Performance of Recycled Polylactic Acid/Amorphous Polyhydroxyalkanoate Blends.

Blends of polylactic acid (PLA) with amorphous polyhydroxyalkanoate (aPHA) are less brittle than neat PLA, thus enabling their use as biodegradable packaging. This work investigated the impact of recycling on the properties of neat PLA and PLA/aPHA blends with 90 and 75 wt. % PLA. After the materials were subjected to five heat histories in a single-screw extruder, the mechanical, rheological, and thermal properties were measured. All recycled compounds with 100% PLA and 75% PLA had similar decomposition behavior, whereas the decomposition temperatures for the blends with 90% PLA decreased with each additional heat cycle. The glass transition and melting temperatures were not impacted by reprocessing, but the crystallinity increased with more heat cycles. The complex viscosity of the reprocessed PLA and PLA/aPHA blends was much lower than for the neat PLA and increasing the number of heat cycles produced smaller reductions in the complex viscosity of 100% PLA and the blend with 90% PLA; no change in complex viscosity was observed for blends with 75% PLA exposed to 2 to 5 heat cycles. The tensile properties were not affected by reprocessing, whereas the impact strength for the 75% PLA blend decreased with reprocessing. These properties suggest that users will be able to incorporate scrap into the neat resin for thermoformed packaging.

Tandem Hydroperoxyl-Alkylperoxyl Radical Quenching by an Engineered Nanoporous Cerium Oxide Nanoparticle Macrostructure (NCeONP): Toward Efficient Solid-State Autoxidation Inhibitors.

The use of nanomaterials as inhibitors of the autoxidation of organic materials is attracting tremendous interest in petrochemistry, food storage, and biomedical applications. Metal oxide materials and CeO2 in particular represent one of the most investigated inorganic materials with promising radical trapping and antioxidant abilities. However, despite the importance, examples of the CeO2 material's ability to retard the autoxidation of organic substrates are still lacking, together with a plausible chemical mechanism for radical trapping. Herein, we report the synthesis of a new CeO2-derived nanoporous material (NCeONP) with excellent autoxidation inhibiting properties due to its ability to catalyze the cross-dismutation of alkyl peroxyl (ROO•) and hydroperoxyl (HOO•) radicals, generated in the system by the addition of the pro-aromatic hydrocarbon γ-terpinene. The antioxidant ability of NCeONP is superior to that of other nanosized metal oxides, including TiO2, ZnO, ZrO2, and pristine CeO2 nanoparticles. Studies of the reaction with a sacrificial reductant allowed us to propose a mechanism of inhibition consisting of H atom transfer from HOO• to the metal oxides (MOx + HOO• → MOx-H• + O2), followed by the release of the H atom to an ROO• radical (MOx-H• + ROO• → MOx + ROOH). Besides identifying NCeONP as a promising material for developing effective antioxidants, our study provides the first evidence of a radical mechanism that can be exploited to develop novel solid-state autoxidation inhibitors.

Impact of Melt Processing Conditions on the Degradation of Polylactic Acid.

To reduce the degradation of polylactic acid (PLA) during processing, which reduces the molecular weight of PLA and its properties, prior studies have recommended low processing temperatures. In contrast, this work investigated the impact of four factors affecting shear heating (extruder type, screw configuration, screw speed, and feed rate) on the degradation of PLA. The polylactic acid was processed using a quad screw extruder (QSE) and a comparable twin screw extruder (TSE), two screw configurations, higher screw speeds, and several feed rates. The processed PLA was characterized by its rheological, thermal, and material composition properties. In both screw configurations, the QSE (which has a greater free volume) produced 3-4 °C increases in melt temperature when the screw speed was increased from 400 rpm to 1000 rpm, whereas the temperature rise was 24-25 °C in the TSE. PLA processed at low screw speeds, however, exhibited greater reductions in molecular weight-i.e., 9% in the QSE and 7% in the TSE. Screw configurations with fewer kneading blocks, and higher feed rates in the QSE, reduced degradation of PLA. At lower processing temperatures, it was found that an increase in melt temperature and shear rate did not significantly contribute to the degradation of PLA. Reducing the residence time during processing minimized the degradation of PLA in a molten state.

Fabrication of Flexible Polymer Molds for Polymer Microstructuring by Roll-to-Roll Hot Embossing.

Roll-to-roll hot embossing could revolutionize the manufacturing of multifunctional polymer films with the ability to process large area at a high rate with reduced cost. The continuous hot embossing of the films, however, has been hindered due to the lack of durable and flexible molds, which can replicate micro and nanofeatures with reliability over several embossing cycles. In this work, we demonstrate for the first time the fabrication of a flexible polymer (polyimide) mold from the commercially available sheet by a maskless photolithography approach combined with inductively coupled plasma etching and its potential application to the roll-to-roll hot embossing process. The flexible polyimide mold consisted of holes with controlled dimensions: diameter: 14 µm, spacing: 16.5 µm, and depth: 6.8 µm. The reliability of flexible polyimide mold was tested and implemented by embossing micron-sized features on a commercial thermoplastic polymer, polyamide, and thermoplastic elastomer (TPE) sheet. The polyimide mold replicated micron-sized features on polymer substrates (polyamide and TPE) with excellent fidelity and was durable even after numerous embossing cycles.