Influence of Processing Additives on the Degradation of Melt-Pressed Films of Poly(ε-Caprolactone) and Poly(Lactic Acid)

Melt-pressed films of polycaprolactone (PCL) and poly(lactic acid) (PLA) with processing additives, CaCO₃, SiO₂, and erucamide, were subjected to pure fungal cultures Aspergillus fumigatus and Penicillium simplicissimum and to composting. The PCL films showed a rapid weight loss with a minor reduction in the molecular weight after 45 days in A. fumigatus. The addition of SiO₂ to PCL increased the rate of (bio)erosion in A. fumigatus and in compost. The use of a slip additive, erucamide, was shown to modify the properties of the film surface without decreasing the rate of bio(erosion). Both the rate of weight loss and the rate of molecular weight reduction of PCL increased with decreasing film thickness. The addition of CaCO₃ to PLA significantly reduced the thermal degradation during processing, but it also reduced the rate of the subsequent (bio)degradation in the pure fungal cultures. PLA without additives and PLA containing SiO₂ exhibited the fastest (bio)degradation, followed by PLA with CaCO₃. The degradation of the PLA films was initially governed by chemical hydrolysis, followed by an acceleration of the weight change and of the molecular weight reduction. PLA film subjected to composting exhibits a rapid decrease in molecular weight, which then remains unchanged during the measurement period, probably because of crystallization.     

Radiation Effects on Blends of Poly(ε-Caprolactone) and Diatomites

Poly(-caprolactone) (PCL) was blended with diatomaceous earth (diatomite) and irradiated with -rays to introduce cross-linking between PCL molecules or both components. The unwashed diatomite containing a little of a volatile component showed high efficiency of introduction of cross-linking, whereas that with no volatile component showed low efficiency of introduction of cross-linking. Elongational viscosity, melt viscosity, and modulus of PCL/diatomite blend irradiated at various doses were significantly improved. Enzymatic degradation of the PCL/diatomite blend became faster than that of the PCL, though that of the blend irradiated became slower.     

Critical Review of Norms and Standards for Biodegradable Agricultural Plastics Part Ι. Biodegradation in Soil

A critical review of norms and standards and corresponding tests to determine the biodegradability in soil for biodegradable plastics, possibly applicable also to biodegradable agricultural plastics, is presented. There are only a few norms available at the international level about biodegradable plastics in soil. The criteria, parameters and testing methodologies for the characterization, labelling and validation of the agricultural plastic waste streams with respect to possible biodegradation in soil according to existing international standards are analysed while the relevant controversies are identified. To derive the best suited for agricultural plastics specs and testing methods, the possible developments or adaptation of available specs, is investigated. Considering the existing types of biodegradable plastic products in agriculture and their effective life management at the agricultural field, only a few norms appear to provide suitable tests that could be adapted, following appropriate research work, for testing biodegradability in soil under real field conditions. It is shown that some major revisions are needed, with the support of systematic research work, before a new universal norm and standard testing methods become available for testing agricultural plastics for biodegradation under real, and highly variable, soil conditions. Based on the analysis of the different norms and their content it appears necessary to incorporate provisions for transferability of results to different soils and climates, validation of tests through a positive reference and also, set prerequisites for soil media. Long term biodegradation in soil prediction is another open issue.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.     

Effects of Alkali Treatment on the Properties of Short Flax Fiber–Poly(Lactic Acid) Eco-Composites

In this study, the influence of alkali (NaOH) treatment on the mechanical, thermal and morphological properties of eco-composites of short flax fiber/poly(lactic acid) (PLA) was investigated. SEM analysis conducted on alkali treated flax fibers showed that the packed structure of the fibrils was deformed by the removal non-cellulosic materials. The fibrils were separated from each other and the surface roughness of the alkali treated flax fibers was improved. The mechanical tests indicated that the modulus of the untreated fiber/PLA composites was higher than that of PLA; on the other hand the modulus of alkali treated flax fiber/PLA was lower than PLA. Thermal properties of the PLA in the treated flax fiber composites were also affected. T_g values of treated flax fiber composites were lowered by nearly 10 °C for 10% NaOH treatment and 15 °C for 30% NaOH treatment. A bimodal melting behavior was observed for treated fiber composites different than both of neat PLA and untreated fiber composites. Furthermore, wide angle X-ray diffraction analysis showed that the crystalline structure of cellulose of flax fibers changed from cellulose-I structure to cellulose-II.     

Mechanical Properties and Lipase-Catalyzed Biodegradation of α-Methyl, ε-Caprolactone/ ε-Caprolactone Copolymers Obtained by Chemical Modification of Poly(ε-caprolactone)

Novel (-caprolactone)-based copolymers of different compositions were synthesized by allowing methyl iodide to react with the polycarbanion that resulted from the action of lithium diisopropylamide on poly(-caprolactone) in THF at –70°C under argon atmosphere. The copolymers were characterized by various techniques, namely ¹H nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry, x-ray diffraction and viscoelasticimetry. They were submitted to hydrolytic and lipase-catalyzed enzymatic degradation in comparison with genuine PCL. The Young modulus depended on the degree of methylation. In contrast, loss angle and glass transition temperature did not depend on this parameter. It is shown that the lipase-catalyzed degradation of methylated PCL is much slower than in the case of genuine PCL.     

Thermal and Biodegradable Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Poly(ε-Caprolactone) Compounded with Functionalized Organoclay

Poly(l-lactide) (PLLA)/Poly(ε-caprolactone) (PCL) blends were compounded with commercially available organoclay Cloisite 25A (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Functionalized Organoclay (F-C25A). The silicate layers of PLLA/PCL/F-C25A were exfoliated to a larger extent than PLLA/PCL/C25A. Incorporation of the epoxy groups on C25A improved significantly mechanical properties of PLLA/PCL/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PCL/F-C25A as compared with that in PLLA/PCL/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that the nanocomposites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. The biodegradability of the neat PLLA/PCL and corresponding nanocomposite was studied under compost, and the rate of biodegradation of PLLA/PCL increased after nanocomposite preparation.     

Electrospun Composite Nanofibers Based on Poly (ε-Caprolactone) and Styrax Liquidus (Liquidambar orientalis Miller) as a Wound Dressing: Preparation,Characterization, Biological and Cytocompatibility Results

Journal of Polymers and the Environment - In this study, styrax liquidus (sweet gum balsam) extracted from Liquidambar orientalis Mill. incorporated PCL fibrous scaffolds were prepared using the...     

Thermoplastic Blends Based on Poly(Butylene Succinate-co-Adipate) and Different Collagen Hydrolysates from Tanning Industry—II: Aerobic Biodegradation in Composting Medium

Journal of Polymers and the Environment - Two different raw hydrolyzed collagens (HCs), by-products of the Tannery industry, were investigated in blends with a bioplastic, as poly(butylene...