Estudo da redução do NO pelo CO usando catalisadores de ródio suportado em óxido misto de cério e zircônio e óxido misto derivado de hidrotalcita

Esta tese teve como objetivo avaliar o desempenho de catalisadores de Rh suportados em cério-zircônio (CZ) e em óxido misto de magnésio e alumínio (HT) derivado de hidrotalcita na reação de redução do NO pelo CO em meio estequiométrico. Os suportes puros e impregnados com Rh foram nomeados CZ, RhCZ, HT e RhHT. Os suportes foram preparados por coprecipitação e o metal nobre foi adicionado no teor de 0,15% (m/m) por impregnação a seco. Foram realizados testes de caracterização como fisissorção de N2, DRX, TPR, espectroscopia Raman, DRIFTS, TGA-DTA e TPD-CO/NO. Para a avaliação catalítica, foi utilizada uma mistura de 1%NO + 1%CO em He e a atividade e seletividade foram expressas através das concentrações dos gases envolvidos ao longo de uma rampa de temperatura desde a temperatura ambiente até 500C. Os resultados de caracterização indicaram nítidas diferenças estruturais e físico-químicas entre os dois tipos de catalisadores nas isotermas de adsorção de N2, nos perfis de redução e nos difratogramas, já dando indícios de que os mecanismos de reação seriam diferentes. Pelas análises de DRIFTS identifica-se a presença de bandas características de espécies de CO adsorvidas no Rh somente para o catalisador RhCZ a baixa temperatura, ressaltando a interação Rh-CZ, também evidenciadas pelos resultados de Raman, mas que provavelmente não ocorrem com o óxido misto de Al e Mg. Observou-se que o suporte de CZ foi mais ativo a baixas temperaturas que o suporte de HT, porém o catalisador RhHT foi mais seletivo a N2 a 350C e emitiu menos N2O ao longo da faixa de temperatura avaliada do que o catalisador RhCZ. Resultados de TPD de NO e comparações de curvas experimentais e teóricas envolvendo as concentrações de CO, CO2 e NOx durante os testes catalíticos, acompanhados também pelas análises de DRIFTS nas mesmas condições, indicam que a redução do Rh e a afinidade do catalisador pelo NO são importantes para favorecer a maior seletividade da reação de redução do NO pelo CO a N2.

Influence of particle properties on the erosive wear of sintered boron carbide

Sintered boron carbide is very hard, and can be an attractive material for wear-resistant components in critical applications. Previous studies of the erosion of less hard ceramics have shown that their wear resistance depends on the nature of the abrasive particles. Erosion tests were performed on a sintered boron carbide ceramic with silica, alumina and silicon carbide erodents. The different erodents caused different mechanisms of erosion, either by lateral cracking or small-scale chipping; the relative values of the hardness of the erodent and the target governed the operative mechanism. The small-scale chipping mechanism led to erosion rates typically an order of magnitude lower than the lateral fracture mechanism. The velocity exponents for erosion in the systems tested were similar to those seen in other work, except that measured with the 125 to 150 μm silica erodent. With this erodent the exponent was initially high, then decreased sharply with increasing velocity and became negative. It was proposed that this was due to deformation and fragmentation of the erodent particles. In the erosion testing of ceramics, the operative erosion mechanism is important. Care must be taken to ensure that the same mechanism is observed in laboratory testing as that which would be seen under service conditions, where the most common erodent is silica.

The response of antioxidant systems in Nostoc sphaeroides against UV-B radiation and the protective effects of exogenous antioxidants

UV radiation is one of many harmful factors found in space that are detrimental to organisms on earth in space exploration. In the present work, we examined the role of antioxidant system in Nostoc sphaeroides Kutz (Cyanobacterium) and the effects of exogenously applied antioxidant molecules on its photosynthetic rate under UV-B radiation. It was found that UV-B radiation promoted the activity of antioxidant system to protect photosystem 11 (PSII) and exogenously applied antioxidant: sodium nitroprusside (SNP) and N-acetylcysteine (NAC) had an obvious protection on PSII activity under UV-B radiation. The activity of superoxide dismutase (SOD, EC 1.15.1.1), catalase (CAT, EC 1.11.1.6), peroxidase (POD, EC 1.11.1.7) and content of NIDA (malondialdehyde) and ASC (ascorbate) were improved by 0.5 mM and 1 mM SNP, but 0.1 mM SNP decreased the activity of antioxidant system. Addition of exogenous NAC decreased the activity of SOD, POD, CAT and the content MDA and ASC. In contrast, exogenously applied NAC increased GSH content. The results suggest that exogenous SNP and NAC may protect algae by different mechanisms: SNP may play double roles as both sources of reactive free radicals as well as ROS scavengers in mediating the protective role of PSII on algae under UV-B radiation. On the other hand, NAC functions as an antioxidant or precursor of glutathione, which could protect PSII directly from UV-B radiation. (c) 2007 COSPAR, Published by Elsevier Ltd. All rights reserved.

