Characterization of porous silicon nitride/silicon oxynitride composite ceramics produced by sol infiltration

Porous silicon nitride/silicon oxynitride composite ceramics were fabricated by silica sol infiltration of aqueous gelcasting prefabricated Si3N4 green compact. Silica was introduced by infiltration to increase the green density of specimens, so suitable properties with low shrinkage of ceramics were achieved during sintering at low temperature. Si2N2O was formed through reaction between Si3N4 and silica sol at a temperature above 1550 degrees C. Si3N4/Si2N2O composite ceramics with a low linear shrinkage of 1.3-5.7%, a superior strength of 95-180 MPa and a moderate dielectric constant of 4.0-5.0 (at 21-39 GHz) were obtained by varying infiltration cycle and sintering temperature. (C) 2010 Published by Elsevier B.V.

Surface transformation and inversion domain boundaries in gallium nitride nanorods

Phase transformation and subdomain structure in [0001]-oriented gallium nitride (GaN) nanorods of different sizes are studied using molecular dynamics simulations. The analysis concerns the structure of GaN nanorods at 300 K without external loading. Calculations show that a transformation from wurtzite to a tetragonal structure occurs along {0110} lateral surfaces, leading to the formation of a six-sided columnar inversion domain boundary (IDB) in the [0001] direction of the nanorods. This structural configuration is similar to the IDB structure observed experimentally in GaN epitaxial layers. The transformation is significantly dependent on the size of the nanorods.

Damage accumulation in gallium nitride irradiated with various energetic heavy ions

In this work a study of damage production in gallium nitride via elastic collision process (nuclear energy deposition) and inelastic collision process (electronic energy deposition) using various heavy ions is presented. Ordinary low-energy heavy ions (Fe+ and Mo+ ions of 110 keV), swift heavy ions (Pb-208(27+) ions of 1.1 MeV/u) and slow highly-charged heavy ions (Xen+ ions of 180 keV) were employed in the irradiation. Damage accumulation in the GaN crystal films as a function of ion fluence and temperature was studied with RBS-channeling technique, Raman scattering technique, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). For ordinary low-energy heavy ion irradiation, the temperature dependence of damage production is moderate up to about 413 K resulting in amorphization of the damaged layer. Enhanced dynamic annealing of defects dominates at higher temperatures. Correlation of amorphization with material decomposition and nitrogen bubble formation was found. In the irradiation of swift heavy ions, rapid damage accumulation and efficient erosion of the irradiated layer occur at a rather low value of electronic energy deposition (about 1.3 keV/nm(3)),. which also varies with irradiation temperature. In the irradiation of slow highly-charged heavy ions (SHCI), enhanced amorphization and surface erosion due to potential energy deposition of SHCI was found. It is indicated that damage production in GaN is remarkably more sensitive to electronic energy loss via excitation and ionization than to nuclear energy loss via elastic collisions.

The reaction route and active site of catalytic decomposition of hydrazine over molybdenum nitride catalyst

The catalytic properties of the passivated, reduced passivated, and fresh bulk molybdenum nitride for hydrazine decomposition were evaluated in a microreactor. The reaction route of hydrazine decomposition over molybdenum nitride catalysts seems to be the same as that of Ir/gamma-Al2O3 catalysts. Below 673 K, the hydrazine decomposes into N-2 and NH3. Above 673 K, the hydrazine decomposes into N-2 and NH3 first, and then the produced NH3 further dissociates into N-2 and H-2. From the in situ FT-IR spectroscopy, hydrazine is adsorbed and decomposes mainly on the Mo site of the Mo2N/gamma-Al2O3 catalyst. (C) 2004 Elsevier Inc. All rights reserved.

Effect of support on chromium based catalysts for the oxidative dehydrogenation of C2H6 with CO2 to C2H4

The oxidative dehydrogenation of ethane (ODE) with CO2 to C2H4 has been studied over a series of Cr-based catalysts using SiO2, Al2O3, (MCM-41 zeolite) MCM-41, MgO and Silicate-2 (Si-2) as the supports. TPR, NH3-TPD, and EPR characterizations of catalysts were carried out to investigate the reduction property of Cr species on different supports, the acidities of catalysts and Cr species of 6Cr/SiO2 catalysts, respectively.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Microcalorimetric and IR spectroscopic studies of CO adsorption on molybdenum nitride catalysts

The adsorption of CO on both nitrided and reduced passivated Mo(2)N catalysts in either alumina supported or unsupported forms was studied by adsorption microcalorimetry and infrared (IR) spectroscopy. The CO is adsorbed on nitrided Mo(2)N catalysts on three different surface sites: 4-fold vacancies, Mo(delta+) ( 0 < delta < 2) and N sites, with differential heats of CO adsorption decreasing in the same order. The presence of the alumina-support affects the energetic distribution of the adsorption sites on the nitrided Mo(2)N, i.e. weakens the CO adsorption strength on the different sites and changes the fraction of sites adsorbing CO in a specific form, revealing that the alumina supported Mo(2)N phase shows lower electron density than pure Mo(2)N. On reduced passivated Mo(2)N catalysts the CO was found to adsorb mainly on Mo(4+) sites, although some slightly different surface Mo(delta+) d (0 < delta < 2) sites are also detected. The nature, density and distribution of surface sites of reduced passivated Mo(2)N/gAl(2)O(3) were similar to those on reduced MoO(3)/gamma-Al(2)O(3).

