Spreading ceramic stereolithography pastes: Insights from shear- and orthogonal-rheology

We study the shear rheological behavior of a commercial stereolithography paste containing ≈50 vol. % of zirconia particles (diameter ≈ 100 nm) with the aim to clarify physical mechanisms occurring during the “scraping” step of this yield stress fluid. Beyond a flow curve characterized by a high zero-shear viscosity accompanied with an overall shear-thinning behavior, we investigate in a systematic way the transient regime through start-up experiments. We demonstrate that a structural transition occurs between 10−2 and 10−1 s−1, resulting in an apparent interruption of the shear-thinning. The corresponding transient response presents a pronounced extra-growth of the shear stress before to stabilize at high strain amplitude and a negative first normal stress difference peak, both effects become stronger at higher shear rates. These observations are rationalized based on the high interparticle friction owing to the polyhedral shape and the roughness of the particles. In addition, relaxation tests following the start-up experiments reveal that the samples submitted to shear rates higher than 10−1 s−1 cannot relax the shear stress to the same level as in low shear rate experiments, suggesting a durable structural modification likely to impact the quality of the parts prior to their debinding and densification. Finally, we utilize orthogonal superposition rheology to illustrate how the application of an oscillatory deformation during the scraping procedure could help to reduce the shear-thinning interruption and improve the stereolithography processing as already observed empirically during scraping.