A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability

We report the manufacture of printable, sustainable polymer systems to address global challenges associated with high-volume utilization of lignin, an industrial waste from biomass feedstock. By analyzing a common three-dimensional printing process—fused-deposition modeling—and correlating the printing-process features to properties of materials such as acrylonitrile-butadiene-styrene (ABS) and nylon, we devised a first-of-its-kind, high-performance class of printable renewable composites containing 40 to 60 weight % (wt %) lignin. An ABS analog made by integrating lignin into nitrile-butadiene rubber needs the presence of a styrenic polymer to avoid filament buckling during printing. However, lignin-modified nylon composites containing 40 to 60 wt % sinapyl alcohol–rich, melt-stable lignin exhibit enhanced stiffness and tensile strength at room temperature, while—unexpectedly—demonstrating a reduced viscosity in the melt. Further, incorporation of 4 to 16 wt % discontinuous carbon fibers enhances mechanical stiffness and printing speed, as the thermal conductivity of the carbon fibers facilitates heat transfer and thinning of the melt. We found that the presence of lignin and carbon fibers retards nylon crystallization, leading to low-melting imperfect crystals that allow good printability at lower temperatures without lignin degradation.