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

Abstract

Formulation design and rheology are critical for successful manufacturing <i>via</i> 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 <i>in situ</i> 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 (<i>ϕ</i>) 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, <i>ϕ</i> values consistently increase in the LVR and at any given <i>γ</i>₀, 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, <i>λ</i>_I, 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.