Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Intrinsic terahertz plasmon signatures in chemical vapour deposited graphene

Plasmonic resonance at terahertz (THz) frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz, which appear as absorption peaks when the graphene is electrostatically p-doped and change to enhanced transmission when the graphene is n-doped. Superimposed on the Drude-like frequency response of graphene, these resonance features are related to the inherent poly-crystallinity of CVD graphene. An understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. © 2013 AIP Publishing LLC.

All-chemical vapor deposited graphene/silicon nitride TFTs

All-chemical vapor deposited silicon nitride / monolayer graphene TFTs have been fabricated. Polychromatic Raman spectroscopy shows high quality monolayer graphene channels with uniform coverage and significant interfacial doping at the source-drain contacts. Nominal mobilities of approximately 1900 cm 2V-1s-1 have been measured opening up a potentially useful platform for analogue and RFR-based applications fabricated through allchemical vapor deposition processes. © The Electrochemical Society.

Synthesis and characterization of ZnO nanoflowers grown on AIN films by solution deposition

ZnO nanoflowers are synthesized on AIN films by solution method. The synthesized nanoflowers are composed of nanorods, which are pyramidal and grow from a central point, thus forming structures that are flower-shaped as a whole. The nanoflowers have two typical morphologies: plate-like and bush-like. The XRD spectrum corresponds to the side planes of the ZnO nanorods made up of the nanoflowers. The micro-Raman spectrum of the ZnO nanoflowers exhibits the E-2 (high) mode and the second order multiple-phonon mode. The photoluminescence spectrum of the ZnO nanoflowers exhibits ultraviolet emission centred at 375 nm and a broad green emission centred at 526 nm.

Bulge testing and fracture properties of plasma-enhanced chemical vapor deposited silicon nitride thin films

The mechanical properties and fracture behavior of silicon nitride (SiNx) thin film fabricated by plasma-enhanced chemical vapor deposition is reported. Plane-strain moduli, prestresses, and fracture strengths of silicon nitride thin film; deposited both oil a bare Si substrate and oil a thermally oxidized Si substrate were extracted using bulge testing combined with a refined load-deflection model of long rectangular membranes. The plane-strain modu i and prestresses of SiNx thin films have little dependence on the substrates, that is, for the bare Si substrate, they are 133 +/- 19 GPa and 178 +/- 22 MPa, respectively, while for the thermally oxidized substrate, they are 140 +/- 26 Gila and 194 +/- 34 MPa, respectively. However, the fracture strength values of SiNx films grown on the two substrates are quite different, i.e., 1.53 +/- 0.33 Gila and 3.08 +/- 0.79 GPa for the bare Si substrate a A the oxidized Si substrate, respectively. The reference stresses were computed by integrating the local stress of the membrane at the fracture over the edge, Surface, and volume of the specimens and fitted with the Weibull distribution function. For SiNx thin film produced oil the bare Si Substrate, the Volume integration gave a significantly better agreement between data and model, implying that the volume flaws re the dominant fracture origin. For SiNx thin film grown on the oxidized Si substrate, the fit quality of surface and edge integration was significantly better than the Volume integration, and the dominant surface and edge flaws could be caused by buffered HF attacking the SiNx layer during SiO2 removal. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.

Synthesis and characterization of ZnO nanorods and nanoflowers grown on GaN-based LED epiwafer using a solution deposition method

We report the growth of hexagonal ZnO nanorods and nanoflowers on GaN-based LED epiwafer using a solution deposition method. We also discuss the mechanisms of epitaxial nucleation and of the growth of ZnO nanorods and nanoflowers. A GaN-based LED epiwafer was first deposited on a sapphire substrate by MOCVD with no electrode being fabricated on it. Vertically aligned ZnO nanorods with an average height of similar to 2.4 mu m were then grown on the LED epiwafer, and nanoflowers were synthesized on the nanorods. The growth orientation of the nanorods was perpendicular to the surface, and the synthesized nanoflowers were composed of nanorods. The micro-Raman spectra of the ZnO nanorods and nanoflowers are similar and both exhibit the E-2 (high) mode and the second-order multiple-phonon mode. The photoluminescence spectrum of ZnO nanostructures exhibits ultraviolet emission centred at about 380 nm and a broad and enhanced green emission centred at about 526 nm. The green emission of the ZnO nanostructures combined with the emission of InGaN quantum wells provides a valuable method to improve the colour rendering index (CRI) of LEDs.

