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The effect of accelerated weathering exposure time on the bioplastic, poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) was studied. The chemical structure and thermophysical property changes of solvent cast PHBV films were examined by a combination of optical microscopy, size exclusion chromatography, FTIR and 1 H NMR spectroscopies, tensile testing, and differential scanning calorimetry (DSC). The exposed PHBV surfaces experienced surface crazing upon weathering. The molar mass of weathered PHBV was shown to decrease due to chain scission which was dominant over the crosslinking reaction mechanism, and compositional analysis showed the polymer degradation was non-random between the hydroxybutyrate-hydroxyvalerate units. The degree of crystallinity for PHBV was shown to increase significantly (by about 20%) upon weathering. Tensile tests showed that the weathered PHBV exhibited reduced ultimate strength and elongation to break, while the Young's modulus increased ascribing to an increase in crystallinity. Different degradation mechanisms (Norrish I/II, radical initiation, crosslinking, and hydrolysis) of PHBV are proposed and confirmed based on the experimental findings. This study provides degradation insight for PHBV exposed to both UV radiation and moisture. [ABSTRACT FROM AUTHOR]

Corn stover and rice straw lignin samples received from ethanol pilot plants, along with softwood kraft lignin samples, were characterized using pyrolysis GC-MS, 13C CP/MAS NMR spectroscopy, and permanganate oxidation degradation. The lignins were then esterified using 1-methylimidazole as a catalyst in a pyridine-free reaction, and the thermal properties of the products were evaluated. Solid state NMR showed the rice straw lignin contained 18% residual polysaccharides. Pyrolysis GC-MS showed the softwood kraft, corn stover, and rice straw lignins to be G - type, H/G/S - type, and G/S - type, respectively. However, some discrepancy was apparent between the pyrolysis and permanganate oxidation studies as to the ratios of the monomeric makeup of the lignins. The kraft and rice straw lignins were determined to have high degrees of condensation, while the corn stover lignin was uncondensed. Little to no increase in solubility was noticed for corn stover or rice straw lignin esters in organic solvents. Glass transition temperatures (Tg) of the lignin derivatives were determined by a combination of differential scanning calorimetry, dynamic mechanical analysis, and parallel plate rheometry. [ABSTRACT FROM AUTHOR]