Grafting of Bacterial Polyhydroxybutyrate (PHB) onto Cellulose via In Situ Reactive Extrusion with Dicumyl Peroxide

Polyhydroxybutyrate (PHB) was grafted onto cellulose fiber by dicumyl peroxide (DCP) radical initiation via in situ reactive extrusion. The yield of the grafted (cellulose-<i>g</i>-PHB) copolymer was recorded and grafting efficiency was found to be dependent on the reaction time and DCP concentration. The grafting mechanism was investigated by electron spin resonance (ESR) analysis and showed the presence of radicals produced by DCP radical initiation. The grafted copolymer structure was determined by nuclear magnetic resonance (NMR) spectroscopy. Scanning electronic microscopy (SEM) showed that the cellulose-<i>g</i>-PHB copolymer formed a continuous phase between the surfaces of cellulose and PHB as compared to cellulose-PHB blends. The relative crystallinity of cellulose and PHB were quantified from Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) results, while the absolute degree of crystallinity was evaluated by differential scanning calorimetry (DSC). The reduction of crystallinity indicated the grafting reaction occurred not just in the amorphous region but also slightly in crystalline regions of both cellulose and PHB. The smaller crystal sizes suggested the brittleness of PHB was decreased. Thermogravimetric analysis (TGA) showed that the grafted copolymer was stabilized relative to PHB. By varying the reaction parameters the compositions (%PHB and %cellulose) of resultant cellulose-<i>g</i>-PHB copolymer are expected to be manipulated to obtain tunable properties

Lignin-Containing Cellulose Nanofibril-Reinforced Polyvinyl Alcohol Hydrogels

Two lignin-containing cellulose nanofibril (LCNF) samples, produced from two unbleached kraft pulps with very different lignin contents, were used to produce reinforced polyvinyl alcohol (PVA) hydrogels. The effects of LCNF loading (0.25–2 wt %) and lignin content on the rheological and mechanical properties of the reinforced hydrogels were investigated. The 2 wt % LCNF-reinforced PVA hydrogels exhibited up to a 17-fold increase in storage modulus and a 4-fold increase in specific Young’s modulus over that of pure PVA hydrogel. Both the mechanical and rheological properties of LCNF-reinforced PVA hydrogels can be tuned by varying LCNF loading and LCNF lignin content. During LCNF production, lignin reduced cellulose depolymerization, resulting in LCNF with high aspect ratios that promoted entanglement and physical bridging of the hydrogel network. Free lignin particles generated during LCNF production acted as multifunctional nanospacers that increased porosity of the hydrogels. Because LCNFs were produced from unbleached chemical pulps, which have high yields and do not require bleaching, this study provides a more sustainable approach to utilize lignocelluloses to produce biomass-based hydrogels than by methods using commercial bleached pulps

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

A smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigidity are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs