Visible light emission from silicon: a quantum effect in highlyporous materials

The authors discuss progress in the control of the luminescent properties of porous silicon and in the understanding of the basic mechanisms which govern the light emission. The main features of porous silicon formation and properties are briefly recalled. The photoluminescence characteristics are reported. It is shown that anodic oxidation of porous silicon is a technique which provides photoluminescent layers with good mechanical properties and enhanced emission efficiency. A model accounting for the quite long measured carrier lifetimes is outlined. The electroluminescence which appears during the anodic oxidation of porous silicon in pure water was studied     

The evolution of the exhaust diesel soot adsorptive properties after NO2 exposure and according to their SOF content

Several samples of exhaust diesel soot are investigated by inverse gas chromatography and linear solvation energy relationship (LSER) modelling according to their soluble organic fraction content and their time of exposure in oxidative conditions. The results demonstrate the evolution of the adsorptive properties of the studied materials towards volatile compounds during the oxidation under NO₂.     

Evaluating the effectiveness of photocatalysts based on titanium dioxide in the degradation of the dye Ponceau 4R

The performance of different titanium dioxide (TiO₂) catalysts and a composite based on the association between TiO₂ P25 and Zinc Phthalocyanine (TiO₂/ZnPc 1.6%) was evaluated in the photocatalytic degradation of the dye Ponceau 4R (C.I. 16255). The results show that the composite presents a better performance than the other, reaching about 50% mineralization of the dye in 120 min of reaction, around three times higher than that observed under the action of pure TiO₂ P25, although this catalyst presents a quantum yield of hydroxyl radical generation about three times higher than that estimated for the composite. This result seems to be a consequence of the synergism between the electronically excited ZnPc aggregates and the TiO₂ surface.A parallel study, based on methods from quantum mechanics also suggested the most feasible routes for the photodegradation of the dye in the absence of the catalyst.     

Prediction of work piece geometry in electrochemical cavity sinking

A computer-implemented model for predicting ECM work piece geometry has been developed and experimentally verified with a commercial ECM machine for cavity sinking in copper and 302-stainless steel with 2N K NO₃ electrolyte. Constant tool piece feed rates of 7–10 × 10^?4 cm/s, and applied voltages of 11–25 V were used. The model predicts the dependence of work piece geometry on operating conditions and on the electrochemical and physical properties of the metal—electrolyte pair. Comparison of eight equilibrium and six unsteady state experimental cavity profiles in copper showed satisfactory agreement with predictions, as did five equilibrium profiles for cavity sinking in 302-stainless steel.     

Effect of blend ratio and elongation flow on the morphology and properties of epoxy resin‐poly(trimethylene terephthalate) blends

The effect of processing conditions on the morphology of polymer blends is a topic of tremendous practical interest especially for thermoset–thermoplastic blends. The effect of blend ratio and the nature of the flow field (shear flow vs. elongation flow) on the morphology is followed here using blends of diglycidyl ether of bisphenol A (DGEBA)‐poly(trimethylene terephthalate) (PTT). Morphology of the blends prepared by the conventional melt mixing technique is compared with that prepared by using an elongation mixer (RMX device invented by Muller et al.). The blends prepared by the elongation mixer showed excellent transparency and higher storage modulus at room temperature than the conventional mixer. In the case of samples prepared by the RMX device T_g of the epoxy phase has been shifted to lower temperatures indicating a molecular level mixing between PTT and DGEBA. However the conventional melt mixed samples showed only a marginal shift in T_g to low temperatures indicating that the system is not as miscible as that prepared by the RMX device. The use of RMX device for thermoset–thermoplastic blends is novel and no work has been reported in this relation. The properties of the blends were strongly affected by the composition and the crystallization of the semicrystalline PTT phase. POLYM. ENG. SCI., 55:1679–1688, 2015. © 2014 Society of Plastics Engineers     

Dynamic mechanical behaviour of random copolymers of a LC-methacrylate and octyl methacrylate

