Towards Photocrosslinkable Lyotropic Blends of Organosolv Lignin and Hydroxypropyl Cellulose for 3D Printing by Direct Ink Writing

Polymer blends containing up to 70% organosolv lignin content and lyotropic cellulose derivatives have been established as "lignin inks" for direct ink writing of fully biobased 3D parts. However, a fast-crosslinking mechanism is needed to improve throughput and design space. In this paper, UV-photocrosslinkable organosolv lignin/hydroxypropyl cellulose inks are formulated through doping with common photocrosslinkers. The most potent photocrosslinkers for neat hydroxypropyl cellulose, lignin and their blends are determined through a series of DOEs. Hydroxypropyl cellulose is significantly more amenable to photocrosslinking than organosolv lignin. The optimal photocrosslinkable ink formulations are printable and exhibit up to 70% gel content, although thermal post-curing remains essential. Chemical, thermal, and mechanical investigations of the photocrosslinked 3D parts evidence efficient crosslinking of HPC through its hydroxyl groups, while lignin appears internally plasticized and/or degraded during inefficient photocrosslinking. Despite this, photocrosslinkable inks exhibit improved tensile properties, shape flexibility, and fidelity. The heterogeneous crosslinking and residual creep highlight the need to further activate lignin for homogeneous photocrosslinking in order to fully exploit the potential of lignin inks in DIW.