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.     

The greenhouse effect; Impact upon and the role to be played by construction

The authors highlight several possible ways in which the construction industry could lower present emissions of the greenhouse gas, carbon dioxide. It is an excellent discussion document and is recommended reading.     

Effect of Bi and Sr concentrations on the formation of the 2223 phase in Bi-Pb-Sb-Sr-Ca-Cu-O materials, obtained under different conditions of thermal treatment

The superconducting properties and the phase and chemical composition of Bi _x Pb_0.3Sb_0.1Sr _y Ca₂Cu₃O_z (x=1.5, 1.6, and 1.7;y=1.9, 2.0, and 2.1) materials synthesized by one-step and multistep thermal treatments have been investigated. The multistep annealing between 825–875°C promotes the 2223 phase. The change of Bi concentration has little effect on the 2223 phase formation, regardless of the kind of thermal treatment used, but increasing the Sr concentration (y> 2) strongly inhibits this phase. It has also been established that the loss of Pb after synthesis depends on the initial Bi concentration. The loss of Pb decreases when the initial Bi content is lower.     

Investigation of texture effect on visual colour difference evaluation

The texture effect on visual colour difference evaluation was investigated in this study. Five colour centers were selected and textured colour pairs were generated using scanned textile woven fabrics and colour‐mapping technique. The textured and solid colour pairs were then displayed on a characterized cathode ray tube (CRT) monitor for colour difference evaluation. The colour difference values for the pairs with texture patterns are equal to 5.0 CIELAB units in lightness direction. The texture level was represented by the half‐width of histogram, which is called texture strength in this study. High correlation was found between texture strength and visual colour difference for textured colour pairs, which indicates that an increasing of 10 units of texture strength in luminance would cause a decreasing of 0.25 units visual difference for the five colour centers. The ratio of visual difference between textured and solid colour pairs also indicates a high parametric effect of texture. © 2005 Wiley Periodicals, Inc. Col Res Appl, 30, 341–347, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.     

Evaporation and Evolution of Suspended Solution Droplets at Atmospheric and Reduced Pressures

Thermal history and solute precipitation behavior of suspended solution droplets of sodium chloride (NaCl), magnesium sulphate (MgSO₄), and zirconium hydroxychloride (ZrO(OH)Cl) evaporating at atmospheric and reduced pressures are studied. Experimental measurements on the variation of droplet diameter, solution concentration, and temperature during the evaporation period are presented and discussed. The results of solute precipitation behavior in solution droplets observed under an optical microscope are displayed and discussed. Results indicate that reducing the pressure (∼ 33 kPa) results in a change in the solution droplet evaporation rate, but the thermal histories of a particular solution droplet are similar at the atmospheric and reduced pressures. At atmospheric and reduced pressures used in this study, the d² law for solution droplets is valid at early stages of the evaporation and before the solute precipitation initiates. Drying of MgSO₄ and ZrO(OH)Cl solution droplets results in the formation of spherical particles, whereas drying of spherical NaCl solution droplets results in the formation of cubic particles.     

Monte Carlo simulation of hydrogen absorption in palladium and palladium–silver alloys

A modified Monte Carlo (MC) simulation was performed to investigate the hydrogen absorption behavior in Pd and Pd–Ag alloys of the composition Pd_xAg_1−x (x=0.7–0.8) under H₂ pressure (0.1 MPa) at different temperatures. The present method employed can consider the dissociative adsorption of hydrogen molecule and the subsequent absorption of hydrogen atom by formalizing the relationship between the pressure of hydrogen molecule and hydrogen atom. The potential parameters were determined to reproduce the solution enthalpy of hydrogen in pure metals. The results are in good agreement with experimental findings as well as previous theoretical studies. We confirmed that our method is useful to simulate the absorption of hydrogen in metals and alloys.     

Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds

The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH₄ traces under lean-burn conditions was studied in the presence or the absence of water or H₂S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H₂S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H₂S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H₂S-poisoned Pd/Al₂O₃ catalyst was studied by TPD in O₂/He. Poisoning species decompose above 873 K as SO₂ and O₂ in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O₂/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H₂S-poisoned Pd/Al₂O₃. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested.     

Schäden durch kerbinduzierte Schwingbrüche

Failures by notch induced fatigue fractures Notches produce local stress concentrations and promote the formation of fatigue cracks. Characteristic types of notches as a result of design, manufacturing and operation are presented and remedial measures are discussed. Examples demonstrate the effect of different kinds of notches on various components.     

Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.