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PE vitrimer rheology_chemrxiv_revised.pdf (5.98 MB)
Linear Viscoelasticity and Flow of Self-Assembled Vitrimers: The Case of a Polyethylene/dioxaborolane System
Preprints are manuscripts made publicly available before they have been submitted for formal peer review and publication. They might contain new research findings or data. Preprints can be a draft or final version of an author's research but must not have been accepted for publication at the time of submission.
revised on 17.02.2020 and posted on 18.02.2020by RALM RICARTE, François Tournilhac, Michel Cloître, Ludwik Leibler
For vitrimer systems obtained by dynamic cross-linking of polymer chains, incompatibility effects between the cross-links and polymer backbone can lead to microphase separation, resulting in a network made of cross-linked aggregates. Additionally, when there is a wide distribution of the number of cross-links per chain, macrophase separation can occur. Here, we investigate the linear viscoelasticity and flow of a polyethylene (PE) vitrimer that has cross-linkable dioxaborolane maleimide grafts, which aggregate into a hierarchical nanostructure. To elucidate the role of self-assembly, noncross-linked graft functionalized PE was first studied. It had a terminal relaxation time that was orders of magnitude larger than both neat PE and partially peroxide cross-linked PE. When dioxaborolane cross-linker was added to form the vitrimer, the resulting material could not achieve terminal relaxation within 8 hr. The graft-poor soluble and graft-rich insoluble portions of the PE vitrimer were then isolated and characterized. The soluble portion expressed similar flow behavior as neat PE, while the insoluble portion – which is a network of cross-linked aggregates – relaxed very little over 8 hr. When the insoluble and soluble portions were blended, the rheological behavior of the original vitrimer was basically recovered, showing that the soluble portion acts as a lubricant. When the insoluble portion was blended with neat PE, the material relaxed much more stress, but still did not reach steady-state flow within 8 hr. When high stresses were applied, however, PE vitrimer flowed. Nonlinear rheology experiments revealed melt fracture at high strains and suggested that flow is enabled by rapid healing, which follows fracture events. The presence of macroscopic phase separation facilitated flow.