No abstract

In the present work, cellulose nanocrystals (CNCs) have been surface-modified either via covalent grafting or through physisorption of poly(n-butyl methacrylate) (PBMA) and employed as reinforcement in PCL. Covalent grafting was achieved by surface-initiated atom transfer radical polymerization (SI-ATRP). Two approaches were utilized for the physisorption: using either micelles of poly(dimethyl aminoethyl methacrylate)-block-poly(n-butyl methacrylate) (PDMAEMA-b-PBMA) or latex nanoparticles of poly(dimethyl aminoethyl methacrylate-co-methacrylic acid)-block-poly(n-butyl methacrylate) (P(DMAEMA-co-MAA)-b-PBMA). Block copolymers (PDMAEMA-b-PBMA)s were obtained by ATRP and subsequently micellized. Latex nanoparticles were produced via reversible addition-fragmentation chain-transfer (RAFT) mediated surfactant-free emulsion polymerization, employing polymer-induced self-assembly (PISA) for the particle formation. For a reliable comparison, the amounts of micelles/latex particles adsorbed and the amount of polymer grafted onto the CNCs were kept similar. Two different chain lengths of PBMA were targeted, below and above the critical molecular weight for chain entanglement of PBMA (M ∼ 56 000 g mol). Poly(ε-caprolactone) (PCL) nanocomposites reinforced with unmodified and modified CNCs in different weight percentages (0.5, 1, and 3 wt %) were prepared via melt extrusion. The resulting composites were evaluated by UV-vis, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and tensile testing. All materials resulted in higher transparency, greater thermal stability, and stronger mechanical properties than unfilled PCL and nanocomposites containing unmodified CNCs. The degradation temperature of PCL reinforced with grafted CNCs was higher than that of micelle-modified CNCs, and the latter was higher than that of latex-adsorbed CNCs with a long PBMA chain length. The results clearly indicate that covalent grafting is superior to physisorption with regard to thermal and mechanical properties of the final nanocomposite. This unique study is of great value for the future design of CNC-based nanocomposites with tailored properties.

Poly(ε-caprolactone) (PCL) is a ductile thermoplastic, which is biodegradable in the marine environment. Limitations include low strength, petroleum-based origin, and comparably high cost. Cellulose fiber reinforcement is therefore of interest although uniform fiber dispersion is a challenge. In this study, a one-step wet compounding is proposed to validate a sustainable and feasible method to improve the dispersion of the cellulose fibers in hydrophobic polymer matrix as PCL, which showed to be insensitive to the presence of the water during the processing. A comparison between unmodified and acetylated cellulosic wood fibers is made to further assess the net effect of the wet feeding and chemical modification on the biocomposites properties, and the influence of acetylation on fiber structure is reported (ATR-FTIR, XRD). Effects of processing on nanofibrillation, shortening, and dispersion of the cellulose fibers are assessed as well as on PCL molar mass. Mechanical testing, dynamic mechanical thermal analysis, FE-SEM, and X-ray tomography is used to characterize composites. With the addition of 20 wt % cellulosic fibers, the Young's modulus increased from 240 MPa (neat PCL) to 1850 MPa for the biocomposites produced by using the wet feeding strategy, compared to 690 MPa showed for the biocomposites produced using dry feeling. A wet feeding of acetylated cellulosic fibers allowed even a greater increase, with an additional 46% and 248% increase of the ultimate strength and Young's modulus, when compared to wet feeding of the unmodified pulp, respectively.