Effects of Heat-Treatment on Photoluminescence Spectra and Photocatalytic Properties of Solution-Combusted ZnO Nanopowders.

ZnO nanopowders were prepared by a solution combustion method (SCM). The SCM ZnO nanopowders were heat-treated at 200, 400, 500, or 700 °C for 30 min in air and the photoluminescence (PL) of the nanopowders was evaluated. Two strong PL emission peaks are generally recognized as the unique PL signature of ZnO, one is from the band-edge emission and the other corresponds to green emission. The green emission is derived from crystalline defects, and is a critical obstacle for the electrooptical applications of ZnO. Surprisingly, the PL spectra of the SCM ZnO powders showed a single sharp peak near 390 nm. Furthermore, the intensity of this blue emission doubled when the synthesized ZnO powder was heat-treated at 400 °C. The green emission appeared for the sample treated at 500 °C, and was the highest for that treated at 700 °C. To comfirm the photocatalytic activity of the ZnO powder heat-treated at 400 °C, the removal of Ag ions from a used photofilm developer was evaluated, with complete removal within 10 min. The removal of the Ag ions by the ZnO powder heat-treated at 400 °C was more than two orders of magnitude faster than that achieved with the SCM ZnO powder. The relation between PL and photocatalytic activity was explained in terms of recombination of the photogenerated electrons. These results might be very useful for highly efficient photocatalyst applications.

Photoluminescence and Electrical Properties of ZnO Nanopowders Prepared by a Solution Combustion Method for Optoelectronic Device Application.

Nano-sized powders of ZnO phosphor were prepared by a solution combustion method (SCM). The ZnO powder prepared using Zn(OH)2 and glycine as the oxidant and fuel, respectively, (fuel/oxidant = 0.8), show good powder characteristics such as an average grain size of 30 nm and specific surface area of 120 m²/g. Single-phase ZnO powders were obtained regardless of the fuel/ oxidant ratio. The photoluminescence spectra of the obtained ZnO powders show a single sharp peak near 390 nm corresponding to a deep blue color. This was confirmed by cathodoluminescence measurement and CIE color coordinate values. The PL spectra, powder characteristics and electrical properties show very good consistency. Furthermore, the electron carrier concentration of the ZnO nanopowders prepared by SCM is more than 3 orders of magnitude higher than that of the purest ZnO single crystal, which is commercially available. These powders could be potentially applied as blue phosphors of displays such as A.C. powder electroluminescent devices and plasma display panels.

High Temperature Corrosion of TiAlCrSiN Films in N2/0.1%H2S Gas.

Nanomultilayered TiAlCrSiN film was corroded in N2/0.1%H2S-mixed gas at 900 °C for 5-300 h. It corroded to TiO2, α-Al2O3, and Cr2O3. From the early corrosion stage, not only the outward diffusion of Al, Ti, Cr, and Si but also the inward migration of oxygen occurred. As the corrosion proceeded, the outermost TiO2 layer, outer (Ti-depleted, (Al,Cr)-rich)-oxide layer, inner (Ti-rich, (Al,Cr)-depleted)-oxide layer, and partially oxidizing innermost film formed on the oxygenaffected film.

Effect of Al2O3 nano-filler on properties of glass-based seals for solid oxide fuel cells.

This study compares the viscosity and strength of three glass-based seals prepared with or without nano or micron-sized alumina powder used as filler material. Measurements of the viscosity and bending strength of the glass-based seals showed that addition of the nano-sized alumina powder to the glass increased both the high-temperature viscosity and the strength of the sintered glass matrix. Strength tests and observations of the microstructure of the fracture surface of the seal samples confirmed the strengthening of the glass network structure. Conversion of non-bridging oxygen to bridging oxygen is presumed to occur upon the addition of alumina to the glass sample. The strengthening of the alumina-glass composite seal was attributed to the alumina nano-filler and prolonged heat treatment at elevated temperatures.

High temperature oxidation of ZrO2/Al2O3 thin films deposited on steel.

