Kinetic modelling of gibbsite dehydration/amorphization in the temperature range 823-923 K

In this work, the kinetics of gibbsite dehydration/amorphization were investigated in the temperature range from 823 to 923 K. Different kinetic models were evaluated to find the appropriate formalizations that best describe or predict the kinetic behavior of this process. Gibbsite dehydration/amorphization is a complex process involving a set of chain reactions:

     

Shock-tube study of the ignition of methane/ethane/hydrogen mixtures with hydrogen contents from 0% to 100% at different pressures

The ignition delay times of diluted hydrogen/reference gas (92% methane, 8% ethane)/O₂/Ar mixtures with hydrogen contents of 0%, 40%, 80% and 100% were determined in a high-pressure shock tube at equivalence ratios ? = 0.5 and 1.0 (dilution 1:5). The temperature range was 900 K ? T ? 1800 K at pressures of about 1, 4 and 16 bar.The reference gas and the 40% hydrogen/60% reference gas data showed typical characteristics of hydrocarbon systems and can be represented by:

     

One-dimensional defects in iodine adlayers on Pt(1 0 0)

One-dimensional defect structures of closed-packed adlayers of iodine on Pt(1 0 0) were studied with scanning tunneling microscopy (STM). On the terraces of the Pt(1 0 0) surface we observed rotational domains with line defects running in [0 1 0] directions, in coexistence with nearly defect-free domains. In addition to these prevailing line defects (A-defects) with a local coverage lower than that of a defect-free surface, we report on much less frequently observed line defects with higher local coverages (B- and C-defects). The strong dependence of the concentration of these defects on the adsorption temperature is governed by the decrease of the overall iodine coverage with increasing temperature. Iodine adsorption at ∼1100 K leads to self-organization of A-defects in quasi-periodic arrangements. The relevance of these defects as important structural elements of commensurate superstructures of iodine on Pt(1 0 0) is stressed.     

Surface phase diagram and temperature induced phase transitions of Sn/Cu(1 0 0)

Room temperature deposition of Sn on Cu(1 0 0) gives rise to a rich variety of surface reconstructions in the submonolayer coverage range. In this work, we report a detailed investigation on the phases appearing and their temperature stability range by using low-energy electron diffraction and surface X-ray diffraction. Previously reported reconstructions in the submonolayer range are p(2 × 2) (for 0.2 ML), p(2 × 6) (for 0.33 ML), ()R45° (for 0.5 ML), and c(4 × 4) (for 0.65 ML). We find a new phase with a structure for a coverage of 0.45 ML. Furthermore, we analyze the temperature stability of all phases. We find that two phases exhibit a temperature induced reversible phase transition: the ()R45° phase becomes ()R45° phase above 360 K, and the new phase becomes p(2 × 2) also above 360 K. The origin of these two-phase transitions is discussed.     

Photoelectron spectroscopy study of Pb/Ag(1 1 1) in the submonolayer range

The vacuum deposition of Pb onto Ag(1 1 1) gives rise to two different surface structures depending on coverage and deposition temperature. At room temperature (RT), low energy electron diffraction (LEED) reveals a sharp reconstruction completed at 1/3 Pb monolayer (ML). Beyond, a close-packed Pb(1 1 1) incommensurate overlayer develops. At low temperature (LT, ∼100 K) the incommensurate structure is directly observed whatever the coverage, corresponding to the growth of close-packed two-dimensional Pb(1 1 1) islands. Synchrotron radiation Pb 5d core-level spectra clearly demonstrate that in each surface structure all Pb atoms have essentially a unique, but different, environment. This reflects the surface alloy formation between the two immiscible metals in the reconstruction and a clear signature of the de-alloying process at RT beyond 1/3 ML coverage.     

The decomposition of normal hexyl radicals

Normal hexyl radicals generated from the decomposition of n-hexyl iodide have been decomposed in single pulse shock tube experiments. All the products arising from the decomposition of 1-hexyl (the initial reactant) and 2-hexyl and 3-hexyl (isomerization products) have been detected in the temperature range 890-1020 K and 1.5-5 bar pressures. We find that

     

First-principles study of the H and F centers in LiYF4

We have investigated the electronic structures of the LiYF₄ containing interstitial fluorine atoms and F center (a fluorine ion vacancy trapping an electron) using first-principles density functional theory. It is found that the interstitial fluorine atoms in two different interstitial positions would combine with its nearest neighbor two or three formal lattice fluorine ions forming fluorine molecular ions or by different ways, which would cause the 260 nm absorption band. Simultaneously, our study indicates that one electronic state appears in the forbidden band of the perfect LiYF₄ crystal resulting from the F center in the LiYF₄ crystal. And the energy difference of this electronic state and the bottom of the conduction band is 3.74 eV, corresponding to the 331 nm absorption band. It is predicted that the 330 nm absorption band could arise from the F center in LiYF₄ crystals.     

