Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N2O. HCl greatly increases CO and CH4 emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO2 system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K. (C) 2009 Elsevier Ltd. All rights reserved.

Structure and UV emission of nanocrystal ZnO films by thermal oxidation of ZnS films

ZnO films prepared by the thermal oxidation of the ZnS films through thermal evaporation are reported. The as-deposited ZnS films have transformed to ZnO films completely at 400 degrees C. The 400-700 degrees C annealed films with a preferential c-axis (002) orientation have a hexagonal wurtzite structure. The band gap of ZnO films shifts towards longer wavelength with the increase of the annealing temperature. The relationship between the band gap energy of ZnO films and the grain size is discussed. The shift of the band gap energy can be ascribed to the quantum confinement effect in nanocrystal ZnO films. The photoluminescence spectra of ZnO films show a dominant ultraviolet emission and no deep level or trap state defect emission in the green region. It confirms the absence of interstitial zinc or oxygen vacancies in ZnO films. These results indicate that ZnO film prepared by this simple thermal oxidation method is a promising candidate for optoelectronic devices and UV laser. (c) 2005 Elsevier BN. All rights reserved.

Rapid quantification of total microcystins in cyanobacterial samples by periodate-permanganate oxidation and reversed-phase liquid chromatography

Microcystins (MCs) comprise a family of more than 80 related cyclic hepatotoxic heptapeptides. Oxidation of MCs causes cleavage of the chemically unique C-20 beta-amino acid (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda) amino to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB), which has been exploited to enable analysis of the entire family. In the present study, the reaction conditions (e.g. concentration of the reactants. temperature and pH) used in the production of MMPB by oxidation of cyanobacterial samples with permanganate-periodate were optimized through a series of well-controlled batch experiments. The oxidation product (MMPB) was then directly analyzed by high-performance liquid chromatography with diode array detection. The results of this study provided insight into the influence of reaction conditions on the yield of MMPB. Specifically, the optimal conditions, including a high dose of permanganate (>= 50 mM) in saturated periodate solution at ambient temperature under alkaline conditions (pH similar to 9) over 1-4 h were proposed, as indicated by a MMPB yield of greater than 85%. The technique developed here was applied to determine the total concentration of MCs in cyanobacterial bloom samples, and indicated that the MMPB technique was a highly sensitive and accurate method of quantifying total MCs. Additionally, these results will aid in development of a highly effective analytical method for detection of MMPB as an oxidation product for evaluation of total MCs in a wide range of environmental sample matrices, including natural waters, soils (sediments) and animal tissues. (C) 2009 Elsevier B.V. All rights reserved.

Kinetic study of the 2-methyl-3-methoxy-4-phenylbutanoic acid produced by oxidation of microcystin in aqueous solutions

Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.

Kinetics of the oxidation of MCRR by potassium permanganate

The occurrence of the microcystins in the water bodies, especially in drinking water resources, has received considerable attentions. In situ chemical oxidation is a promising cost-effective treatment method to remove MC from water body. This research investigated the reaction kinetics of the oxidation of MCRR by permanganate. Experimental results indicate that the reaction is second order overall and first order with respect to both permanganate and MCRR, and has an activation energy of 18.9 kJ/mol. The second-order rate constant ranges from 0.154 to 0.225 l/mg/min at temperature from 15 to 30 degrees C. The MCRR degradation rates can be accelerated through increasing reaction temperature and oxidant concentration. The reaction under acid conditions was slightly faster than under alkaline conditions. The half-life of the reaction was less than 1 min, and more than 99.5% of MCRR was degraded within 10 min. (c) 2005 Elsevier Ltd. All rights reserved.

Sulfur-induced exciton localization in Te-rich ZnSTe alloy

Exciton localization in Te-rich ZnSTe epilayers has been studied by photoluminescence (PL) and time-resolved PL. The sulfur-related exciton emission is found to dominate the radiative recombination at low temperature and is shifted to the low energy with the increase of S concentration. By measuring the PL dependence on temperature and by analyzing the PL decay process, we have clarified the localization nature of the sulfur-related exciton emission. Furthermore, the difference of the localization effect in Te- and S-rich ZnSTe is also compared and discussed. © 2005 American Institute of Physics.

