Quantitative Prediction of Stress Relaxation Kinetics in Dissociative Covalent Adaptable Networks
Year: 2025
Type: article
Abstract: A kinetic-structural model was developed to quantitatively describe the stress relaxation behavior of covalent adaptable networks based on the reversible Diels-Alder chemistry. The model draws on the analogy between stress relaxation and network de-cross-linking, where residual stress is attributed to elastically active network strands. A recursive network analysis, based on the Macosko-Miller approach, is coupled with a model that incorporates the reversible Diels-Alder reaction kinetics, stress-induced bond activation, and the reduced efficiency of bond exchanges during late-stage relaxation. The model was validated using rheological data from two Diels-Alder-based networks, with cross-linking kinetics and equilibrium conversions used to predict initial stresses. The stress relaxation behavior, including characteristic times and shape parameters across varying temperatures and cross-link densities, was accurately predicted using only two temperature-independent parameters. Beyond predictive capabilities, the model enables the extraction of kinetic and thermodynamic parameters from experimental data, supporting its use in both direct simulation and inverse design. Thanks to its low computational cost, the framework facilitates rapid exploration of compositional and structural scenarios, aiding the design of application-specific materials. This approach offers a robust and efficient tool for bridging the gap between dynamic covalent chemistries and the development of functional materials and their advanced processing.
Source: Macromolecules
Authors: Jessica Mangialetto, Osman Konuray, Sasan Moradi, Xavier Fernández-Francos, Joost Brancart, Niko Van den Brande, Xavier Ramis, Guy Van Assche
Language: English
Subfield: Polymers and Plastics
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G1175115578, G121809054, G1855990336, G2064873908, G2262748287, G2309174360, G2660406951, G279363373, G3005324705, G300979063, G34346518, G3480869486, G4074946077, G4176647807, G425668148, G430777504, Double dynamic polymer network architectures for multi-stimuli-responsive materials, G5080475149, G5421974903, G5805502524, G5991818737, G6305986374, Towards fast self-healing reversible covalent elastomeric and thermosetting networks for sustainable applications. Synthesis and characterization of new Diels-Alder building blocks with fast dynamics and tunable reversibility, G69051668, G7084143925, G7260864714, G7301165512, G8314348678, G897484643, G99296377
OpenAlex ID: W7108340406