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Thermogravimetric analysis (TGA) simultaneously coupled with mass spectrometry (MS) and Fourier transform infrared spectrometry (FTIR) was developed as an original technique to study the thermal modification/degradation of poly(epsilon-caprolactone) (PCL) through in depth analysis of the evolved gas. Perfectly well-defined PCL samples with controlled end groups, predictable molecular weight, and narrow molecular weight distribution were synthesized by living "coordination-insertion" ring-opening polymerization of epsilon-caprolactone initiated by aluminum triisopropoxide. TGA analyses carried out on purified PCL samples, deprived from any residual catalyst or monomer, highlighted a two-step thermal degradation. Evolved gas analysis by both MS and FTIR showed that the first process implies a statistical rupture of the polyester chains via ester pyrolysis reaction. The produced gases were identified as H(2)O, CO(2), and 5-hexenoic acid. The second step leads to the formation of epsilon-caprolactone (cyclic monomer) as result of an unzipping depolymerization process. The influence of parameters such as polyester molecular weight, nature of the PCL end groups, and presence of catalytic residues as well as the type of purge gas were investigated. The activation energy of the thermal degradation was also studied.

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The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Hoffman theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX (where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-b-PCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.

This article reports on the preparation and partial characterisation of silicone-based coatings filled with low levels of either synthetic multiwall carbon nanotubes (MWCNTs) or natural sepiolite (NS). The antifouling and fouling-release properties of these coatings were explored through laboratory assays involving representative soft-fouling (Ulva) and hard-fouling (Balanus) organisms. The bulk mechanical properties of the coatings appeared unchanged by the addition of low amounts of filler, in contrast to the surface properties, which were modified on exposure to water. The release of Ulva sporelings (young plants) was improved by the addition of low amounts of both NS and MWCNTs. The most profound effect recorded was the significant reduction of adhesion strength of adult barnacles growing on a silicone elastomer containing a small amount (0.05%) of MWCNTs. All the data indicate that independent of the bulk properties, the surface properties affect settlement, and more particularly, the fouling-release behaviour, of the filled materials.

Institutfuer KunststoflechnoZogie Universitaet S w a r t s w a r t , Germany +Centerfor Education and Research on Macromolecules University of Liege Liege, BelgiumPoly(1actide) (PLA), a biodegradable aliphatic polyester with excellent properties for different polymer applications, has been used mostly in the biomedical field, m a d y because of its high price, resulting from expensive polymerization and purification techniques. Although this polymer can play a major role in future markets for biodegradable polymers, the current high price has to be reduced significantly to at least $4 US/kg. Therefore, this paper aims to partially review the polymerization techniques traditionally used in PIA synthesis and to propose new developments that enable us to produce these polymers by an innovative process for just a portion of the costs traditionally charged, using reactive extrusion techniques in a closely intermeshing co-rotating twin screw extruder. This paper gives an overview of attainable mechanical properties and future markets.

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