Thin ZrO2/Al2O3 films that consisted of alternating monoclinic ZrO2 nanolayers and amorphous Al2O3 nanolayers were deposited on a tool steel substrate using Zr and Al cathodes in a cathodic arc plasma deposition system, and then oxidized at 600-900 degrees C in air for up to 50 h. The ZrO2/Al2O3 films effectively suppressed the oxidation of the substrate up to 800 degrees C by acting as a barrier layer against the outward diffusion of the substrate elements and inward diffusion of oxygen. However, rapid oxidation occurred at 900 degrees C due mainly to the increased diffusion and subsequent oxidation of steel as well as the crystallization of amorphous Al2O3.

Effect of solution combusted TiO2 nanopowder within commercial BaTiO3 dielectric layer on the photoelectric properties for AC powder electroluminescence devices.

A unique synthesis method was developed, which is called solution combustion method (SCM). TiO2 nanopowder was synthesized by this method. This SCM TiO2 nanopowder (-35 nm) was added to the dielectric layer of AC powder electroluminescence (EL) device. The dielectric layer was made of commercial BaTiO3 powder (-1.2 microm) and binding polymer. 0, 5, 10 and 15 wt% of SCM TiO2 nanopowder was added to the dielectric layer during fabrication of AC powder EL device respectively. Dielectric constant of these four kinds of dielectric layers was measured. The brightness and current density of AC powder EL device were also measured. When 10 wt% of SCM TiO2 nanopowder was added, dielectric constant and brightness were increased by 30% and 101% respectively. Furthermore, the current density was decreased by 71%. This means that the brightness was double and the power consumption was one third.

Oxidation of nano-multilayered AlTiSiN thin films between 600 and 1000 degrees C in air.

Multilayered AlTiSiN films with a composition of 32.0Al-12.4Ti-4.9Si-50.7N (at.%) were deposited on a steel substrate in a nitrogen atmosphere by cathodic arc plasma deposition. The films consisted of crystalline approximately 8 nm-thick AISiN nanolayers that originated from the Al-Si target and approximately 3 nm-thick TiN nanolayers that originated from the Ti target. Their oxidation characteristics were studied between 600 and 1000 degrees C for up to 20 h in air. They displayed good oxidation resistance due to the formation of a thin, dense Al2O3 surface scale below which an (Al2O3, TiO2, SiO2)-intermixed inner scale existed. They oxidized slower than TiN films because protective Al2O3-rich scales formed on the surface. However, they oxidized faster than CrN films because impure Al2O3 scale formed on the AlTiSiN film. Their oxidation progressed primarily by the outward diffusion of nitrogen and substrate elements, combined with the inward transport of oxygen that gradually reacted with Al, Ti, and Si in the film.

Effect of resin infiltration on the thermal and mechanical properties of nano-sized silica-based thermal insulation.

Several kinds of nano-sized silica-based thermal insulation were prepared by dry processing of mixtures consisting of fumed silica, ceramic fiber, and a SiC opacifier. Infiltration of phenolic resin solution into the insulation, followed by hot-pressing, was attempted to improve the mechanical strength of the insulation. More than 22% resin content was necessary to increase the strength of the insulation by a factor of two or more. The structural integrity of the resin-infiltrated samples could be maintained, even after resin burn-out, presumably due to reinforcement from ceramic fibers. For all temperature ranges and similar sample bulk density values, the thermal conductivities of the samples after resin burn-out were consistently higher than those of the samples obtained from the dry process. Mercury intrusion curves indicated that the median size of the nanopores formed by primary silica aggregates in the samples after resin burn-out is consistently larger than that of the sample without resin infiltration.

Effect of nanoparticle coating on the thermal conductivity of microporous thermal insulations.

Microporous thermal insulations were prepared from mixtures of nano-sized fumed silica, micron-sized fibers and opacifier particles. Those micron-sized particles were dry coated with nano-sized fumed silica particles by mechanical process using a compressive-shear type mill. The effect of nanoparticle coating on the thermal conductivity of the insulation media was investigated using a hot-wire method. Effect of nanoparticle coating was found to be more pronounced for the insulation composed of fumed silica and fiber than for the one composed of fumed silica, fiber and an opacifier. By adding 15% SiC or TiO2 opacifier, the thermal conductivity of the insulation samples could be lowered to 0.08 Wm(-1) K(-1) at temperature range of 805 approximately 817 degrees C. The temperature dependent thermal conductivity of the sample containing glass fiber did not exhibit any remarkable changes compared to the one containing ceramic fiber.

