Thermal polymerization of thiol–ene network‐forming systems

The thermal polymerization of a tetrafunctional thiol (PETMP) and divinyl ether (TEGDVE) was monitored by temperature‐ramping differential scanning calorimetry (DSC) and the effects of inhibitor type and concentration, oxygen inhibition and initiator type were studied. The incorporation of inhibitors was required to produce a stable system at room temperature. Butylated hydroxytoluene (BHT) inhibited polymerization at low temperatures, but was inefficient at high temperatures and polymerization rates, and hence BHT is an ideal stabilizer. In contrast, a nitroxide inhibitor (NO‐67) was a very effective inhibitor and no polymerization occurred until all of the nitroxide was depleted. The presence of oxygen retarded the onset of polymerization but did not change the final conversion significantly. Polymerization with initiators having higher half‐life temperatures shifted the DSC peak to higher temperature because the rate of initiator decomposition and thus initiation was slower. Rheological investigations of the cure at different temperatures revealed that the gel time decreased significantly with increasing cure temperature, and the calculated apparent activation energy for PETMP/TEGDVE was 54 kJ mol^?1. Dynamical mechanical thermal analysis of the cured material was undertaken and frequency‐superposed results revealed that the glass transition region of PETMP/TEGDVE/azobisisobutyronitrile was much narrower than that of free‐radically cured dimethacrylate, but was similar to that of an epoxy resin cured with an aromatic diamine. This behaviour could be attributed to PETMP/TEGDVE network homogeneity, or to the less constrained crosslinks in the PETMP/TEGDVE network. Copyright © 2007 Society of Chemical Industry     

Spectral Conformal Parameterization

We present a spectral approach to automatically and efficiently obtain discrete free‐boundary conformal parameterizations of triangle mesh patches, without the common artifacts due to positional constraints on vertices and without undue bias introduced by sampling irregularity. High‐quality parameterizations are computed through a constrained minimization of a discrete weighted conformal energy by finding the largest eigenvalue/eigenvector of a generalized eigenvalue problem involving sparse, symmetric matrices. We demonstrate that this novel and robust approach improves on previous linear techniques both quantitatively and qualitatively.     

The full cost of high-speed rail: an engineering approach

This paper examines the full costs, defined as the sum of private and social costs, of a high-speed rail system proposed for a corridor connecting Los Angeles and San Francisco in California. The full costs include infrastructure, fleet capital and operating expenses, the time users spend on the system, and the social costs of externalities, such as noise, pollution, and accidents. Comparing these full costs to those of other competing modes contributes to the evaluation of the feasibility of high-speed rail in the corridor. The paper concludes that high-speed rail is significantly more costly than expanding existing air service, and marginally more expensive than auto travel. This suggests that high-speed rail is better positioned to serve shorter distance markets where it competes with auto travel than longer distance markets where it substitutes for air. Received: May 1996 / Accepted in revised form: December 1996     

Residence time distributions of gases in lab-scale polymer electrolyte membrane fuel cells (PEMFC)

The paper was aimed at modelling hydrodynamics in lab-scale polymer electrolyte fuel cells, more particularly in the distribution plates. Residence time distributions (RTD) were measured in a wide range of flow rates, using UV absorption of ozone injected as a tracer in the cell. The volume of the inlet and outlet systems, being of the order of the volume of the gas circuit machined in the distribution plates, was taken into account in calculations. Hydrodynamic behaviour of two flow patterns of the commercialised fuel cell investigated was successfully described using ideal reactor models.     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

On the Pre-oxidation Treatments of Four Commercial Ni-Based Superalloys in Air and in Ar–H<Subscript>2</Subscript>O at 950 °C

The short-term oxidation behaviour of RA 602CA, Inconel 693, Manaurite 40XO and Sumitomo 696, which are four alloys recommended for hydrocarbon processing, was studied both in air and in Ar–H₂O to determine the conditions of pre-oxidation treatments. Regardless of the considered material, the oxidation rate at 950 °C was systematically higher in Ar–H₂O than in dry air. Surface examination of the Al-containing alloys indicated that they were not uniformly oxidized all over the surface. All Al-containing alloys (from 1.6 to 3.2% wt) formed an external protective alumina scale and behaved as alumina-forming alloys in dry air at 950 °C. In contrast, these alloys developed a rate-controlling chromia scale and severe internal oxidation in a H₂O-containing atmosphere. Compared with their oxidation behaviour in air + H₂O, the phenomenon was significantly enhanced in the atmosphere that coupled water vapour with a low oxygen pressure. Consequently, the Al-containing alloys should not be pre-oxidized in a water vapour atmosphere prior to long exposure to a corrosive atmosphere. In contrast, the chromia-forming Al-free 696 alloy exhibited identical oxidation behaviour in both atmospheres, demonstrating that the degradation of this alloy was not significantly affected by water vapour.     

Conducting polyaniline composite: From syntheses in waterborne systems to chemical sensor devices

The development of a conducting composite from its one-step synthesis in aqueous dispersed medium to the characterization of its chemical sensor performance is detailed. Composite films of polyaniline and polyacrylate were processed from the crude dispersion with no need for post-formulation. The synthesis has been optimized to be as simple, cheap and transferable as possible. The composite composition is tunable, i.e. the nature of the dopant was varied and its effect on kinetic parameters was observed. Ab initio calculations have been performed on a series of six ionic systems to gain a deeper insight into the contribution of both the stability of the anilinium salts in the composite polymerization. The conductivities of all composites were recorded from room temperature to 150 °C and the thermal stability versus dopant highlighted. The conducting films were then studied as active layers in a chemical sensor. The results showed that these composites, easily synthesized and processed, are ammonia sensitive and exhibit a fast response when exposed to air pollution.