Probing Viscoelastic Properties and Interfaces in High-Density Polyethylene Vitrimers at the Nanoscale Using Dynamic Mode Atomic Force Microscopy.

Vitrimers are a new class of heterogeneous polymers that combine the best features of thermosets with those of thermoplastics. The introduction of cross-links strongly changes the viscoelastic behavior of vitrimer materials. However, the characterization and understanding of the nanostructures and interfaces in vitrimers resulting from dynamic cross-linking formation remain a major challenge. Here, using dynamic modes of atomic force microscopy (AFM), namely intermodulation AFM (ImAFM) and AFM-based dynamic mechanical analysis (AFM-nDMA), local viscoelastic properties and interfaces at the nanoscale length of high-density polyethylene (HDPE) vitrimer materials are reported. ImAFM imaging in combination with the k-means clustering algorithm clearly reveals two distinct phases in the vitrimer system with highly different viscoelastic properties. AFM-nDMA further provides quantitative nanoviscoelastic properties at the nanoscale to confirm that there is a cross-linking-rich aggregation area forming a nanosize network structure in the cross-linking-poor matrix phase. The cross-linking-rich region shows a similar elastic modulus but much higher adhesion force measured by AFM compared to the cross-linking-poor HDPE matrix. Furthermore, the frequency influence on the local viscoelastic properties of HDPE vitrimer at the nanoscale was initially screened. The observed HDPE vitrimer nanostructures and viscoelastic properties at the nanoscale also provide explanations on the observed bulk HDPE vitrimer crystallinity decrease and dimensional stability increase compared to HDPE. Therefore, probing the viscoelastic properties and interfaces of HDPE vitrimer provides important insights into understanding of the correlations between the vitrimer nanostructure and the bulk mechanical and rheological behaviors.

Characterizing graft distribution in maleic anhydride grafted polyethylene - GPC with IR and UV-detection.

As commodity plastics, polyolefins are in high demand and used in innumerable applications. An important reason for their success-story is their high versatility in terms of applications. The application range of polyolefins was significantly extended through the development of functionalization. A common functionalization for improving the compatibility of polyolefins with more polar polymers and surfaces is grafting with maleic anhydride. While maleic anhydride-grafted polyolefins have found widespread application, methods for their characterization remain rudimentary compared to the developments seen in the structural characterization of polyolefins in general. Herein, we propose two new approaches for determining the degree of functionalization as a function of the molar mass of maleic anhydride grafted polyolefins. On the one hand, the latest generation bandpass filter-based IR detectors are shown to be sensitive to the carbonyl moiety of MAH. After optimization of analysis conditions, the relation between MAH content and molar mass could be unraveled in an easily applicable approach suitable for routine analysis. On the other hand, the high reactivity of MAH was leveraged in a tagging approach. By imidization with a UV chromophore, MAH distribution can be assessed by HT-GPC-UV with significantly higher sensitivity compared to HT-GPC-IR.