The dynamic mechanical behaviour of random copolymers of LC monomer-1-(hexyloxycarbonyl)ethyl 4-[4-(methacryloyloxy)benzoyloxy]benzoate (HB) and octyl methacrylate (OMA) was studied in the main transition and flow regions. Even though the aliphatic end groups of the side chain of HB and OMA are roughly the same, the T _g temperature of poly(HB) is ∼ 80 K higher than that of poly(OMA); this fact is due to the presence of the stiff phenyl benzoate mesogenic group in the side chain of HB. With increasing content of OMA in the copolymer the superimposed curves of the storage G′ _p and loss G′′ _p moduli at a constant temperature shift towards shorter frequencies. It has been shown that this shift is mainly due to an increase of the free volume in the copolymers with increasing content of OMA. While HB monomer shows liquid crystalline (LC) properties, its polymer (poly(HB)) and random copolymers with OMA show only isotropic thermal behaviour because no flexible spacer is present in the side chain of HB which would decouple the main chain and mesogenic group motions. This means that neither the homopolymer of HB, nor its copolymers with a flexible comonomer retain the LC properties of the starting LC monomer, HB. Received: 26 September 1996/Revised: 7 November 1996/Accepted: 7 November 1996     

Observations of solid–liquid systems in anchor agitated vessels

Although process development is often done in well agitated vessels (e.g. with a retreat curve, pitched blade turbine etc.), there are a sizeable number of contract manufacturers’ still deploying a significant number of anchor agitated process units. For the purpose of observing the Zwietering constant value ‘S’ and few industrially important solid–liquid systems, we conducted extensive suspension experiments with anchor agitated vessels for varying D/T ratios (0.74 and 0.73). In this study, Zwietering's N_js (just suspension speed) and the corresponding ‘S’ factor were obtained for each system over a range of solid loadings. We found that the Zwietering constant was strongly dependent on the nature of the solid–liquid system; i.e. different systems had different ‘S’ values for the same geometrical configuration.     

Effect of processing route on the properties of Ni-based catalytic filters obtained from natural amorphous silica fibers

In this work catalytic fibrous filters were produced through two distinct processing routes from natural amorphous silica fibers (NASF) and Ni(NO₃)₂ solution (wet route) and NiO (dry route) as catalyst precursors. The Ni–SiO₂ fibers were characterized for X-ray powder diffraction, scanning electron microscope, particle size distribution, specific surface area, nickel contents, porosity, tortuosity, permeability, compressive strength, degree of dispersion, filtration and gas conversion efficiency. Morphological characterization revealed that Ni from wet route was distributed over the silica fibers with significantly lower particle size than the Ni produced through the dry route. Both methods led to a homogeneous distribution of Ni. The catalytic fibrous filter obtained from the dry route showed higher conversion efficiency for both propylene and propane, especially at high temperatures, due to the higher degree of dispersion of Ni particles over the NASF surfaces.     

Secondary effects of antioxidant on PS/PVME blends

Interactions between the antioxidant Santonox (4,4′-thiobis(6-tert-butyl-m-cresol)) and the LCST polymer blend of polystyrene (PS) and polyvinylmethylether (PVME) were examined. The presence of the antioxidant caused inhomogeneities in blend films cast from toluene solutions at antioxidant compositions greater than 0.25 wt% of the PVME. Also, the cloud-point of the blend decreased linearly with antioxidant content with a slope of 21 °C/wt%. As expected, the ability of the antioxidant to prevent degradation of the PVME within the blend was found to increase with increasing Santonox composition. Based on these results, an antioxidant composition of no more than 0.10 wt% is recommended in the studies of PS/PVME blends.     

Support and precursor effects on the preparation of new heterogenized Pt/Sn catalysts for the selective hydroformylation of 1-pentene

New heterogenized Pt/Sn catalysts selective for the hydroformylation of 1-pentene have been synthesized. The complex cis-[PtCl₂(PPh₃)₂] and the SnCl₂.2H₂O or SnC₂O₄ precursors have been anchored on silica-, magnesia- and alumina-carriers. X-ray photoelectron spectroscopy was used to determine the surface composition and the nature of the anchored species. The hydroformylation activity was found to depend on the type of support and tin precursor used. Only the silica supported catalysts were active in the hydroformylation reaction. Samples prepared from SnCl₂-2H₂O were 200-fold more active than those prepared from SnC₂O₄. Selectivity ton-hexanal of the silica-supported catalyst prepared from SnCl₂-2H₂O was as high as 94.4% at 39.2% conversion of 1-pentene.