Cellulose nanocrystals as nucleating agents for the strain induced crystallization in natural rubber.

Vulcanized natural rubber (NR)/cellulose nanocrystals (CNC) composites with a CNC content of up to 5 wt% using physical blending and dicumyl peroxide crosslinking were prepared. The tensile properties were investigated at slow and high strain rates. The slow strain rate tests revealed an increase of the elastic modulus concomitant with a decrease of strain at the crystallization onset while increasing the CNC fraction. The high strain rate tests performed near adiabatic conditions demonstrated the ability of the CNC to improve the elastocaloric properties of the NR matrix, with an increase of 30% and 15% of heating and cooling capacities, respectively, in the presence of 3 wt% CNC. Such results were ascribed to (i) a higher thermoelastic effect, due to strain amplification in the NR matrix in the presence of CNC and (ii) a nucleating effect of the CNC on strain induced crystallization. This series of materials can be proposed as a promising eco-friendly alternative to conventional carbon black filled rubber as potential green elastocaloric materials (heating pump, cooling machines).

An Investigation on the Thermally Induced Compatibilization of SBR and α-Methylstyrene/Styrene Resin.

The miscibility between two polymers such as rubbers and performance resins is crucial to achieve given targeted properties in terms of tire performances. To this aim, α-methylstyrene/styrene resin (poly(αMSt-co-St)) are used to modify the viscoelastic behavior of rubbers and to fulfill the requirements of the final applications. The initial aim of this work was to understand the influence of poly(αMSt-co-St) resins blended at different concentrations in a commercial styrene-butadiene rubber (SBR). Interestingly, while studying the viscoelastic properties of SBR blends with poly(αMSt-co-St), crosslinking of the rubber was observed under conditions where it was not expected to happen. Surprisingly, after the crosslinking reactions, the poly(αMSt-co-St) resin was irreversibly miscible with SBR at concentrations far above its immiscibility threshold. A detailed investigation involving characterization technics including solid state nuclear magnetic resonance led to the conclusion that poly(αMSt-co-St) is depolymerizing under heating and can graft onto the chains of SBR. It results in an irreversible compatibilization mechanism between the rubber and the resin.

Fused Metalloporphyrin Thin Film with Tunable Porosity via Chemical Vapor Deposition.

Porous and highly conjugated multiply fused porphyrin thin films are prepared from a fast and single-step chemical vapor deposition approach. While the solution-based coupling of porphyrins is usually undertaken at room temperature, the gas phase reaction of nickel(II) 5,15-(diphenyl)porphyrin and iron(III) chloride (FeCl3) is investigated for temperatures as high as 200 °C. Helium ion and atomic force microscopy, supported by weight and thickness measurements, shows a drastic decrease of the fused porphyrin thin film's density accompanied by the formation of a mesoporous morphology upon increase of the reaction temperature. The increase of the film's porosity is attributed to formation of a greater amount of HCl (originated from both the oxidative coupling and chlorination reactions) and the release of gaseous FeCl3 byproducts, i.e., Cl2, at higher deposition temperatures. In addition, high resolution mass spectrometry reveals that increase of the reaction temperature promotes a higher degree of conjugation of the fused porphyrins chains, which ensures that high electronic conductivities are maintained along with high porosity. The method reported herein could enable the engineering of fused porphyrin thin films in sensing and catalytic devices.