Interplay between yielding, 'recovery', and strength of yield stress fluids for direct ink writing: new insights from oscillatory rheology.

Formulation design and rheology are critical for successful manufacturing direct ink writing (DIW), thus linking rheology and printability is a growing area of research amongst the DIW and rheology communities. This work provides an extensive rheological investigation into the material strength, yielding and 'recovery' properties of graphite (Gr)-hydrogel based formulations. Using state-of-the-art Large Amplitude Oscillatory Shear (LAOS) techniques, Fourier Transform (FT) rheology and sequence of physical process (SPP) analysis, and 3-step 'recovery' tests we provide new insights on the yielding phenomenon, energy transitions and microstructural changes that the formulations undergo. The insights from the rheology experiments are combined with and continuous monitoring during the printing process. From these analyses, we select rheological metrics or descriptors to quantify flowability, recoverability, and material strength. There is a threshold concentration of Gr powders (30 wt%) at which there is a shift in the yielding process. Below this threshold (for the F127 hydrogel and mixtures with low Gr content), perfect plastic dissipation ratio () values are close to 0 in the LVR and then steeply increase to close to 1 after the cross-over in a narrow strain (and stress) space. As Gr concentration increases, and print quality gets worse, values consistently increase in the LVR and at any given , evidencing an increased energy dissipation throughout the flow transition region. Lissajous-Bowditch curves and SPP Cole-Cole plots illustrate these trends. The extent of the 'recovery' (quantified by the mutation time, , and the storage modulus 'recovered' after large deformations ) is also directly related to Gr content, with higher loading resulting in lesser recovery. Our findings provide a comprehensive set of metrics to characterise complex (yield stress) fluids for DIW using three property maps, one for each stage: flowability or yielding process, recoverability and material strength. The results demonstrate that considering these three maps holistically provides insightful trends to guide formulation design and assess performance in DIW.