The involvement of the antioxidant system in protection of desert cyanobacterium Nostoc sp against UV-B radiation and the effects of exogenous antioxidants

In this study, we found that UV-B radiation decreased photosynthetic activity and boosted lipid peroxidation of desert Nostoc sp., and exogenous chemicals (ascorbate acid (ASC), N-acetylcysteine (NAC), and sodium nitroprusside (SNP)) had obvious protective effects on photosynthesis and membranes under UV-B radiation. High-concentration SNP boosted the activities of antioxidant enzymes, but low-concentration SNP reduced the activities of antioxidant enzymes. Both NAC and ASC treatments of cells decreased activities of antioxidant enzymes. The results suggested that those chemicals possibly had different mechanisms of protection of algae cells against UV-B radiation. SNP might play double roles as a signal molecule in the formation of algae cell protection of Photosystem 11 under UV-B radiation and as a (reactive oxygen species) scavenger, while NAC and ASC might function as antioxidant reagents or precursors of other antioxidant molecules, which could protect cells directly against ROS initiated by UV-B radiation. (c) 2006 Elsevier Inc. All rights reserved.

Fourier spectrum based extraction of an equivalent trap state density in indium gallium zinc oxide transistors

Segregating the dynamics of gate bias induced threshold voltage shift, and in particular, charge trapping in thin film transistors (TFTs) based on time constants provides insight into the different mechanisms underlying TFTs instability. In this Letter we develop a representation of the time constants and model the magnitude of charge trapped in the form of an equivalent density of created trap states. This representation is extracted from the Fourier spectrum of the dynamics of charge trapping. Using amorphous In-Ga-Zn-O TFTs as an example, the charge trapping was modeled within an energy range of ΔEt 0.3 eV and with a density of state distribution as Dt(Et-j)=Dt0exp(-ΔEt/ kT)with Dt0 = 5.02 × 1011 cm-2 eV-1. Such a model is useful for developing simulation tools for circuit design. © 2014 AIP Publishing LLC.

Quantum mechanical effects in nanometer field effect transistors

The atomistic pseudopotential quantum mechanical calculations for million atom nanosized metal-oxide-semiconductor field-effect transistors (MOSFETs) are presented. When compared with semiclassical Thomas-Fermi simulation results, there are significant differences in I-V curve, electron threshold voltage, and gate capacitance. In many aspects, the quantum mechanical effects exacerbate the problems encountered during device minimization, and it also presents different mechanisms in controlling the behaviors of a nanometer device than the classical one. (c) 2007 American Institute of Physics.

Time-resolved photoluminescence studies of AlInGaN alloys

We study the two samples of AIInGaN, i.e., 1-mum GaN grown at 1030degreesC on the buffer and followed by a 0.6-mum-thick epilayer of AIInGaN under the low pressure of 76 Torr and the AIInGaN layer deposited directly on the buffer layer without the high-temperature GaN layer, by temperature-dependent photoluminescence (PL) spectroscopy and picosecond time-resolved photoluminescence (TRPL) spectroscopy. The TRPL signals of both the samples were fitted well as a stretched exponential decay at all temperatures, indicating significant disorder in the material. We attribute the disorder to nanoscale quantum dots or discs of high indium concentration. Temperature dependence of dispersive exponent beta shows that the stretched exponential decay of the two samples comes from different mechanisms. The different depths of the localization potential account for the difference, which is illustrated by the results of temperature dependence of radiative recombination lifetime and PL peak energy.

Growth and photoluminescence of InAlGaN films

Two quaternary InAlGaN films were grown by metal-organic chemical-vapor deposition (MOCVD) on sapphire (0001) substrates with and without high-temperature GaN interlayer, respectively. The structural and optical properties of the quaternary films were investigated by high-resolution X-ray diffraction (HRXRD), high-resolution electron microscopy (HREM), temperature-dependent photoluminescence (PL) spectroscopy and time-resolved photoluminescence (TRPL) spectroscopy. According to the HRXRD and PL results, it is demonstrated that two samples have the same crystal quality. The TRPL signals of both samples were fitted well as a stretched exponential decay from 14 K to 250 K, indicating significant disorder in the materials, which is attributed to recombination of excitons localized in disorder quantum nanostructures such as quantum dots or quantum disks originating from indium (In) clusters or In composition fluctuation. The cross-section HREM measurement further proves that there exist disorder quantum nanostructures in the quaternary. By investigating the temperature dependence of the dispersive exponent beta, it is shown that the stretched exponential decays of the two samples originate from different mechanisms. (C) 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