A review on the recycling processes of spent auto-catalysts: Towards the development of sustainable metallurgy.

Spent auto-catalysts are considered as promising platinum group metals (PGMs) resources based on their rapidly increasing demand along with the underlying uncertainty of the sustainability and long-term availability of PGMs. Recycling spent auto-catalysts presents attractive advantages, particularly for the conservation of primary resources reserves, and for the reduction of negative environmental impact due to exploitation. PGM reclamation is the major aim of recycling operations despite their minor concentration in spent auto-catalysts, which implies that the remaining materials are disposed of as unwanted solid waste after the extraction process. This poses a genuine challenge, as well as a motivation to develop recycling processes for spent auto-catalysts capable of recovering all components/valuable metals, while moderating environmental pollution and global warming. The focus herein involves the description of the available technologies, including pyro- and hydro-metallurgical processes, to recover PGMs from spent auto-catalysts, and specifically an analysis of the developmental trends in recycling methods to ensure "sustainable metallurgy".

Enrichment of the metallic components from waste printed circuit boards by a mechanical separation process using a stamp mill.

Printed circuit boards incorporated in most electrical and electronic equipment contain valuable metals such as Cu, Ni, Au, Ag, Pd, Fe, Sn, and Pb. In order to employ a hydrometallurgical route for the recycling of valuable metals from printed circuit boards, a mechanical pre-treatment step is needed. In this study, the metallic components from waste printed circuit boards have been enriched using a mechanical separation process. Waste printed circuit boards shredded to <10mm were milled using a stamp mill to liberate the various metallic components, and then the milled printed circuit boards were classified into fractions of <0.6, 0.6-1.2, 1.2-2.5, 2.5-5.0, and >5.0mm. The fractions of milled printed circuit boards of size <5.0mm were separated into a light fraction of mostly non-metallic components and a heavy fraction of the metallic components by gravity separation using a zig-zag classifier. The >5.0mm fraction and the heavy fraction were subjected to two-step magnetic separation. Through the first magnetic separation at 700 Gauss, 83% of the nickel and iron, based on the whole printed circuit boards, was recovered in the magnetic fraction, and 92% of the copper was recovered in the non-magnetic fraction. The cumulative recovery of nickel-iron concentrate was increased by a second magnetic separation at 3000 Gauss, but the grade of the concentrate decreased remarkably from 76% to 56%. The cumulative recovery of copper concentrate decreased, but the grade increased slightly from 71.6% to 75.4%. This study has demonstrated the feasibility of the mechanical separation process consisting of milling/size classification/gravity separation/two-step magnetic separation for enriching metallic components such as Cu, Ni, Al, and Fe from waste printed circuit boards.

Total recycling of all the components from spent auto-catalyst by NaOH roasting-assisted hydrometallurgical route.

Total recycling of all valuable metals such as PGMs, Ce, Al and Mg from the spent automobile catalysts has been explored. The alkali roasting was performed under NaOH, 0.5-3.0 g; temperature, 300-800 °C; and time, 10-60 min. The phase transformation from cordierite to the soluble products (NaAlO2, Na2MgSiO4) was influenced by the temperature, following the diffusion-controlled model (Ea(roasting), 6.4 kJ/mol). XRD analysis of the roasted mass revealed that the refractory phases of cordierite and γ-alumina could be eliminated at ≥600 °C at sample-to-NaOH mass ratio, 1:1. The leaching of the roasted mass followed an intermediate-controlled mechanism for aluminum leaching with (Ea(Al-leaching) value of 20.3 kJ/mol), while it was diffusion-controlled for magnesium leaching (Ea(Mg-leaching), 8.9 kJ/mol). At the optimum leaching condition (1.0 M H2SO4, 90 °C, 60 min, yielding >95% aluminum and magnesium), a significant amount of PGMs was also leached. Thereafter, the cementation process was investigated with Al0-powder that could precipitate >99% PGMs within 15 min at 90 °C. The yielded concentrate of PGMs and CeO2 was subsequently leached in 6.0 M HCl with 2.0 M NaClO3 that dissolved >97% PGMs, leaving the residue as the CeO2 concentrate. Individual metals can be recovered by following established separation and purification techniques.

