Process and Material Modifications to Enable New Material for Material Extrusion Additive Manufacturing

The overall goal of this work is to expand the materials library for the fused filament fabrication (FFF) material extrusion additive manufacturing (AM) process through innovations in the FFF process, post-process, and polymer composition. This research was conducted at two opposing ends of the FFF-processing temperature: low processing temperature (<100 °C) for pharmaceutical applications and high processing temperatures (>300 °C) for high-performance structural polymer applications. Both applications lie outside the typical range for FFF (190-260 °C). To achieve these goals, both the material and process were modified.

Due to the low processing temperature requirements for pharmaceutical active ingredients, a water-soluble, low melting temperature material (sulfonated poly(ethylene glycol)) series was used to explore how different counterions affect FFF processing. The strong ionic interaction within poly(PEG8k-co-CaSIP) resulted in the best print quality due to the higher viscosity (105 Pa∙s) allowing the material to hold shape in the melt and the high-nucleation producing small spherulites mitigating the layer warping. Fillers were then explored to observe if an ionic filler would produce a similar effect. The ionic filler (calcium chloride) in poly(PEG8k-co-NaSIP) altered the crystallization kinetics, by increasing the nucleation density and viscosity, resulting in improved printability of the semi-crystalline polymer.

A methodology for embedding liquids and powders into thin-walled capsules was developed for the incorporation of low-temperature active ingredients into water-soluble materials that uses a higher processing temperature than the actives are compatible with. By tuning the thickness of the printed walls, the time of internal liquid release was controlled during dissolution. This technique was used to enable the release of multiple liquids and powders at different times during dissolution.

To enable the printing of high-temperature, high-performance polymers, an inverted desktop-scale heated chamber with the capability of reaching over 300 °C was developed for FFF. The design was integrated onto a FFF machine and was used to successfully print polyphenylsulfone which resulted in a 48% increase in tensile strength (at 200 °C) when compared to printing at room temperature.

Finally, the effects of thermal processing conditions for printing ULTEM® 1010 were studied by independently varying the i) nozzle temperature, ii) environment temperature, and iii) post-processing conditions. The nozzle temperature primarily enables flow through the nozzle and needs to be set to at least 360 °C to prevent under extrusion. The environment temperature limits the part warping, as it approaches Tg (217 °C), and improves the layer bonding by decreasing the rate of cooling that allows more time for polymer chain entanglement. Post-processing for a longer time above Tg (18 hrs at 260 °C) promotes further entanglement, which increases the part strength (50% increase in yield strength); however, the part is susceptible to deformation. A post-processing technique was developed to preserve the parts' shape by packing solid parts into powdered salt.