碳化硅中氦离子高温注入引入的缺陷及其退火行为的光谱研究

对氦(He)离子高温(600K)注入6H-SiC中的辐照缺陷,在阶梯温度退火后演化行为的拉曼光谱和室温光致发光谱的特征进行了分析.这两种方法的实验结果表明,离子注入所产生晶格损伤的程度与注入剂量有关;高温退火导致损伤的恢复,不同注入剂量造成的晶格损伤需要不同的退火温度才可恢复.在阶梯温度退火下呈现出了点缺陷的复合、氦-空位团的产生、氦泡的形核、长大等特性.研究表明:高温(600K)注入在一定剂量范围内是避免注入层非晶化的一个重要方法,为后续利用氦离子注入空腔掩埋层吸杂或者制备低成本、低缺陷密度的绝缘层上碳化硅(SiCOI)材料提供了可能.

Asymmetric heat conduction in nonlinear lattices

In this Letter, we conduct an extensive study of the two-segment Frenkel-Kontorova model. We show that the rectification effect of the heat flux reported in recent literature is possible only in the weak interfacial coupling limit. The rectification effect will be reversed when the properties of the interface and the system size change. These two types of asymmetric heat conduction are governed by different mechanisms though both are induced by nonlinearity. An intuitive physical picture is proposed to interpret the reversal of the rectification effect. Since asymmetric heat conduction depends critically on the properties of the interface and the system size, it is probably not an easy task to fabricate a thermal rectifier or thermal diode in practice.

Experimental investigation of transfer ionization mechanism in slow He2+ -He collisions

The processes of transfer ionization in He2+ -He collisions at energies ranging from 20 to 40 keV have been studied experimentally by means of cold target recoil ions momentum spectroscopy. From the longitudinal momentum spectra of recoil ions, different mechanisms of transfer ionization have been obtained. The results show that one of the electrons of helium atom being captured into the ground state of projectile ion He2+ and the other one emitted to the continuum state of projectile or target are the dominant mechanisms of transfer ionization. The autoionization cross section of projectile after two-electron capture into a double excited state is small. Transfer ionization for one target electron capture into ground state and the other one into the continuum of projectile mainly occurs at large impact parameter collisions.

Unique properties of Ir/ZSM-5 catalyst for NO reduction with CO in the presence of excess oxygen

The reduction of NO with CO in the presence of excess oxygen was investigated over different noble metal catalysts for probing the relationship between catalytic properties and adsorption behaviors. Among the four precious metal catalysts investigated, Ir/ZSM-5 was found to be the only active one for NO reduction with CO under lean conditions. With the decreasing of the Ir content, higher NO conversion and CO selectivity was obtained. Temperature-programmed reaction (TPR) studies of NO/H-2/O-2 and NO/CO/O-2 showed that the Pt/ZSM-5 was active when H-2 was used as the reductant, whereas, the Ir/ZSM-5 was active when CO was the reducing agent. This difference is due to the different mechanisms of the two reactions. Temperature-programmed desorption (TPD) of NO, CO and O-2 showed that NO could dissociate more easily over the Ir/ZSM-5 than on the Pt/ZSM-5, while the oxidation of CO by O-2 proceeded more rapidly on the Pt/ZSM-5 than on the Ir/ZSM-5. The presence of excess O-2 inhibited drastically the dissociation of NO, which is considered as the key step for the NO-CO reaction. The high dissociation rate of NO over the Ir/ZSM-5 is visualized as the key factor for its superior high activity in NO reduction with CO under lean conditions. (C) 2002 Elsevier Science B.V. All rights reserved.

Ultrathin-film growth of para-sexiphenyl (I): Submonolayer thin-film growth as a function of the substrate temperature

The para-sexiphenyl (p-6P) monolayer film induces weak epitaxy growth (WEG) of disk-like organic semiconductors, and their charge mobilities are increased dramatically to the level of the corresponding single crystals [Wang et al., Adv. Mater. 2007, 19, 2168]. The growth behavior and morphology of p-6P monolayer film play decisive roles on WEG. Here, we investigated the growth behavior of p-6P submonolayer film as a function of the substrate temperature. Its growth exhibited two different mechanisms at high and low substrate temperature.

Mechanism on flame retardancy of polystyrene/clay composites-The effect of surfactants and aggregate state of organoclay

Effects of organically modified montmorillonites (OMMTs) with different type and amount of modifiers on flame retardancy of polystyrene (PS) have been studied. The results from morphology analysis, gas chromatography-mass spectrometry and cone calorimeter have showed different mechanisms for the flame retardancy of PS/OMMTs composites, depending on surface property of OMNTrs. One is the catalysis of acid sites formed on the surface of octadecylammonium modified MMT (c-MMT) via Hoffman decomposition on the carbonization of degradation products, which promotes the formation of clay-enriched char barrier.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.