Inter-layer adhesion in material extrusion 3D printing: effect of processing and molecular variables

There has been extensive research in the field of material-extrusion (Mat-Ex) 3D printing to improve the inter-layer bonding process. Much research focusses on how various printing conditions may be detrimental to weld strength; many different feedstocks have been investigated along with various additives to improve strength. Surprisingly, there has been little attention on how fundamental molecular properties of the feedstock, in particular the average molar mass of the polymer, may contribute to microstructure of the weld. Here we show that weld strength increases with decreasing average molar mass, contrary to common observations in specimens processed in more traditional ways, e.g., by compression molding. Using a combination of synchrotron infra-red polarization modulation microspectroscopy measurements and continuum modelling, we demonstrate how residual molecular anisotropy in the weld region leads to poor strength and how it can be eradicated by decreasing the relaxation time of the polymer. This is achieved more effectively by reducing the molar mass than by the usual approach of attempting to govern the temperature in this hard to control non-isothermal process. Thus, we propose that molar mass of the polymer feedstock should be considered as a key control parameter for achieving high weld strength in Mat-Ex.