Additive manufacturing of ceramics from preceramic polymers: A versatile stereolithographic approach assisted by thiol-ene click chemistry

TL;DR

This paper presents a rapid, cost-effective stereolithographic method using thiol-ene click chemistry to produce high-density, defect-free Si-based ceramics from preceramic polymers, suitable for advanced structural applications.

Contribution

It introduces a novel additive manufacturing process combining thiol-ene chemistry with stereolithography for fabricating high-performance ceramics from preceramic polymers.

Findings

Ceramic structures are nearly fully dense with smooth surfaces.

The process enables shape preservation during polymer-to-ceramic transformation.

The SiOC honeycomb exhibits superior strength-to-weight ratio.

Abstract

Here we introduce a versatile stereolithographic route to produce three different kinds of Si-containing thermosets that yield high performance ceramics upon thermal treatment. Our approach is based on a fast and inexpensive thiol-ene free radical addition that can be applied for different classes of preceramic polymers with carbon-carbon double bonds. Due to the rapidity and efficiency of the thiol-ene click reactions, this additive manufacturing process can be effectively carried out using conventional light sources on benchtop printers. Through light initiated cross-linking, the liquid preceramic polymers transform into stable infusible thermosets that preserve their shape during the polymer-to-ceramic transformation. Through pyrolysis the thermosets transform into glassy ceramics with uniform shrinkage and high density. The obtained ceramic structures are nearly fully dense, have smooth surfaces, and are free from macroscopic voids and defects. A fabricated SiOC honeycomb was shown to exhibit a significantly higher compressive strength to weight ratio in comparison to other porous ceramics.