Photocatalytic removal of Cu ions from aqueous Cu-EDTA solution using solution combusted zinc oxide nanopowder.

Nano-sized ZnO powder was prepared by "solution-combustion method (SCM)." The ZnO powder using Zn(OH)2 and glycine as an oxidant and a fuel (F/O = 0.8), showed good powder characteristics, such as average grain size of 30 nm and the specific surface area of 120 m2/g. and it was used as a semiconductor photocatalyst to remove Cu ions from aqueous Cu-EDTA solution. The result was then compared with other semiconductor photocatalyst powders such as titanium dioxide (TiO2) powder (P25, Degussa) and TiO2 powder prepared by homogeneous precipitation process at low temperature (HPPLT). The SCM ZnO nanopowder showed excellent photocatalytic properties. The Cu++ ions were completely removed from the solution within 90 min. However, for the other two powders, no complete removal of the ions was observed within the reaction time of 180 min. The ZnO powder synthesized at the fuel/oxidant ratio of 0.8, showed higher PL intensity at UV region than the other photocatalytic powders. The superior photoreduction ability of SCM ZnO nanopowder might be due to its excellent UV absorption capacity.

Effect of composition on thermal conductivity of silica insulation media.

Nano-sized fumed silica-based insulation media were prepared by adding TiO2 powders and ceramic fibers as opacifiers and structural integrity improvers, respectively. The high temperature thermal conductivities of the fumed silica-based insulation media were investigated using different types of TiO2 opacifier and by varying its content. The opacifying effects of nanostructured TiO2 powders produced by homogeneous precipitation process at low temperatures (HPPLT) were compared with those of commercial TiO2 powder. The nanostructured HPPLT TiO2 powder with a mean particle size of 1.8 microm was more effective to reduce radiative heat transfer than the commercial one with a similar mean particle size. The insulation samples with the HPPLT TiO2 powder showed about 46% lower thermal conductivity at temperatures of about 820 degrees C than those with the commercial one. This interesting result might be due to the more effective radiation scattering efficiency of the nanostructured HPPLT TiO2 powder which has better gap filling and coating capability in nano-sized composite compacts.

Hydrometallurgical recycling of surface-coated metals from automobile-discarded ABS plastic waste.

The ammoniacal leaching of surface-coated metals from automobile-discarded ABS plastics followed by their recovery through solvent extraction has been investigated. The leaching of ABS (typically containing 4.1% Cu, 1.3% Ni, and 0.03% Cr) could efficiently dissolve the ammine complexes of Cu and Ni, leaving Cr unleached as fine particles. The optimization studies for achieving the maximum efficiency revealed that the leaching of metal ions in different ammoniacal solutions follows the order CO32- > Cl- > SO42-. The leaching carried out in a carbonate medium by maintaining the total NH3 concentration 5.0 M at a NH4OH/(NH4)2CO3 ratio of 4:1, pulp density of 200 g/L, agitation speed of 400 rpm, temperature of 20 °C, and time of 120 min yielded the optimum efficiency of >99% Cu and Ni (i.e., 8.14 g/L and 2.57 g/L, respectively, in the leach liquor). Subsequently, the solvent extraction of metals from ammoniacal leach liquor as a function of extractant (LIX 84-I) concentration and organic-to-aqueous (O:A) phase ratio was examined. Based on the extraction data, a three-stage counter-current extraction at O:A = 1:1 was validated using 0.8 M LIX 84-I, yielding the quantitative extraction of both metals into the organic phase. Thereafter, the stripping of metals in acid solutions indicated that 0.5 M H2SO4 could quantitatively strip Ni from the loaded organic phase; however, ∼27% Cu was also co-stripped. The rest of Cu from the Ni-depleted organic phase was separately stripped with 1.0 M H2SO4 that can be directly sent to the electrowinning process. On the other hand, the co-stripped metals from the acidic solution can be easily separated, again using LIX 84-I as the extractant, by adopting the pH-swing method. Finally, a process has been proposed for the hydrometallurgical recovery of surface-coated metals from waste ABS plastics; that does not affect the physicochemical characteristics of the polymer substances for their reuse.

