Spray-Dried Cellulose Nanofibril-Reinforced Polypropylene Composites for Extrusion-Based Additive Manufacturing: Nonisothermal Crystallization Kinetics and Thermal Expansion

Isotactic polypropylene (iPP) is a versatile polymer. It accounts for the second-largest polymer consumption worldwide. However, iPP is difficult to 3D print via extrusion-based processing. This is attributable to its rapid crystallization rate. In this study, spray-dried cellulose nanofibrils (SDCNF) and maleic anhydride polypropylene (MAPP) were investigated to reveal their effects on the nonisothermal crystallization kinetics and thermal expansion of iPP. SDCNF at 3 wt % and 30 wt % accelerated the crystallization rate of iPP, while SDCNF at 10 wt % retarded the crystallization rate by restricting crystal growth and moderately increasing the nucleation density of iPP. Additionally, adding MAPP into iPP/SDCNF composites accelerated the crystallization rate of iPP. The effective activation energy of iPP increased when more than 10 wt % SDCNF was added. Scanning electron microscopy and polarized light microscopy results indicated that high SDCNF content led to a reduced gap size among SDCNF, which hindered the iPP crystal growth. The coefficient of thermal expansion of iPP/SDCNF10% was 11.7% lower than the neat iPP. In summary, SDCNF, at 10 wt %, can be used to reduce the warping of iPP during extrusion-based additive manufacturing.