Polyhydroxyalkanoate (PHA) is a biodegradable plastic with great potential for tackling plastic waste and marine pollution issues, but its commercial applications have been limited due to its poor processability. In this study, surface-modified cellulose nanocrystals were used to improve the mechanical properties of PHA composites produced via a melt-extrusion process. Double silanization was conducted to obtain hydrophobically treated CNC-based fillers, using tetraethyl orthosilicate (TEOS) and methyltrimethoxysilane (MTMS). The morphology, particle size distributions, and surface characteristics of the silanized CNCs and their compatibility with a PHA polymer matrix differed by the organosiloxane treatment and drying method. It was confirmed that the double silanized CNCs had hydrophobic surface characteristics and narrow particle size distributions, and thereby showed excellent dispersibility in a PHA matrix. Adding hydrophobically treated CNCs to form a PHA composite, the elongation at break of the PHA composites was improved up to 301%, with little reduction of Young’s modulus, compared to pure PHA. Seemingly, the double silanized CNCs added played a similar role to a nucleation agent in the PHA composite. It is expected that such high ductility can improve the mechanical properties of PHA composites, making them more suitable for commercial applications.

Polyhydroxyalkanoate (PHA), with a long chain length and high poly(4–hydroxybutyric acid) (P4HB) ratio, can be used as a base polymer for eco-friendly and biodegradable adhesives owing to its high elasticity, elongation at break, flexibility, and processability; however, its molecular structures must be adjusted for adhesive applications. In this study, surface-modified cellulose nanofibers (CNFs) were used as a hydrophobic additive for the PHA-based adhesive. For the surface modification of CNFs, double silanization using tetraethyl orthosilicate (TEOS) and methyltrimethoxysilane (MTMS) was performed, and the thermal and structural properties were evaluated. The hydrophobicity of the TEOS- and MTMS-treated CNFs (TMCNFs) was confirmed by FT-IR and water contact angle analysis, with hydrophobic CNFs well dispersed in the PHA. The PHA–CNFs composite was prepared with TMCNFs, and its morphological analysis verified the good dispersion of TMCNFs in the PHA. The tensile strength of the composite was enhanced when 10% TMCNFs were added; however, the viscosity decreased as the TMCNFs acted as a thixotropic agent. Adding TMCNFs to PHA enhanced the flowability and infiltration ability of the PHA–TMCNFs-based adhesive, and an increase in the loss tangent (Tan δ) and adjustment of viscosity without reducing the adhesive strength was also observed. These changes in properties can improve the flowability and dispersibility of the PHA–TMCNFs adhesive on a rough adhesive surface at low stress. Thus, it is expected that double-silanized CNFs effectively improve their interfacial adhesion in PHA and the adhesive properties of the PHA–CNFs composites, which can be utilized for more suitable adhesive applications.

The effect of drying on the enzymatic hydrolysis of cellulose was determined by analysis of porosity and crystallinity. Fiber hornification induced by drying produced an irreversible reduction in pore volume due to shrinkage and pore collapse, and the decrease in porosity inhibited enzymatic hydrolysis. The drying effect index (DEI) was defined as the difference in enzymatic digestibility between oven- and never-dried pulp, and it was determined that more enzymes caused a higher DEI at the initial stage of enzymatic hydrolysis and the highest DEI was also observed at the earlier stages with higher enzyme dosage. However, there was no significant difference in the DEI with less enzymes because cellulose conversion to sugars during hydrolysis did not enhance enzymatic hydrolysis due to the decrease in enzyme activity. The water retention value (WRV) and Simons’ staining were used to measure pore volume and to investigate the cause of the decrease in enzymatic hydrolysis. A decrease in enzyme accessibility induced by the collapse of enzymes’ accessible larger pores was determined and this decreased the enzymatic hydrolysis. However, drying once did not cause any irreversible change in the crystalline structure, thus it seems there is no correlation between enzymatic digestibility and crystalline structure.