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Imprinting macroscopic fracture during gelation: A mechanism for tuning colloidal gels

Wilbert J. Smit1, Thomas Gibaud1,2, Sébastien Manneville1,3, and Thibaut Divoux1,*

  • *Contact author: Thibaut.Divoux@ens-lyon.fr
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Phys. Rev. Materials 10, 045602 – Published 3 April, 2026

DOI: https://doi.org/10.1103/ng2j-nrfv

Abstract

Colloidal gels form through the sol-gel transition of attractive particle suspensions, where local aggregation leads to a space-spanning network with solidlike properties. Their microstructure and mechanical properties are highly sensitive to external perturbations, which can substantially alter the pathway of network formation. Here, we investigate how nonlinear oscillatory shear affects the sol-gel transition of colloidal silica suspensions. Using large-amplitude oscillatory shear (LAOS), we vary both the strain amplitude and the duration of oscillatory forcing, varying between one and two times the gelation time. We find that sufficiently large strain amplitudes or prolonged exposure to oscillations in the nonlinear regime irreversibly alter the gel properties: The storage modulus G′ decreases while its frequency dependence remains unchanged. In contrast, the loss modulus G″, which decreases monotonically with frequency under quiescent gelation, exhibits an upturn at high frequencies when the gel is formed under strong oscillatory shear. The viscoelastic spectra of gels formed under quiescent conditions are well captured by a fractional Maxwell model, while gels formed under LAOS require an additional fractional element to account for damage-induced dissipation. Rheo-imaging experiments corroborate this interpretation by revealing the growth of cracks in gels formed under LAOS. We further show that these gels display a progressively more ductile nonlinear response for prolonged exposure to LAOS during gelation. These results demonstrate that the interplay between nonlinear shear and gelation can permanently imprint a macroscopic fracture pattern into colloidal gels, offering a route to tune their viscoelastic properties.

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Phys. Rev. Materials 10, 045602– Published 3 April, 2026
  • Received 30 November 2025
  • Accepted 11 March 2026
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