Kinetics and transport model for the chemical vapor epitaxy of GexSi1-x

A numerical model that combines mass transport and surface kinetics was applied, for the first time, to the chemical vapor epitaxy of GexSi1-x. The temperature, velocity and concentration fields were calculated from the conservation equations for energy, momentum and species coupled with the boundary conditions on the growth surface which were determined by surface kinetics. The deposition rates of Si and Ge were assumed to be limited, respectively, by surface kinetics and mass transport. A theoretical relation between the initial conditions and the Ge composition in the solid was established. The calculated growth rate as well as the Ge composition in the solid and its dependence on growth temperature agree well with experimental data.

Dependence of wet etch rate on deposition, annealing conditions and etchants for PECVD silicon nitride film

The influence of deposition, annealing conditions, and etchants on the wet etch rate of plasma enhanced chemical vapor deposition (PECVD) silicon nitride thin film is studied. The deposition source gas flow rate and annealing temperature were varied to decrease the etch rate of SiN_x:H by HF solution. A low etch rate was achieved by increasing the SiH_4 gas flow rate or annealing temperature, or decreasing the NH_3 and N_2 gas flow rate. Concen-trated, buffered, and dilute hydrofluoric acid were utilized as etchants for SiO_2 and SiN_x:H. A high etching selectivity of SiO_2 over SiN_x:H was obtained using highly concentrated buffered HF.

Morphology observation of carbon deposition by CH4 decomposition over Ni-based catalysts

We found a novel morphology variation of carbon deposition derived from CH4 decomposition over NI-based catalysts. By altering the chemical composition and particle size of Ni-based catalysts, carbon filaments, nanofibres and nanotubes were observed over conventional Ni/y-Al2O3, Ni-Co/gamma-Al2O3 and nanoscale Ni-Co/gamma-Al2O3 catalysts, respectively. The simple introduction of Co into a conventional Ni/gamma-Al2O3 catalyst can vary the carbon deposition from amorphous filamentous carbon to ordered carbon fibres. Moreover, carbon nanotubes with uniform diameter distribution can be obtained over nanosized Ni-Co/gamma-Al2O3 catalyst particles. In addition, the oxidation behaviour of the different deposited carbon was studied by using a temperature-programmed oxidation technique. This work provides a simple strategy to control over the size and morphology of the carbon deposition from catalytic decomposition of CH4.

Double-ceramic-layer thermal barrier coatings of La2Zr2O7/YSZ deposited by electron beam-physical vapor deposition

Double-ceramic-layer(DCL) thermal barrier coatings (TBCs) of La2Zr2O7 (LZ) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphologies and cyclic oxidation behavior of the DCL coating were studied. Both the X-ray diffraction (XRD) and thermogravimetric-differential thermal analysis (TG-DTA) prove that LZ and YSZ have good chemical applicability to form a DCL coating. The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ coating. and even longer than that of the single layer YSZ coating. The failure of the DCL coating is a result of both the bond coat oxidation and the thermal strain between bond coat and ceramic layer generated by the thermal expansion mismatch.