Catalytic decomposition of hydrazine over supported molybdenum nitride catalysts in a monopropellant thruster

The catalytic decomposition of hydrazine over a series of MoNx/gamma-Al2O3 catalysts with different Mo loadings was investigated in a monopropellant thruster (10 N). When the Mo loading is equal to or higher than the monolayer coverage of MoO3 on gamma-Al2O3, the catalytic performance of the supported molybdenum nitride catalyst is close to that of the conventionally used Ir/gamma-Al2O3 catalyst. The MoNx/gamma-Al2O3 catalyst with a loading of about 23wt% Mo (1.5 monolayers) shows the highest activity for hydrazine decomposition. There is an activation process for the MoNx/gamma-Al2O3 catalysts at the early stage of hydrazine decomposition, which is probably due to the reduction of the oxide layer formed in the passivation procedure.

Novel Potentiometric Membrane Sensor for the Determination of Trace Amounts of Chromium(III) Ions

A plasticized Cr3+ ion sensor by incorporating 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene (TTCT) ionophore exhibits a good potentiometric response for Cr3+ over a wide concentration range (1.0×10-6-1.0×10-1 M) with a slope of 19.5 mV per decade. The sensor response is stable for at least three months. Good selectivity for Cr3+ in comparison with alkali, alkaline earth, transition and heavy metal ions, and minimal interference are caused by Li+, Na+, K+, Co2+, Hg2+, Ca2+, Pb2+ and Zn2+ ions, which are known to interfere with other chromium membrane sensors. The TTCT-based electrode shows a fast response time (15 s), and can be used in aqueous solutions of pH 3 - 5.5. The proposed sensor was used for the potentiometric titration of Cr3+ with EDTA and for a direct potentiometric determination of Cr3+ content in environmental samples.

Selective, peroxidase substrate based "signal-on" colorimetric assay for the detection of chromium (VI)

Due to the potentially adverse effects of the chromium (VI) on the human health and also on the environment, the quantitative determination of Cr(VI) is of particular interest. This work herein reports a facile, selective and rapid colorimetric determination of Cr(VI) based on the peroxidase substrate-2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) as the color developing agent. ABTS, which was usually acted as peroxidase substrate for the enzyme linked immunosorbent assay, is used here for the first time to fabricate the "signal-on" colorimetric Assay for Cr(VI).

Effect of substitution of chromium for nickel on structure and electrochemical characteristic of Ti0.26Zr0.07V0.24Mn0.1Ni0.33 multi-phase hydrogen storage alloy

Ti-Zr-V-Mn-Ni-based multi-component alloys demonstrate high discharge capacity in KOH electrolyte. However, the drastic decrease in their discharge capacities makes them unsuitable for use as negative electrode material in the Ni/MH battery. In present work, Ni is partially replaced by Cr in the Ti-Zr-V-Mn-Ni-based alloys to improve their cycle life. The effects of Cr substitution on microstructures and the electrochemical characteristics of the alloys are investigated. It is found that Cr substitution is very effective to improve the cyclic durability of the alloys although the discharge capacity decreases with changing x from 0.05 to 0.20. Some kinetic performances have been also investigated using electrochemical impedance spectroscopy (EIS) and potentiostatic discharge technique.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Ethylene Polymerization by the New Chromium Catalysts Based on Amino-Pyrrolide Ligands

A series of amino-pyrrolide ligands (1-4a) and their derivatives aminothiophene ligand (5a), amino-indole ligand (6a) were prepared. Chromium catalysts, which were generated in situ by mixing the ligands with CrCl3(thf)(3) in toluene, were tested for ethylene polymerization. The preliminary screening results revealed that the tridentate amino-pyrrolide ligands containing soft pendant donor, 3a, 4a/CrCl3(thf)(3) systems displayed high catalytic activities towards ethylene polymerization in the presence of modified methyaluminoxane. The electronic and steric factors attached to the ligand backbone significantly affected both the catalyst activity and the polymer molecular weight. Complex 4b was obtained by the reaction of CrCl3(thf)(3) with one equivalent of the lithium salts of 4a, which was the most efficient ligand among the tested ones. The effect of polymerization parameters such as cocatalyst concentration, ethylene pressure, reaction temperature, and time on polymerization behavior were investigated in detail. The resulting polymer obtained by 4b display wax-like and possess linear structure, low molecular weight, and unimodal distribution.