Petr Stloukal

Assessment of the interrelation between photooxidation and biodegradation of selected polyesters after artificial weathering.

Three commercially available biodegradable polymers, two different aromatic-aliphatic copolyesters and polylactic acid, intended for the fabrication of agricultural mulching films, in addition to other applications, were subjected to a series of tests with the aim of studying the relationship between their photooxidation and biodegradation. Photooxidation resulted in the rearrangement of polymeric chains, in the case of both copolyesters the events led to polymeric chain crosslinking and the formation of insoluble polymeric gel. The tendency was significantly more pronounced for the copolyester with the higher content of the aromatic constituent. As regards polylactic acid photochemical reactions were not accompanied by crosslinking but instead provoked chain scissions. A biodegradation experiment showed that, despite marked structural changes, the extent of photooxidation was not the decisive factor, which significantly modified the rate of biodegradation in all three materials investigated. The specific surface area of the sample specimens was shown to be more important.

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.

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.

Low molecular weight poly(lactic acid) microparticles for controlled release of the herbicide metazachlor: preparation, morphology, and release kinetics.

The preemergence chloroacetamide herbicide metazachlor was encapsulated in biodegradable low molecular weight poly(lactic acid) micro- and submicroparticles, and its release to the water environment was investigated. Three series of particles, S, M, and L, varying in their size (from 0.6 to 8 μm) and with various initial amounts of the active agent (5%, 10%, 20%, 30% w/w) were prepared by the oil-in-water solvent evaporation technique with gelatin as biodegradable surfactant. The encapsulation efficiencies reached were about 60% and appeared to be lower for smaller particles. Generally, it was found that the rate of herbicide release decreased with increasing size of particles. After 30 days the portions of the herbicide released for its highest loading (30% w/w) were 92%, 56%, and 34% for about 0.6, 0.8, and 8 μm particles, respectively. The release rates were also lower for lower herbicide loadings. Metazachlor release from larger particles tended to be a diffusion-controlled process, while for smaller particles the kinetics was strongly influenced by an initial burst release.

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.

The Effect of Plasma Treatment on the Release Kinetics of a Chemotherapy Drug from Biodegradable Polyester Films and Polyester-Urethane Films

ABSTRACT Investigation was made into the effect of plasma treatment on the release kinetics of the drug Temozolomide (TMZ) from thin, biodegradable polyester films, comprising polylactic acid (PLA) and polyester urethane. The authors utilized two systems to achieve this, the first being diffuse coplanar surface barrier discharge, applying air as the gaseous medium, while the other involved capacitively coupled radio frequency discharge plasma under an argon atmosphere with hexamethyldisiloxane. Results showed that both forms of plasma treatment positively reduced the undesirable burst effect and benefited the release rate of TMZ. The hydrolytic degradability of the materials was slightly enhanced following hydrophilization, whereas the same diminished after hydrophobization had taken place. This was especially true for PLA due to modification of its wettability. GRAPHICAL ABSTRACT

PLA based bionanocomposites and their transport properties

This paper deals with the evaluation of gas transport properties of bionanocomposites based on polylactic acid 2003D (PLA). Montmorillonite based fillers, Cloisite® 10A, 20A, 30B and natural Cloisite® Na+, were incorporated into PLA polymer films. PLA/clay mixtures were produced by twin screw extruder ZSK-25. Further testing sheets were prepared from PLA/clay mixtures by Brabender Plasti-Corder equipped by flat die. The prepared composites were evaluated for water absorption, permeability of gases and water vapors. Further material morphology was assessed using X-ray diffraction as well as transmission electron microscopy. The best results achieved compositions with PLA/Cloisite10A and Cloisite 30B.This paper deals with the evaluation of gas transport properties of bionanocomposites based on polylactic acid 2003D (PLA). Montmorillonite based fillers, Cloisite® 10A, 20A, 30B and natural Cloisite® Na+, were incorporated into PLA polymer films. PLA/clay mixtures were produced by twin screw extruder ZSK-25. Further testing sheets were prepared from PLA/clay mixtures by Brabender Plasti-Corder equipped by flat die. The prepared composites were evaluated for water absorption, permeability of gases and water vapors. Further material morphology was assessed using X-ray diffraction as well as transmission electron microscopy. The best results achieved compositions with PLA/Cloisite10A and Cloisite 30B.

Effect of A Hybrid Zinc Stearate-Silver System on the Properties of Polylactide and Its Abiotic and the Biotic Degradation and Antimicrobial Activity Thereof

This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the properties of the composite is investigated by electron microscopy, differential scanning calorimetry and tensile tests. Furthermore, the antimicrobial activities of the systems are examined. The degradation behaviour of the composites is studied in both abiotic and biotic (composting) environments at an elevated temperature of 58 °C. The results reveal good dispersion of the additive in the PLA matrix, a stabilizing effect exerted by the same on the polylactide matrix during processing, and slight reduction in glass transition temperature. The zinc stearate-silver component also reduces brittleness and extends elongation of the composite. Abiotic hydrolysis is not significantly affected, which is in contrast with pure PLA, although mineralization during the early stage of biodegradation increases noticeably. The composite exhibits antimicrobial activity, even at the lowest dosage of the zinc stearate/silver component (1 wt%). Moreover, Ag and Zn contents were found to be present in the composite during abiotic hydrolysis, which was demonstrated by minimal diffusion of Ag ions from the matrix and very extensive washing of compounds that contained Zn.

Influence of Polylactide Modification with Blowing Agents on Selected Mechanical Properties

The article presents research of modification of PLA with four types of blowing agents with a different decomposition characteristic. Modifications were made in both cellular extrusion and injection molding processes. The obtained results show that dosing blowing agents have the influence on mechanical properties and structure morphology. Differences in the obtained results are also visible and significant between cellular processes.

Biodegradation of high molecular weight polylactic acid

Polylactid acid seems to be an appropriate replacement of conventional non-biodegradable synthetic polymer primarily due to comparable mechanical, thermal and processing properties in its high molecular weight form. Biodegradation of high molecular PLA was studied in compost for various forms differing in their specific surface area. The material proved its good biodegradability under composting conditions and all investigated forms showed to be acceptable for industrial composting. Despite expectations, no significant differences in resulting mineralizations were observed for fiber, film and powder sample forms with different specific surface areas. The clearly faster biodegradation was detected only for the thin coating on porous material with high specific surface area.