Polymers2014, 6(4), 1232-1250; doi:10.3390/polym6041232 - published online 22 April 2014 Show/Hide Abstract
Abstract: In order to reduce the effects of hydrolytic degradation and to maintain sufficient viscosity during processing of biomass based poly(l-lactic acid) (PLLA), various epoxy functional reactive oligomers have been characterized and incorporated into the degraded fragments as chain extenders. The molecular weight of PLLA increased with the increase in functionality of the reactive oligomers. No further increase in molecular weight was observed for oligomers with functionality of greater than five. Under our experimental conditions, no gelation was found even when the highest functionality reactive oligomers were used. This is attributed to the preferential reaction of the carboxylic acid versus the negligible reactivity of the hydroxyl groups, present at the two ends of the degraded PLLA chains, with the epoxy groups. The study provides a clear understanding of the degradation and chain extension reaction of poly(lactic acid) (PLA) with epoxy functional reactive oligomers. It is also shown that a higher functionality and concentration of the reactive oligomers is needed, to bring about a sufficient increase in the molecular weight and hence the hydrolytic stability in circumstances when PLA chains suffer significant degradation during processing.
Polymers2014, 6(4), 1207-1231; doi:10.3390/polym6041207 - published online 22 April 2014 Show/Hide Abstract
Abstract: In this review, we focus on the electrical conductivity of aqueous polyelectrolyte solutions in the light of the dynamic scaling laws, recently proposed by Dobrynin and Rubinstein, to take into account the polymer conformations in different concentration regimes, both in good and poor solvent conditions. This approach allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to dilute and semidilute regimes. The electrical conductivity in the light of the scaling approach compares reasonably well with the observed values for different polyelectrolytes in aqueous solutions, over an extended concentration range, from the dilute to the semidilute regime.
Polymers2014, 6(4), 1187-1206; doi:10.3390/polym6041187 - published online 17 April 2014 Show/Hide Abstract
Abstract: The goal of this research project is to model the effect of confinement by means of fiber reinforced polymer (FRP) externally bonded wrapping, hence to provide a simplified closed form solution to determine directly the ultimate confined concrete strength. Common cross-section shapes for reinforced concrete (RC) columns are considered herein, namely square and rectangular. The simplified model is derived from a more refined iterative confinement model proposed by the same authors to evaluate the entire stress-strain relationship of confined concrete. Based on a detailed analysis of the stress state through Mohr’s circle, a simplified closed form solution is proposed to account for the non-uniformly confined concrete performance exhibited in non-axisymmetric sections. The non-uniform confining stress field exhibited in such cross-sections is explicitly considered by means of the mean value integral of the pointwise variable stress state over the cross-section. The key aspect of the proposed methodology is the evaluation of the effective equivalent pressure to be inserted in any triaxial confinement model, to account for the peculiarities of square and rectangular cross-sections. Experimental data, available in the literature and representative of a wide stock of applications, were compared to the results of the theoretical simplified model to validate the proposed approach, and satisfactory results were found.
Polymers2014, 6(4), 1178-1186; doi:10.3390/polym6041178 - published online 17 April 2014 Show/Hide Abstract
Abstract: Chitosan membranes can undergo a glass transition at room temperature triggered by hydration. The mechanical properties of the membranes were followed by a tension test and dynamic mechanical analysis (DMA), with the sample in wet conditions after being immersed in varying compositions of water/ethanol mixtures. Results show that with the increasing of water content, the Young’s and storage modulus decrease systematically. For water contents of ca. 35 vol%, chitosan (CHT) exhibits a glass transition, showing an elastomeric plateau in the elastic modulus above this hydration level and the occurrence of a peak in the loss factor. Due to the semi-crystalline nature of CHT, membranes of this biomaterial present a shape memory capability induced by water uptake. By fixation of the permanent shape by further covalent cross-linking, the membranes can have different permanent shapes appropriate for different applications, including in the biomedical area.
Polymers2014, 6(4), 1164-1177; doi:10.3390/polym6041164 - published online 15 April 2014 Show/Hide Abstract
Abstract: Thermoresponsive polymer coatings allow the control of adhesion of cells on synthetic substrates. In particular, decreasing the temperature below the lower critical solution temperature (LCST) of the polymer triggers the non-invasive detachment of cells from their cultivation substrate. Widening the range of applications of these coatings in cellular biotechnology requires a better understanding of their interaction with cells. By monitoring the morphological changes of cells during their detachment at various temperatures, we provide evidence that cell detachment is an active process. Analyses of cell residues that are left behind by the cells on the substrate during their detachment, further support this notion. In the second part of this work, we show that the kinetics of adhesion and the efficiency of detachment of cells can be controlled through the coadsorption of molecules bearing the peptide motif RGD (arginine-glycine-aspartic acid) with the polymers.
Polymers2014, 6(4), 1144-1163; doi:10.3390/polym6041144 - published online 11 April 2014 Show/Hide Abstract
Abstract: In this study some new concepts regarding certain aspects related to shape memory polymers are presented. A blend of polylactic acid (PLA) (80%) and polybutylene succinate (PBS) (20%) was prepared first by extrusion, then by injection molding to obtain the samples. Tensile, stress-relaxation and recovery tests were performed on these samples at 70 °C. The results indicated that the blend can only regain 24% of its initial shape. It was shown that, this partial shape memory effect could be improved by successive cycles of shape memory tests. After a fourth cycle, the blend is able to regain 82% of its shape. These original results indicated that a polymer without (or with partial) shape memory effect may be transformed into a shape memory polymer without any chemical modification. In this work, we have also shown the relationship between shape memory and property memory effect. Mono and multi-frequency DMA (dynamic mechanical analyzer) tests on virgin and 100% recovered samples of polyurethane (PU) revealed that the polymer at the end of the shape memory tests regains 100% of its initial form without regaining some of its physical properties like glass transition temperature, tensile modulus, heat expansion coefficient and free volume fraction. Shape memory (with and without stress-relaxation) tests were performed on the samples in order to show the role of residual stresses during recovery tests. On the basis of the results we have tried to show the origin of the driving force responsible for shape memory effect.