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.

Well-Adhering, Easily Producible Photonic Reflective Coatings for Plastic Substrates.

The development of well-adhering, easily producible photonic reflective coatings is still a challenge. Here, an easy-to-produce, industrial viable process is reported that uses a primer layer of the so-called type II photoinitiator to obtain an excellent adhesion between a plastic substrate and one-dimensional (1D) photonic liquid crystalline coatings. Furthermore, a good alignment of the reactive cholesteric liquid crystal mixture is obtained using a bar-coating process, without alignment layers or surfactants. After photopolymerization, cross-hatch tape tests show a good adhesion of the photonic coating having a reflection band of 50% transmission with almost no scattering. Additionally, we demonstrate the ability to create well-adhering ∼100% reflective coatings by coating double layers and the ability to create single-layered cholesteric broadband reflectors using solely a reactivity gradient created by the primer layer. Our new interfacial method gives new opportunities to use reflecting 1D photonic coatings in industrial processes and applications and allows the bonding of almost any polymer to a plastic substrate.

Promising fluorescent dye for solar energy conversion based on a perylene perinone.

We describe the synthesis of a dye based on a perylene perinone and evaluate its potential as the functional material for use in the luminescent solar concentrator (LSC). The dye extends the absorption wavelength of LSCs using the perylene-based dye Lumogen Red 305 by more than ~50 nm, translating into the collection of potentially 25% more photons at a reasonable fluorescent quantum yield and photostability. When the new perinone is used in a two-waveguide LSC in conjunction with Red 305, the integrated edge emission of the total LSC system may be increased more than 24% when compared to the Red 305 dye alone.

Measured surface loss from luminescent solar concentrator waveguides.

The surface and edge emissions from dye-filled and dye-topped polycarbonate and polymethyl methacrylate luminescent solar concentrators were measured. We demonstrate that about 40-50% of the absorbed light energy (and 50-70% of the photons) is lost through the top and bottom surfaces of the filled waveguide. In most cases the escape cone losses are greater at the top than the bottom surface.