Electrothermal properties of porous ceramic fiber media containing carbon materials.

Electrically regenerable porous ceramic fiber media containing nanoporous carbon from 2.5% to 19.2% have been prepared for adsorption/regeneration system. An experimental apparatus was built for in situ measurement of the sample weight during adsorption and electrothermal desorption of gaseous adsorbates. Adsorption and electrothermal desorption behavior of gaseous adsorbates on carbon contained porous ceramic fiber media was explained by physical and electrothermal properties of these materials measured in this work. In situ thermal desorption and adsorption experiments show that a considerable amount of water vapor is adsorbed on the carbon contained media exposed to ambient air.

Photocatalytic reduction of nitrate in wastewater using ZnO nanopowder synthesized by solution combustion method.

ZnO nanopowder was synthesized by a unique method which is called solution combustion method (SCM). This nanopowder was used for a photocatalyst to decompose nitrate that is a toxic pollutant in wastewater. It has been known that TiO2, the most popular photocatalyst, does not decompose the nitrate. In this paper, however, the SCM ZnO nanopowder decomposed about 13% of nitrate. Furthermore, adding methanol as a hole scavenger, the decomposition rate was enhanced by about 5 times. On the other hand, it has been reported that the photocatalytic reduction reaction of nitrate produces ammonia as a final product. The present results, however, suggest that the final product is non-toxic nitrogen gas rather than the toxic ammonia. These results would be very valuable for drinking water purification.

Processing of rayon waste effluent for the recovery of zinc and separation of calcium using thiophosphinic extractant.

Zinc is used in various metallurgical, chemical and textile industries. In textile industries, waste effluent containing zinc is generated during the manufacture of rayon yarn. Due to the strict environmental regulations and the presence of toxic metallic and other constituents, the discharge of effluents in sewage is restricted. In view of above a process has been developed for the recovery of zinc from rayon waste effluent following solvent extraction technique using thiophosphinic extractants Cyanex 272 and 302. Before recycling of zinc sulphate solution in spinning bath, solution must be free from calcium, which is deleterious to the process as gypsum precipitates and forms scale. The extractant Cyanex 302 has been found selective for the recovery of 99.99% of zinc in the form of [R(2)Zn](org) from the effluent above equilibrium pH 3.4 maintaining the O/A ratio of 1/30 leaving all the calcium in the raffinate. The zinc from the loaded Cyanex 302 can be stripped with 10% sulphuric acid at even O/A ratio of 10. The stripped solution thus obtained could be recycled in the spinning bath of the rayon plant and raffinate could be disposed safely without affecting environment.

Recovery of H2SO4 from waste acid solution by a diffusion dialysis method.

A diffusion dialysis method using anion exchange membrane was used to recover H2SO4 from waste sulfuric acid solution produced at the diamond manufacturing process. Effects of flow rate, operation temperature, and metal ion concentration on the recovery of H2SO4 were investigated. The recovery of H2SO4 increased with the concentration of H2SO4 and operation temperature. It also increased with the flow rate ratio of water/H2SO4 solution up to 1, above which no further increase was observed. The flow rate did not affect the rejection of Fe and Ni ions. About 80% of H2SO4 could be recovered from waste sulfuric acid which contained 4.5M free-H2SO4 at the flow rate of 0.26x10(-3) m3/hm3. The concentration of recovered H2SO4 was 4.3M and the total impurity was 2000 ppm. Preliminary economic evaluation has revealed that the dialysis system is highly attractive one that has payback period of only few months.

High-Temperature Corrosion of Nano-Multilayered TiAISiN Thin Films in Ar-0.2%SO2 Gases.

Nano-multilayered TiAlSiN films with a composition of 26Ti-16.3Al-1.2Si-56.5N (at.%) were deposited onto steel via arc ion plating, and corroded at 800-900 °C for 30 h in Ar-0.2%SO2 gases. The films were corrosion resistant, because the oxidation process dominated sulfidation. The scales consisted primarily of Al2O3 and TiO2, where a small amount of Si dissolved.