Thermally self-healing graphene-nanoplate/polyurethane (GNP/PU) nanocomposites were prepared via a bulk in-situ Diels–Alder (DA) reaction. Graphene-nanoplate (GNP) was used as a reinforcement and crosslinking platform by a DA reaction with a furfuryl-based chain extender of polyurethane (PU). Results showed that a DA reaction occurred in GNP during the PU forming cure process. This procedure is simple and solvent free because of the absence of any independent surface modification process. Through the calculation of the interfacial tensions, the conditions of the bulk in-situ DA reaction were determined to ensure that GNP and the furfuryl group can react with each other at the interface during the curing process without a solvent. The prepared composites were characterized in terms of thermal, mechanical, and thermally self-healing properties via the DA reaction. In the PU capable of a DA reaction (DPU), characteristic peaks of DA and retro DA reactions were observed in the Fourier transform infrared (FT-IR) spectroscopy and endothermic peaks of retro DA reactions appeared in differential scanning calorimetry (DSC) thermograms. The DPU showed significantly enhanced physical properties and chemical resistance. The thermally self-healing capability was confirmed at 110 °C via the retro DA reactions. It is inferred that thermally self-healable crosslinked GNP/PU nanocomposites via DA reactions could be prepared in a simple bulk process through the molecular design of a chain extender for the in-situ reaction at the interface.

In this study, a highly concentrated graphite nanoplate (GNP)/polyol masterbatch was prepared by the exfoliation of natural graphite in an aqueous system using cetyltrimethylammonium bromide and the replacement of aqueous solution with a polyol, viz. poly(tetramethylene ether glycol), and it was subsequently used to prepare polyurethane (PU) nanocomposites by simple dilution. The polyol in the masterbatch efficiently prevented the aggregation of GNPs during the preparation of PU nanocomposite. In addition, the dispersed GNPs in the masterbatch exhibited rheological behavior of lyotropic liquid crystalline materials. In this study, the manufacture and application methods of the GNP/polyol masterbatch were discussed, enabling the facile manufacture of the PU/GNP nanocomposites with excellent mechanical properties. In addition, the manner in which the GNP alignment affected the microphase separation of PU in the nanocomposites was investigated, which determined the improvement in the mechanical properties of the nanocomposites. High-performance PU/GNP nanocomposites are thought to be manufactured from the GNP/polyol masterbatch by the simple dilution to 0.1 wt% GNP in the nanocomposite.

In this work, thermally healable graphene-nanoplate/epoxy (GNP/EP) nanocomposites were investigated. GNPs were used as reinforcement and crosslinking platforms for the diglycidyl ether of bisphenol A-based epoxy resin (DGEBA) through the Diels-Alder (DA) reaction with furfurylamine (FA). The GNPs and FA could then be used as a derivative of diene and dienophile in the DA reaction. It was expected that the combination of GNPs and FA in DGEBA would produce composites based on the interfacial properties of the components. We confirmed the DA reaction of GNPs and FA at the interface during curing of the GNP/EP nanocomposites. This procedure is simple and solvent-free. DA and retro DA reactions of the obtained composites were demonstrated, and the thermal healing properties were evaluated. The behavior of the GNP/EP nanocomposites in the DA reaction is similar to that of thermosetting polymers at low temperatures due to crosslinking by the DA reaction, and the nanocomposites can be recycled by a retro DA reaction at high temperatures.

As a part of studies to lower the infrared (IR) emissivity from the surface of exhaust nozzle in the turbo jet engine, stainless steel plate was coated with copper particle/meta-aramid resin composites and the IR emissivity of the plate were investigated. Binders of filler particles based on synthetic polymers generally undergo thermal decomposition before 300℃. It was found that the meta aramid resin was thermally stable after the test at 320℃, confirming the excellent thermal stability. Contents of copper particles in the composites were varied from 0 to 70% by volume. It was observed that the copper particle/meta aramid resin composites showed good adhesion after the tests at 320℃. The specimen coated with the composite containing 50 vol% of copper particles showed the lowest IR emissivity, 0.6, at 320℃.