemical reaction rate. Copper, iron, and manganese in their highest oxidation states, aluminum, zinc, sodium and potassium did not have any effect on gold dissolution rate. The presence of manganous ion dramatically decreased the gold dissolution rate. Kinetic performance of bromine, in the form of Geobram TM 3400, was compared with performance of cyanide and thiourea.

Jan 1, 1990

By Ann M. Hagni

"Ceramic matrix composites are inorganic materials that are particularly resistant to heat and abrasion. A magnesia (MgO) and aluminum nitride (AlN) based composite is formed by exposing a magnesia preform to a metallic alloy block in a nitrogen atmosphere at 950°C. The metallic alloy, which is composed primarily of aluminum, is wicked into the preform. Aluminum nitride matrix is grown between MgO particles as the wicked metallic aluminum reacts with nitrogen. Unused metallic alloy, remnant metallic alloy (carcass), and composite produced after 8 hours, 50 hours, and 225 hours of processing are characterized mineralogically. Reflected light microscopy, transmitted light microscopy, scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction techniques reveal that in addition to anhedral to euhedral AhNi, AbSbSr, and Al crystallizing in the metallic alloy carcass, AIN and (Al,Si)N have formed as well. Nitride rings and nodules in the carcass may hinder AIN growth in the composite. Fine-grained residual AhNi and AhShSr are dispersed throughout the composite matrix. The nitride matrix is composed of AIN and (Al,Si)N. Rim replacement of MgO by spine! occurs in the composite. Aluminum nitrides in the metallic carcass cathodoluminesce deep violet-blue, unlike non-luminescent AIN in the composite matrix. This distinction in cathodoluminescence suggests a different mode of formation for composite AIN than for carcass AIN. Phase interpretations and textural characterizations deduced from the implementation of sophisticated mineralogical techniques have contributed to the understanding, and will aid in the improvement, of MgO/ AlN-based ceramic matrix compositeprocessing."

Jan 1, 1999

By S. N. Ojha, Gouthama, R. K. Mandal

"Spray deposition processing of liquid immiscible alloys, based on AI-Pb and Cu-Pb systems have been investigated. Process variables have been optimized to generate uniform dispersion of ultrafine second phase particles in· the matrix of the primary phase. Mechanisms governing the microstructural evolution in this synthesis methodology are discussed. Results of the present investigation are used to demonstrate that rapid solidification of atomized droplets initially provides a high nucleation rate of the second phase during the liquid phase separation. The solid matrix phase nucleates at a later stage and grows with a high velocity enabling trapping of the dispersed phase. Subsequent alteration in the size and size distribution of the second phase is suggested to arise further during deposition of high velocity droplets. Possible reasons for this effect are brought out. Microstructural features of atomized powders and spray-deposits of these alloys are presented to support the present approach of synthesizing composites. IntroductionIn recent years, synthesis of advanced materials with metastable microstructures and ultra fine dispersion of second phase particles has led to the development of novel techniques of materials processing. The other requirement of such a processing methodology is to achieve near-net shape geometries in less number of processing steps. The solidification processing method via spray deposition route qualifies these criteria. This process primarily involves atomization of a melt by high energy gas jets into spray of droplets which are subsequently propelled by the kinetic energy of the gas towards a deposition substrate to build-up a thick high density preform. Although the concept of spray deposition was pioneered by Singer [1] in the early seventies, the fundamentals of the deposition process has been understood only recently [2-4]. Several benefits of spray deposition processing are by now well established [5,6]. Rapid solidification effects are inherent in spray deposition processing due to high heat exchange rate at the droplet-gas interface and also on the deposition surface by force convection. Since considerable heat extraction occurs from the atomized spray prior to droplet consolidation, a relatively low processing temperature is ensured in this process. As a result deleterious coarsening phenomenon can be minimized. In addition, controlled maneuvering of the substrate provides the capability of the process in producing disc, sheet or tube shape preforms of difficult to work materials in a single operation. A significant improvement in properties, resulting from microstructural homogeneity and refinement in grain size induced by spray deposition has been reported for several alloy systems [7,8]."

Jan 1, 1994

By G. L. Watt

Fine sized titanium diboride (TiB2) powders have been synthesized in a thermal plasma reactor. Precursor for the synthesis were rutile, boron oxide, and methane. The effect of plasma gas type, precursor ratio, and input power on the synthesis was studied. The produced powders were characterized by X-ray diffraction and chemical analysis. The purified powders were CIP&apos;d, HIP&apos;d, sintered and characterized for porosity, hardness, and microstructure and the results compared with a commercially available TiB2 powder sample.

Jan 1, 1995

By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By Wenya Du, Qingbo Yu, Peng Li, Qin Qin

"A new heat recovery system is proposed. This system uses the endothermic heat of gasification reaction instead of sensible heat to recover the energy of molten blast furnace slag. The gasification technological parameter in molten blast furnace was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer. The results showed that, according to different gasification agent, this system can produce syngas with different C-H ratio. The exergy efficiency of this system is high and its internal exergy loss rate is about 11%. This method can bring huge economic and environmental benefits which are important to the survival and sustainable development of iron-steel enterprises. The molten BF slag acts as not only thermal media but also good catalyst. The kinetic parameters on gasification reaction with different types of coal used differ from each other.IntroductionEnergy consumption in the iron-making process is about 50%~60% of the total energy input. The blast furnace is very important in the iron & steel process. So energy conservation and emission reduction about blast furnace is very important. In recent years, in order to recovery energy, many new technologies such as TRT (Top gas pressure Recovery Turbine) and CCPP (Combined Cycle Power Plant) were used in iron-making. But the energy of molten blast furnace (BF) slag has only been used limitedly so far.Molten BF (Blast Furnace) slag is the byproduct of iron-making at the high temperatures range from 1723 to 1923K, and has a large amount of sensible heat remaining. The yield of molten BF slag is about 300 kg per ton of pig iron. In conventional processes, molten BF slag is quenched rapidly using a large amount of water to produce a glassy-granulated slag. The quenching slag must be dried before it can be used in cement manufacture. During the process, a large amount of water was consumed and the energy of molten slag can not be recovered. At the same time, it causes environmental pollution problems. So the critical problems of the process are not only energy recovery of molten slag and reducing emission of H2S and SO2, but also guaranteeing the subsequent use value of slag. For this propose, many new technologies were investigated to recover the thermal energy of molten slag. The promising methods are dry granulation [1-4] and reforming of methane [5-9]. The method, utilization of reaction heat instead of latent heat and sensible heat, is quite attractive from viewpoints of energy storage without heat loss, and makes a connection to other industry. But both of them are in laboratory. In this paper, coal gasification in molten BF slag was used to recover the energy of molten BF slag. The gasification technological parameter in molten BF was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer."

Jan 1, 2011

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014