Molecular mass engineering for filaments in material extrusion additive manufacture

Abstract 3D printing of thermoplastics through local melting and deposition via material extrusion additive manufacturing provides a simple route to the near net‐shape manufacture of complex objects. However, the mechanical properties resulting from these 3D printed structures tend to be inferior when compared to traditionally manufactured thermoplastics. These unfavorable characteristics are generally attributed to the structure of the interface between printed roads. Here, we illustrate how the molecular mass distribution for a model thermoplastic, poly(methyl methacrylate) (PMMA), can be tuned to enhance the Young's modulus of 3D printed plastics. Engineering the molecular mass distribution alters the entanglement density, which controls the strength of the PMMA in the solid state and the chain diffusion in the melt. Increasing the low molecular mass tail increases Young's modulus and ultimate tensile strength of the printed parts. These changes in mechanical properties are comparable to more complex routes previously reported involving new chemistry or nanoparticles to enhance the mechanical performance of 3D printed thermoplastics. Controlling the molecular mass distribution provides a simple route to improve the performance in 3D printing of thermoplastics that can be as effective as more complex approaches.