Combining chemical reduction with an electrochemical technique for the simultaneous detection of Cr(VI), Pb(II) and Cd(II)

This work herein reports the approach for the simultaneous determination of heavy metal ions including cadmium (Cd(II)), lead (Pb(II)), and chromium (Cr(VI)) using a bismuth film electrode (BFE) by anodic stripping voltammertry (ASV). The BFE used was plated in situ. Due to the reduction of Cr(VI) with H2O2 in the acid medium, on one hand, the Cr(III) was produced and Cr(VI) was indirectly detected by monitoring the content of Cr(III) using square-wave ASV. On the other hand, Pb(II) was also released from the complex between Pb(II) and Cr(VI). Furthermore, the coexistence of the Cd(II) was also simultaneously detected with Pb(II) and Cr(VI) in this system as a result of the formation of an alloy with Bi. The detection limits of this method were 1.39 ppb for Cd(II), 2.47 ppb for Pb(II) and 5.27 ppb for Cr(VI) with a preconcentration time of 120 s under optimal conditions (S/N = 3), respectively. Furthermore, the sensitivity of this method can be improved by controlling the deposition time or by using a cation-exchange polymer (such as Nafion) modified electrode.

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

Deposition of GdVO4 : Eu3+ nanoparticles on silica nanospheres by a simple sol-gel method

The deposition and coating of GdVO4: Eu3+ nanoparticles on spherical silica was carried out using a simple sol - gel method at low temperature. The GdVO4: Eu3+-coated silica composites obtained were characterized by differential thermal analysis (DTA), thermogravimetric (TG) analysis, x-ray diffraction (XRD), Fourier-transform IR spectroscopy (FT-IR), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), photoluminescence spectra, and kinetic decay. It is found that the similar to 5 nm GdVO4: Eu3+ nanoparticles coating the silica spheres are crystal in the as-prepared samples and the crystallinity increases with increasing annealing temperature. The composites obtained are spherical in shape with an average size of 100 nm. The GdVO4: Eu3+ nanoparticles are linked with silica cores by a chemical bond. The photoluminescence spectra of the obtained GdVO4: Eu3+-coated silica composites are similar to those of the bulk GdVO4: Eu3+ phosphors. The strongest peak is near 617 nm, which indicates that Eu3+ is located in the low symmetry site with non-inversion centre.

Self-assembling process of alkanethiol monolayers on gold surface via underpotential deposition

It was demonstrated feasible that underpotential deposition(UPD) of copper on a monolayer-modified gold substrate can be used to determine the gold electrode area. The deposition and stripping of a Cu adlayer can take Place reversibly and stably at a bared or a self-assembled monolayer modified gold electrode. The growth kinetics of decanethiol/Au was also investigated via Cu UPD. The difference between the assembling kinetics determined by UPD and that by quartz crystal microbalance measurements reveals the configuration transmutation of the assembled molecules from a disordered arrangement to an ordered arrangement during the self-assembling processes.

Pervasive autocorrelation of the chemical index of alteration in sedimentary profiles and its palaeoenvironmental implications

The chemical index of alteration has been used widely for reconstruction of the palaeoclimate. However, the mechanisms and environmental factors controlling the chemical index of alteration of sediments are not yet fully understood. In this study, autocorrelations of the chemical index of alteration in nine sedimentary profiles, from both the land and the sea, spanning different geological times, are discussed. The sediments of these profiles have different origins (dust, fluvial or ocean sediments) and are from various climate situations and sedimentary environments. Autocorrelations of chemical index of alteration series are ubiquitously evident in all profiles. It is suggested here that autocorrelations may be caused by post-depositional changes such as persistent weathering and diagenesis. As a result, the chemical index of alteration may not reflect climatic conditions during the time of sediment deposition. This study strongly recommends the confirmation of the reliability and veracity of the chemical index of alteration before it is adopted to evaluate the weathering degree of parent rocks and to reconstruct the past climate. Significant autocorrelations in loess profiles were specifically observed, suggesting that the existing understanding of loess deposition in terms of climate conditions requires re-examination, and that previous reconstructions of rapid climate changes (for example, in centennial-millennial scales) should be treated with caution.