No abstract

As direct digital manufacturing, 3D printing (3DP) technology provides new development directions and opportunities for the high-value utilization of a wide range of biological materials. Cellulose nanofibrils (CNF) and polylactic acid (PLA) biocomposite filaments for fused deposition modeling (FDM) 3DP were developed in this study. Firstly, CNF was isolated by enzymatic hydrolysis combined with high-pressure homogenization. CNF/PLA filaments were then prepared by melt-extrusion of PLA as the matrix and CNF as the filler. Thermal stability, mechanical performance, and water absorption property of biocomposite filaments and 3D-printed objects were analyzed. Findings showed that CNF increased the thermal stability of the PLA/PEG600/CNF composite. Compared to unfilled PLA FDM filaments, the CNF filled PLA biocomposite filament showed an increase of 33% in tensile strength and 19% in elongation at break, suggesting better compatibility for desktop FDM 3DP. This study provided a new potential for the high-value utilization of CNF in 3DP in consumer product applications.

Polylactic acid (PLA) is one of the most promising biodegradable and recyclable thermoplastic biopolymer derived from renewable feedstock. Nanocellulose reinforced PLA biocomposites have received increasing attention in academic and industrial communities. In the present study, cellulose nanofibrils (CNFs) was liberated by combined enzymatic pretreatment and high-pressure homogenization, and then subsequently incorporated into the PLA matrix to synthesize PLA/CNF biocomposite films via solution casting and melt compression. The prepared PLA/CNF biocomposite films were characterized in terms of transparency (UV-Vis spectroscopy), chemical structure (attenuated total reflectance-Fourier transform infrared, ATR-FTIR; X-ray powder diffraction, XRD), thermal (thermogravimetric analyzer, TGA; differential scanning calorimetry, DSC), and tensile properties. With 1.0–5.0 wt % additions of CNF to the PLA matrix, noticeable improvements in thermal and physical properties were observed for the resulting PLA/CNF biocomposites. The 2.5 wt % addition of CNF increased the tensile strength by 8.8%. The Tonset (initial degradation temperature) and Tmax (maximum degradation temperature) after adding 5.0 wt % CNF was increased by 20 °C, and 10 °C, respectively in the nitrogen atmosphere. These improvements were attributed to the good dispersibility and improved interfacial interaction of CNF in the PLA matrix.

Fused filament fabrication (FFF) with thermoplastic filaments is the most popular 3D printing technology. The continuous polymer filaments undergo a series of thermal processes, including heating, melting, cooling, and solidification. Therefore, it is necessary to investigate the thermal behavior of polymer filaments. The present study aims to provide a fundamental study of the thermal decomposition behavior and the isothermal melting crystallization behavior of nanocellulose filled polylactic acid (PLA) filaments. The influences of nanocellulose contents on the thermal decomposition properties such as onset temperature (T onset ), the temperature at 20-wt % conversion (T α20 ), and the temperature at the peak decomposition rate (T p ) were examined by thermogravimetric analysis (TGA). The effects of nanocellulose contents on the glass transition temperature (T g ) and the melting temperature (T m ) were studied by differential scanning calorimetry (DSC). Effects of nanocellulose and polyethylene glycol (PEG) incorporation on the thermal decomposition activation energy, isothermal melting crystallization rate, and semi-crystallization time are also investigated. The addition of nanocellulose improves the thermal stability of PLA filament, whereas the addition of plasticizer PEG decreases the thermal stability. TGA and DSC kinetic analyses indicate that nanocellulose alone or together with PEG could drastically increase the crystallization rate and shorten the semi-crystallization time.