Polymer processing often activates material degradation, which affects to some extent the performance or the life cycle of the obtained products. Polymer degradation is usually evidenced by molecular weight variations as consequence of exposure to high processing temperature and to relevant mechanical stresses. The degrading effects of melt extrusion under different thermo‐mechanical conditions on polymethyl‐methacrylate and polystyrene are investigated. Materials were processed at different temperatures and rates in a single screw extruder and in a capillary rheometer. Processed and as‐received materials were analysed by Gel permeation chromatography, solution viscosity, and melt rheology. Evaluations of molecular weight and rheological behavior changes after processing, as compared with as‐received materials, evidenced the extent of degradation in the different conditions. Experimental analysis was accompanied by finite elements simulation of the polymer flow and heat transmission within the extruder. This allowed an estimation of the expected shear stresses and temperatures distributions, thus indicating potentially critical situations. It was found that the materials processed at the highest rates in extruder presented lowest molecular weight reductions. This was attributed to the shorter residence time in the extruder and to the possibility of wall slip phenomena, which likely reduce the actual shear stress and viscous dissipation in the fast processing conditions. POLYM. ENG. SCI., 47:1813–1819, 2007. © 2007 Society of Plastics Engineers

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The development of materials with the ability of intrinsic self-repairing after damage in a fashion resembling that of living tissues has important scientific and technological implications, particularly in relation to cost-effective approaches toward damage management of materials. Natural rubbers with epoxy functional groups in the macromolecular chain (ENR) and ethylene-methacrylic acid ionomers having acid groups partially neutralized with metal ions possess self-repairing behavior following high energy impacts. This research investigates the self-repairing behavior of both ENR and ionomers during ballistic puncture test on the basis of their thermal and mechanical properties. Heterogeneous blending of ionomers and ENR have also been used here as a strategy to tune the thermal and mechanical properties of the materials. Interestingly, blends of sodium ion containing ionomer exhibit complete self-repairing behavior, whereas blends of zinc ion containing ionomer show limited mending. The chemical structure studied by FTIR and thermal analysis shows that both ion content of ionomer and functionality of ENR have significant influence on the self-repairing behavior of blends. The mobility of rubbery phases along with its interaction to ionomer phase in the blends significantly changes the mending capability of materials. The healing behavior of the materials has been discussed on the basis of their thermal, mechanical, and rheological tests for each materials.

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The effect of blending on the self‐healing behavior of an ethylene/methacrylic acid copolymer ionomer is investigated. Binary EMNa/EVA and EMNa/ENR blends are studied by ballistic puncture tests. In the composition range explored (15–50 wt% of EVA and ENR), the self‐healing characteristics decrease with increasing amount of EVA but are maintained in the whole range for EMNa/ENR blends. The bullet impact zones were observed using OM. Tensile tests showed that the blending process gives the opportunity to tune the mechanical characteristics without significant loss in the self‐healing properties, particularly in EMNa/ENR blends. Component compatibility, blend morphology and thermal properties were studied using DSC, SEM, and DMTA. Molecular interactions between the phases in the blends are discussed.

In this research work, biocomposites based on a ternary system containing softwood Kraft lignin (Indulin AT), poly-L-lactic acid (PLLA) and polyethylene glycol (PEG) have been developed. Two binary systems based on PLLA/PEG and PLLA/lignin have also been studied to understand the role of plasticizer (i.e., PEG) and filler (i.e., lignin) on the overall physicomechanical behavior of PLLA. All samples have been prepared by melt-blending. A novel approach has also been introduced to improve the compatibility between PLLA and PEG by using a transesterification catalyst under reactive-mixing conditions. In PEG plasticized PLLA flexibility increases with increasing content of PEG and no significant effect of the molecular weight of PEG on the flexibility of PLLA has been observed. Differential scanning calorimetry and size-exclusion chromatography along with FTIR analysis show the formation of PLLA-b-PEG copolymer for high temperature processed PLLA/PEG systems. On the other hand, binary systems containing lignin show higher stiffness than PLLA/PEG system and good adhesion between the particles and the matrix has been observed by scanning electron microscopy. However, a concomitant good balance in stiffness introduced by the lignin particles and flexibility introduced by PEG has been observed in the ternary systems. This study also showed that high temperature reactive melt-blending of PLLA/PEG leads to the formation of a segmented PLLA-b-PEG block copolymer

SUMMARY A new family of multi-block copolymers having the structure of poly(ester-carboni*te)s was obtained by a chain-extension reaction involving poly(1actic-glycolic acid) oligomers (PLGA) and o'ligomeric a,o-bishydroxy-terminated poly(ecapro1actone)s (PCDT). The latter were first transformed into a,obis(chloroformate)s, which were subsequently condensed in the presence of amines with both the hydroxylic and the carboxylic end-groups of PLGA oligomers. Several samples differing in the length of the PCDT segments and in the composition of the PLGA segments were prepared and characterized for their physico-chemica1 properties. All of them had high molecular weight, good solubility in organic solvents, and modest swellability in aqueous media. As regards their thermal behaviour, some samples showed evidence of the presence of a crystalline phase. Since these products are potentially useful as bioerodible materials in drug delivery systems, some preliminary results on their degradation behaviour under conditions mimicking those found in biological fluids are reported.

In this work the effect of melt mixing condition and of a trans‐esterification catalyst on miscibility of poly(methyl methacrylate) (PMMA)/polycarbonate of bisphenol A (PC) blends is studied. In particular, at high temperature chemical reactions between PMMA and PC phases can take place; these strongly change the compatibility in the blend and materials having single Tg can be obtained. FT‐IR analyses, coupled with solvent extraction, suggest that a grafting reaction of PC on PMMA is involved. SEC and DSC data are consistent with spectroscopic results, and some decrement of the molar weight distribution (MWD) of PC phase is observed. On the other hand, the presence of a fraction of modified material having higher MWD of starting PMMA is also noticed. The single Tg characteristic of some materials has been confirmed by experimental data of structural relaxation performed by differential scanning calorimetry (DSC). These materials showed optical clarity and the morphological analysis performed by scanning electron microscopy (SEM) confirm the homogeneity of these materials.