Published December 20, 2023 | Version v1
Preprint Open

Dual-vat photopolymerization 3D printing of vitrimers

Authors/Creators

  • 1. ROR icon Polymer Competence Center Leoben (Austria)

Description

Vitrimers undergo stimuli-triggered bond exchange reactions, which render the covalently cross-linked networks malleable, repairable and recyclable. While additive manufacturing with single vitrimeric materials has become a well-established strategy for fabricating objects with unique functions, 3D printing of vitrimers with heterogeneous and locally controllable material properties is still in its infancy. Herein, the processing of multi-material vitrimers is demonstrated with a dual-vat digital light processing (DLP) 3D printer. The printer prototype contains two vats and a cleaning station, which are positioned on a linearly moving platform, and are exchanged automatically during the layer-by-layer build-up of the object. Two thiol-acrylate resins are selected containing ample -OH and ester moieties, which undergo thermo-activated transesterification in the presence of an organic phosphate as catalyst. Once cured, the photopolymers greatly differ in their mechanical properties allowing the printing of multi-material structures with soft (E’23°C = 209 kPa) and stiff (E’23°C = 507 MPa) domains. A good interlayer adhesion between the soft and hard domains is evidenced by uniaxial tensile tests, whilst optical microscopy is used to study the interface. Jacobs working curves of the two different resins reveal comparable printing parameters at higher exposure doses, which do not only facilitate the printing of multiple materials between individual layers (z-heterogeneity) but also within the same layer (x,y-heterogeneity). This is confirmed by the printing of a multi-material gripper, which contains soft inner teeth and a stiff outer core. Gripping and releasing of objects is demonstrated by exploiting the glass transition-based shape memory properties of the stiff domains. Moreover, due to the dynamic nature of the covalent bonds, damages inserted into the gripper are intrinsically repairable due to a thermo-activated macroscopic reflow. Shape memory experiments further confirmed that the multi-material gripper fully regains its function after the thermal mending process. Thus, the results clearly show that objects with a high degree of functionality can be realized by combining multi-material 3D printing with the chemistry of vitrimers. This is of particular interest for future soft robotic applications and for mimicking biological composite structures.

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Additional details

Funding

Austrian Research Promotion Agency
Chemitecture 21647048
European Union
Marie Sklodowska-Curie grant 860108

Dates

Submitted
2023-08-02
Preprint

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