Photoluminescence degradation in GaN induced by light enhanced surface oxidation

The exponential degradation of the photoluminescence (PL) intensity at the near-band-gap was observed in heavily doped or low-quality GaN with pristine surface under continuous helium-cadmium laser excitation. In doped GaN samples, the degradation speed increased with doping concentration. The oxidation of the surface with laser irradiation was confirmed by x-ray photoemission spectroscopy measurements. The oxidation process introduced many oxygen impurities and made an increase of the surface energy band bending implied by the shift of Ga 3d binding energy. The reason for PL degradation may lie in that these defect states act as nonradiative centers and/or the increase of the surface barrier height reduces the probability of radiative recombination.

Enhanced near-infrared photoluminescence from isoelectronic luminescent centers in sulfur-implanted silicon with copper or silver coimplantation

Enhanced near-infrared photoluminescence (PL) from sulfur-related isoelectronic luminescent centers in silicon was observed from thermally quenched sulfur-implanted silicon in which additional copper or silver ions had been coimplanted. The PL from the sulfur and copper coimplanted silicon peaked between 70 and 100 K and persisted to 260 K. This result strongly supports the original conjecture from the optical detection of magnetic resonance studies that the strong PL from sulfur-doped silicon comes from S-Cu isoelectronic complexes [Frens , Phys. Rev. B 46, 12316 (1992); Mason , ibid. 58, 7007 (1998).]. (c) 2007 American Institute of Physics.

Effect of oxidation on the optical and surface properties of AlGaN

The chemical properties of AlxGa1-xN surfaces exposed to air for different time periods are investigated by atomic force microscopy (AFM), photoluminescence (PL) measurement and X-ray photoelectron spectroscopy (XPS). PL and AFM results show that AlxGa1-xN samples exhibit different surface characteristics for different air-exposure times and Al contents. The XPS spectra of the Al 2p and Ga 2p core levels indicate that the peaks shifted slightly, from an Al-N to an Al-O bond and from a Ga-N to a Ga-O bond. All of these results show that the epilayer surface contains a large amount of Ga and Al oxides. (c) 2006 Elsevier B.V. All rights reserved.

Effects of the sulfur pressure on pyrite FeS2 films prepared by sulfurizing thermally iron films

The effect of sulfur vapor pressure in preparing the FeS2 films has been discussed and some incongruous views about sulfur pressure have been clarified in this paper based on experimental results and theoretical analysis. It is shown that lower sulfur pressures than the saturation value only result in poorer crystallization and worse performances, and in other words the FeS2 films could be optimized through improving the sulfur pressure till the saturation point. However for a certain temperature the sulfur pressure is limited by its saturated vapor pressure, and further increase of the sulfur quantity reacted with Fe films has little influence on the structure and properties of the pyrite films. (C) 2003 Elsevier B.V. All rights reserved.

Electronic properties of sulfur passivated undoped-n(+) type GaAs surface studied by photoreflectance

Photoreflectance (PR) has been used to study surface electronic properties (electric field, Fermi level pinning, and density of surface states) of undoped-n(+) (UN+) GaAs treated in the solution of ammonium sulfide in isopropanol. Complex Fourier transformation (CFT) of PR spectra from passivated surface shows that the sulfur overlay on GaAs surface makes no contribution to Franz-Keldysh oscillations (FKOs). The barrier height measured by PR is derived from surface states directly, rather than the total barrier height, which includes the potentials derived from Ga-S and As-S dipole layers. Comparing with native oxidated surface, the passivation leads to 80 meV movement of surface Fermi level towards the conduction band minimum, and reduction by more than one order in density of surface states. (C) 2003 Elsevier Science B.V. All rights reserved.

Determination of oxidation states in magnetic multilayers

X-ray photoelectron spectroscopy has been used to characterize the oxidation states in Ta/NiOx/Ni-81/Fe-19/Ta magnetic multilayers prepared by rf reaction and dc magnetron sputtering. The exchange coupling field and the coercivity of NiOx/Ni81Fe19 are studied as a function of the ratio of Ar to O-2 during the deposition process. The chemical states of Ni atoms in the interface region of NiOx/NiFe have also been investigated by x-ray photoelectron spectroscopy and the peak decomposition technique. The results show that the ratio of Ar to O-2 has a great effect on the chemical states of nickel in NiOx films. Thus the exchange coupling field and the coercivity of Ta/NiOx/Ni81Fe19/Ta are seriously affected. Also, the experiment shows that x-ray photoelectron spectroscopy is a powerful tool in characterizing magnetic multilayers.