3D
printing of amorphous and crystalline ceramics is of paramount
importance for the fabrication of a wide range of devices with applications
across different technology fields. Printed ceramics are remarkably
enabled by the sol–gel synthesis method in conjunction with
continuous filament direct ink writing. During printing, multiple
processes contribute to the evolution of inks including shape retention,
chemical conversion, solidification, and microstructure formation.
Traditionally, depending on the ink composition and printing environment,
several mechanisms have been associated with the shape retention and
solidification of 3D printed structures: gelation, rapid solvent evaporation,
energy-driven phase transformation, and chemical-driven phase transformation.
Understanding the fundamental differences between these mechanisms
becomes key since they strongly influence the spatiotemporal evolution
of the materials, as the out-of-equilibrium processes inherent to
the extrusion, relaxation, and solidification of printed materials
have significant effects on the materials properties. In this work,
we investigate the shape retention mechanism and the hydrolysis-induced
material conversion and microstructure formation during the 3D printing
of a water reactive sol–gel ink that transforms into titanium
dioxide-based ceramic. This study aims at identifying characteristic
mechanisms associated with the material transformation, establishing
connections between the microstructure development and the timescales
associated with solidification under operando 3D-printing
conditions. The investigation of this material’s out-of-equilibrium
pathways under processing conditions is enabled by time-resolved coherent
X-ray scattering, providing simultaneous access to temporospatially
resolved microstructural and dynamics information. Furthermore, we
explore X-ray speckle tracking as a tool to resolve deformations of
the microstructure in a printed filament associated with the deposition
of consecutive filaments. Through this work, we aim at providing a
fundamental understanding of the relationships behind these transformative
processes in 3D printing and their timescales as the basis for achieving
unprecedented control over printed materials microstructure.