Changes of physical properties of PLA-based blends during early stage of biodegradation in compost.

Three biodegradable plastics materials, namely pure poly(l-lactide) (PLA), PLA with plasticizer triacetine (TAC) and the mixture PLA/polyhydroxybutyrate (PHB) and TAC were investigated concerning changes of physical properties due to biodegradation in compost at 58°C up to 16days. With rising time of degradation in compost, both number and weight molecular masses were decreasing progressively, but only marginal change of the polydispersity index was observed which indicates that biodegradation is not random process. FTIR spectroscopy revealed that in spite of the extensive decrease of molecular weight, no substantial change in chemical composition was found. The most significant modification of the spectra consisted in an appearing of the broad band in region 3100-3300cm-1, which was assigned to a formation of biofilm on the sample surfaces. This effect appeared for all three materials, however, it was much more pronounced for samples containing also triacetine. Measurement of changes in crystalline portion confirmed that amorphous phase degrades substantially faster compared to crystalline part. The plasticizer triacetine is disappearing also rather fast from the sample resulting besides other effect also in a temporary increase of Tg, which at the beginning grows almost to the value typical for PLA without plasticizer but later the Tg is decreasing due to substantial changes in molecular weight. Generally during composting, the samples keep shape for up to 8days, after that time the material disintegrates to rough powder.

Accelerated Biodegradation of Agriculture Film Based on Aromatic-Aliphatic Copolyester in Soil under Mesophilic Conditions.

A study was conducted on the biodegradation of aromatic-aliphatic copolyester-based agricultural film in soil at 25 °C. The polymer is known to be biodegradable under composting conditions although rather recalcitrant under mesophilic conditions. The material investigated comprised of the copolyester filled with approximately 25% of starch containing biodegradable plasticizers, and its behavior was compared to the corresponding material without the filler. Mineralization followed by CO2 production merely reached the point of about 6% after 100 days of incubation in the pure copolyester film, whereas the value of around 53% was recorded for the filled copolyester film, which exceeded the readily biodegradable starch filler content in the material by more than 20% and could be accounted for biodegradation of the copolyester. It was suggested that the accelerated copolyester biodegradation in the starch-filled material was most likely explained by the increase in the active surface area of the material available for the microbial attack after biodegradation of the filler. The results were supported by changes in molecular weight distributions of the copolyester and observations made by several microscopic techniques. These findings encourage further development of biodegradable agricultural films based on this material.

Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities.

Identification of important abiotic and biotic factors in the biodegradation of poly(l-lactic acid).

The biodegradation of four poly(l-lactic acid) (PLA) samples with molecular weights (MW) ranging from approximately 34 to 160kgmol(-1) was investigated under composting conditions. The biodegradation rate decreased, and initial retardation was discernible in parallel with the increasing MW of the polymer. Furthermore, the specific surface area of the polymer sample was identified as the important factor accelerating biodegradation. Microbial community compositions and dynamics during the biodegradation of different PLA were monitored by temperature gradient gel electrophoresis, and were found to be virtually identical for all PLA materials and independent of MW. A specific PLA degrading bacteria was isolated and tentatively designated Thermopolyspora flexuosa FTPLA. The addition of a limited amount of low MW PLA did not accelerate the biodegradation of high MW PLA, suggesting that the process is not limited to the number of specific degraders and/or the induction of specific enzymes. In parallel, abiotic hydrolysis was investigated for the same set of samples and their courses found to be quasi-identical with the biodegradation of all four PLA samples investigated. This suggests that the abiotic hydrolysis represented a rate limiting step in the biodegradation process and the organisms present were not able to accelerate depolymerization significantly by the action of their enzymes.