Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Electrical properties and positron annihilation study of (Ba<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ho<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)TiO<Subscript>3</Subscript> ceramics

DC resistivity, dielectric constant, dielectric loss and positron annihilation spectra of (Ba_1−x Ho _x )TiO₃ ceramics have been measured as a function of holmium concentration x. It has been found that the DC resistivity of (Ba_1−x Ho _x )TiO₃ is strongly dependent on the Ho content: it decreases three orders of magnitude and reaches a minimum at x = 0.4%. Doping with 0.6% holmium increases the permittivity of BaTiO₃ by approximately three times (from ∼1,300 to ∼4,000), with only a slight increase in the corresponding dielectric loss. The local electron density and defect concentration estimated using positron annihilation technique conforms well to the features found in the dielectric and resistivity measurements. The results have been discussed in terms of a mixed compensation model.     

Preliminary<Emphasis Type="Italic">in vitro</Emphasis> and<Emphasis Type="Italic">in vivo</Emphasis> characterizations of a sol-gel derived bioactive glass-ceramic system

This study investigates quantitatively and qualitatively the sol-gel derived bioactive glass-ceramic system (BGS)—apatite-wollastonite (AW) type granules in the size range of 0.5–1 mm, as an effective graft material for bone augmentation and restoration. Scanning electron micrographs (SEM) of the sintered granules revealed the rough material surface with micropores in the range 10–30 μm. X-ray diffraction (XRD) pattern of the granules revealed the presence of crystalline phases of the hydroxyapatite and wollastonite, and the functional groups of the silicate and phosphates were identified by Fourier transform infrared spectroscopy (FT-IR). Thein vitro cell culture studies with L929 mouse fibroblast cell line showed very few cells adhered on the BGS disc after 24 h. This could be due to the highly reactive surface of the disc concomitant with the crystallization but not due to the cytotoxicity of the material, since the cellular viability (MTT assay) with the material was 80‰ Cytotoxicity and cytocompatibility studies proved that the material was non-toxic and biocompatible. After 12 weeks of implantation of the BGS granules in the tibia bone of New Zealand white rabbits, the granules were found to be well osteointegrated, as observed in the radiographs. Angiogram with barium sulphate and Indian ink after 12 weeks showed the presence of microcapillaries in the vicinity of the implant site implicating high vascularity. Gross observation of the implant site did not show any inflammation or necrosis. SEM of the implanted site after 24 weeks revealed good osteointegration of the material with the newly formed bone and host bone. New bone was also observed within the material, which was degrading. Histological evaluation of the bone healing with the BGS granules in the tibial defect at all time intervals was without inflammation or fibrous tissue encapsulation. After 2 weeks the new bone was observed as a trabeculae network around the granules, and by 6 weeks the defect was completely closed with immature woven bone. By 12 weeks mature woven bone was observed, and new immature woven bone was seen within the cracks of the granules. After 24 weeks the defect was completely healed with lamellar bone and the size of the granules decreased. Histomorphometrically the area percentage of new bone formed was 67.77% after 12 weeks and 63.37% after 24 weeks. Less bone formation after 24 weeks was due to an increased implant surface area contributed by the material degradation and active bone remodeling. The osteostimulative and osteoconductive potential of the BGS granules was established by tetracycline labelling of the mineralizing areas by 2 and 6 weeks. This sol-gel derived BGS granules proved to be bioactive and resorbable which in turn encouraged active bone formation.     

Kinetics of chlorination of tantalum pentoxide in mixture with sucrose carbon by chlorine gas

The mechanism and kinetics of β-Ta₂O₅ chlorination, mixed with sucrose carbon, have been studied by a thermogravimetric technique. The investigated temperature range was 500 °C to 850 °C. The reactants and reaction residues were analyzed by scanning electronic microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller method for surface area (BET). The effect of various experimental parameters was studied, such as carbon percentage, temperature, chlorine partial pressure, and flow, use of the multiple sample method, and carbon previous oxidation. The carbon percentage and previous treatment have an effect on the system reactivity. The temperature has a marked effect on the reaction rate. In the 500 °C to 600 °C temperature interval, the apparent activation energy is 144 kJ/mol of oxide, while at higher temperatures, the activation energy decreases. With high chorine partial pressures, the order of reaction is near zero. The kinetic contractile plate model, X=kt, considering carbon oxidation as the controlling stage, is the one with the best fit to the experimental data. A probable mechanism for the carbochlorination of β-Ta₂O₅ is proposed: (1) activation of chlorine on the carbon surface, (2) chlorination of Ta₂O₅, (3) oxidation of carbon, and (4) recrystallization of β-Ta₂O₅.