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     

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.     

Sooting tendencies of primary reference fuels in atmospheric laminar diffusion flames burning into vitiated air

In this study, the sooting tendencies of primary reference fuels (PRFs) are measured in term of yield sooting indices (YSIs) in methane diffusion flames doped with the vapors of PRFs. The present paper represents an incremental advance complementing the original methodology prescribed by McEnally and Pfefferle. The influence of both PRF formulation and CO₂ dilution of the coflowing air on the YSIs is also assessed. The diffusion flames burning in a coflowing oxidizer stream are established over the Santoro’s burner and vapor of the liquid fuel to be investigated is injected into the fuel stream. Laser extinction measurements are performed to map the two-dimensional field of soot volume fraction in the flame. For the pure liquid hydrocarbons investigated, i.e., n-hexane, n-heptane, isooctane, and benzene, the YSI reported in the original paper by McEnally and Pfefferle quantitatively predict the sooting propensities, measured here at much higher dopant concentrations. The present study therefore extends the consistency of the YSI methodology on the Santoro’s burner. For blends of n-heptane and isooctane, the sooting tendency of doped flames exhibits regular and monotonic trends and decreases with increasing n-heptane mole fraction or CO₂ dilution. Interestingly, the evolution of YSI with the isooctane mole fraction exhibits a strong similarity for varying CO₂ mole fraction. A quadratic least-squares fit is then derived, providing a phenomenological model of YSI as a function of both isooctane mole fraction in the fuel stream and CO₂ mole fraction in the oxidizer. A non-negligible cross effect of PRF formulation and CO₂ dilution on YSI is revealed. The method elaborated within the framework of the present paper could be extended to surrogate fuels. This would help develop a comprehensive database and empirical correlations that could predict the sooting propensities of different surrogate fuels, therefore their potentially mitigationed soot production through control of fuel composition and/or exhaust gas recirculation. This database would also be useful for the validation of CFD simulations incorporating sophisticated model of soot production.     

Acoustic emission: Towards a real-time diagnosis technique for Proton Exchange Membrane Fuel Cell operation

This paper deals with one of the needs for PEMFC to be economically reliable: diagnosis tool for water management. This issue is actually a key parameter for both performance and durability improvement. Acoustic emission (AE) technique was employed to survey PEM single cell under various operating conditions. AE events coming from different sources have thus been identified, classified and finally ascribed to different phenomena induced by MEA water uptake and/or biphasic flow in the gas channel thanks to a statistical post-treatment of the acoustic data. Results, although qualitative, seems trusty enough to unravel hidden correlations between AE hits and physicochemical phenomena taking place during the cell operation and open up the way for an innovative and non-invasive online diagnosis tool.     

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     

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.     

Modeling adaptation of breast cancer treatment decision protocols in the <Emphasis Type=SmallCaps>Kasimir</Emphasis> project

Medical decision protocols constitute theories for health-care decision making that are applicable for “standard” medical cases but have to be adapted for the other cases. This holds in particular for the breast cancer treatment protocol studied in the Kasimir research project. Protocol adaptations can be seen as knowledge-intensive case-based decision support processes. Some examples of adaptations that have been performed by oncologists are presented in this paper. Several issues are then identified that need to be addressed while trying to model such processes, namely: the complexity of adaptations, the lack of relevant information about the patient, the necessity to take into account the applicability and the consequences of a decision, the closeness to decision thresholds, and the necessity to consider some patients according to different viewpoints. As handling these issues requires some additional knowledge, which has to be acquired, different methods are presented that perform adaptation knowledge acquisition either from experts, or in a semi-automatic manner. A discussion and a conclusion end the paper.     

Learning correct responses and errors in the Hebb repetition effect: Two faces of the same coin.

In a serial recall task, the Hebb repetition effect occurs when recall performance improves for a sequence repeated throughout the experimental session. This phenomenon has been replicated many times. Nevertheless, such cumulative learning seldom leads to perfect recall of the whole sequence, and errors persist. Here the authors report evidence that there is another side to the Hebb repetition effect that involves learning errors produced in a repeated sequence. A learning measure based on past recalls (correct or incorrect) shows that the probability of a given response increases with the number of prior occurrences of that response. The pattern of results reveals another manifestation of the Hebb repetition effect and speaks to the nature of implicit learning. (PsycINFO Database Record (c) 2010 APA, all rights reserved)