Amorphous Coatings Deposited on Aluminum Alloy by Plasma Electrolytic Oxidation

Amorphous [Al-Si-O] coatings were deposited on aluminum alloy by plasma electrolytic oxidation (PEO). The process parameters, composition, micrograph, and mechanical property of PEO amorphous coatings were investigated. It is found that the growth rate of PEO coatings reaches 4.44 mu m/min if the current density is 0.9 mA/mm(2). XRD results show that the PEO coatings are amorphous in the current density range of 0.3-0.9 mA/mm(2). EDS results show that the coatings are composed of O, Si and At elements. SEM results show that the coatings are porous. Nano indentation results show that the hardness of the coatings is about 3 - 4 times of that of the substrate, while the elastic modulus is about the same with the substrate. Furthermore, a formation mechanism of amorphous PEO coatings was proposed.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Effect of hydrogen dilution on the deposition of carbon-rich a-SiC:H films by the electron cyclotron resonance method

The deposition of hydrogenated amorphous silicon carbide (a-SiC:H) films from a mixture of silane, acetylene and hydrogen gas using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) process is reported. The variation in the deposition and film characteristics such as the deposition rate, optical band gap and IR absorption as a function of the hydrogen dilution is investigated. The deposition rate increases to a maximum value of about 250 Å min-1 at a hydrogen dilution ratio of about 20 (hydrogen flow (sccm)/acetylene + silane flow (sccm)) and decreases in response to a further increase in the hydrogen dilution. There is no strong dependence of the optical band gap on the hydrogen dilution within the dilution range investigated (10-60) and the optical band gap calculated from the E04 method varied marginally from about 2.85 to 3.17 eV. The room temperature photoluminescence (PL) peak energy and intensity showed a prominent shift to a maximum value of about 2.17 eV corresponding to maximum PL intensity at a moderate hydrogen dilution of about 30. The PL intensity showed a strong dependence on the hydrogen dilution variation.

Local hydrogen reactions of H*2 in a-Si:H

Hydrogen rearrangements at the H*2 complex are used as a model of low energy, local transitions in the two-hydrogen density of states of hydrogenated amorphous silicon (a-Si:H). These are used to account for the low activation energy motion of H observed by nuclear magnetic resonance, the low energy defect annealing of defects formed by bias stress in thin film transistors, and the elimination of hydrogen from the growth zone during the low temperature plasma deposition of a-Si:H. © 1998 Elsevier Science B.V. All rights reserved.

Chemical kinetics and self-ignition in a model supersonic hydrogen-air combustor

Self-ignition tests of a model scramjet combustor were conducted by using parallel sonic injection of gaseous hydrogen from the base of a blade-like strut into a supersonic vitiated airstream. The range of stagnation pressure and temperature studied varied from 1.0 to 4.5 MPa and from 1300 to 2200 K, respectively. Experimental results show that the self-ignition limit, in terms of either global or local quantities of pressure and temperature, exhibits a nonmonotonic behavior resembling the classical homogeneous explosion limit of the hydrogen-oxygen system. Specifically, for a given temperature, increasing pressure from a low value can render a nonignitable mixture to first become ignitable, then nonignitable again, This correspondence shows that, despite the globally supersonic nonpremixed configuration studied herein, ignition is strongly influenced by the intricate chemical reaction mechanism and thereby exhibits the homogeneous explosion character. Consequently, self-ignition criteria based on a global reaction rate approximating the complex chemistry are inadequate. An auxiliary computational study on counterflow ignition was also conducted to systematically investigate the contamination effects of vitiated air. Results indicate that the net contamination effects for the present experimental data are expected to be substantially smaller than contributions from the individual contamination species because of the counterbalancing influences of the H2O-inhibition and NO-promotion reactions in effecting ignition.

Effect of diffusion on coating microstructure and oxidation resistance of aluminizing steel

The effect of diffuse treatment on coating microstructure and oxidation resistance at high-temperature of hot-dip aluminum were studied by means of TEM, SEM and XRD. The results show that, the diffusion temperature has significant effect on structure of coatings and its oxidation resistance. After diffusion at 750 degreesC, the coating consists of thick outer surface layer (Fe2Al5+ FeAl2), thin internal layer (FeAl + stripe FeAl2), and its oxidation resistance is poor. After diffusion at 950 degreesC, the outer surface layer is composed of single FeAl2 phase, the internal layer is composed of FeAl phase, and its oxidation resistance declines due to the occurrence of early stage internal oxidation cracks in the coating. After diffusion at 850 degreesC, the outer surface layer becomes thinner and consists of FeAl2 Fe2Al5(small amount), the internal layer becomes thicker and consists of FeAl+spherical FeAl2, and the spheroidized FeAl2 phase in the internal layer and its existing in FeAl phase steadily improve the oxidation resistance of the coating.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

In the present study, we report the hydrogen content estimation of the hydrogenated amorphous carbon (a-C:H) films using visible Raman spectroscopy in a fast and nondestructive way. Hydrogenated diamondlike carbon films were deposited by the plasma enhanced chemical vapor deposition, plasma beam source, and integrated distributed electron cyclotron resonance techniques. Methane and acetylene were used as source gases resulting in different hydrogen content and sp2/sp3 fraction. Ultraviolet-visible (UV-Vis) spectroscopic ellipsometry (1.5-5 eV) as well as UV-Vis spectroscopy were provided with the optical band gap (Tauc gap). The sp2/sp3 fraction and the hydrogen content were independently estimated by electron energy loss spectroscopy and elastic recoil detection analysis-Rutherford back scattering, respectively. The Raman spectra that were acquired in the visible region using the 488 nm line shows the superposition of Raman features on a photoluminescence (PL) background. The direct relationship of the sp2 content and the optical band gap has been confirmed. The difference in the PL background for samples of the same optical band gap (sp2 content) and different hydrogen content was demonstrated and an empirical relationship between the visible Raman spectra PL background slope and the corresponding hydrogen content was extracted. © 2004 American Institute of Physics.

Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.