Profile imaging of reconstructed polar and non-polar surfaces of ZnO

The atomic scale surface structures of ZnO non-polar as well as and ±(0 0 0 1) polar surfaces have been directly imaged by high-resolution transmission electron microscopy (HRTEM). The observations were made on clean surfaces created by irradiating a single ZnO nanobelt using 400 keV electron beam in TEM, under which ZnO dots were grown epitaxially and in situ on the surface of the nanobelt. A technique is demonstrated for directly distinguishing the surface polarity of the ±(0 0 0 1) polar surfaces. For the non-polar surface, HRTEM images and simulation results indicate that the Zn ions in the first and second layer suffer from inward and outward relaxation, respectively; the oxygen ions in the first and second layer prefer shifting to vicinal Zn ions to shorten the bonding distance. For the oxygen-terminated polar surface, the oxygen ions at the outmost top layer were directly imaged. a × 2 reconstruction has also been observed at the surface, and its atomic structure has been proposed based on image simulation. Oxygen-terminated polar surface is flat and shows no detectable reconstruction. For the Zn-terminated (0 0 0 1) polar surface, HRTEM may indicate the existence of Zn vacancies and a possibly c-axis, random outward displacement of the top Zn ions. Our data tend to support the mechanism of removal of surface atoms for maintaining the stability of (0 0 0 1) polar surfaces.     

Ge adsorption on SiC(0 0 0 1): An ab initio study

In this work we have performed an ab initio total energy investigation of the Ge adsorption process on the Si-terminated SiC(0 0 0 1)- and (3 × 3) surfaces. We find that Ge adatoms lying on the topmost sites of the and (3 × 3) surfaces represent the energetically more stable configurations at the initial stage of the Ge adsorption on the SiC(0 0 0 1) surface. The Si → Ge substitutional adsorption processes have been examined as a function of the Si and Ge chemical potentials. Increasing the Ge coverage, we verify that the formation of Ge wetting layer on the surface, and Ge nanocluster on the (3 × 3) surface are the energetically more stable configurations, in accordance with recent experimental findings.     

Aromatic interactions in the close packing of phenyl-imides at Cu(1 1 0) surfaces

The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C₆H₅N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 10¹⁴ mol cm⁻² and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 10¹⁴ mol cm⁻² were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.     

Surface diffusion of copper on tantalum substrates by Ostwald ripening

In this work, we report on the determination of surface diffusion coefficient of copper on tantalum substrates by Ostwald ripening. It is shown that impurities, such as oxygen, strongly influence the kinetics of dewetting of copper films on tantalum substrates. Two technologically important interfaces with copper were investigated: Cu/β-Ta and Cu/α-Ta. For copper surface diffusion on β-Ta surface, a surface diffusion coefficient of was measured at 550 °C. The temperature dependence of surface diffusion was investigated between 400 °C and 550 °C. Using an Arrhenius relationship, an activation energy of 0.83 ± 0.1 eV and a pre-exponential factor of were calculated. For copper surface diffusion on α-Ta surface, a diffusion coefficient of was measured at 550 °C. We discuss the diffusion mechanism involved during the cluster growth and the origin of the faster surface diffusion of copper on the β-Ta substrate as compared to the α-Ta phase.     

Anisotropic defect reduction in non-polar a-plane GaN grown by hydride vapor phase epitaxy on maskless patterned templates

Several non-polar a-plane GaN films had been grown by hydride vapor phase epitaxy (HVPE) on different designed metal organic chemical deposition (MOCVD) GaN templates, which exhibited various ridge-like sidewall facets surface morphologies. The templates induced a lateral growth at the early stage of the HVPE growth, and resulted in a kind of maskless epitaxy lateral overgrown (ELO) process. It is found that the dislocation reduced differently along [1 0 0 0] and [] directions in these HVPE a-plane GaN layers. In [0 0 0 1] direction, the dislocation reduction resulted from the optimal surface roughness value of the template. In [] direction, the inclined facet might be a main factor for the dislocation reduction in HVPE-GaN films. The maskless ELO process had a significant influence on decreasing the dislocation density.     

Surface-energy-anisotropy-induced orientation effects on Rayleigh instabilities in sapphire

Arrays of controlled-geometry, semi-infinite pore channels of systematically varied crystallographic orientation were introduced into undoped m-plane sapphire substrates using microfabrication techniques and ion-beam etching and subsequently internalized by solid-state diffusion bonding. A series of anneals at 1700 °C caused the breakup of these channels into discrete pores via Rayleigh instabilities. In all cases, channels broke up with a characteristic wavelength larger than that expected for a material with isotropic surface energy, reflecting stabilization effects due to surface-energy anisotropy. The breakup wavelength and the time required for complete breakup varied significantly with channel orientation. For most orientations, the instability wavelength for channels of radius R was in the range of 13.2R-25R, and complete breakup occurred within 2-10 h. To first order, the anneal times for complete breakup scale with the square of the breakup wavelength. Channels oriented along a direction had a wavelength of ≈139R, and required 468 h for complete breakup. Cross-sectional analysis of channels oriented along a direction showed the channel to be completely bounded by stable c(0 0 0 1), , and facets.