functionalization-single-walled-carbon-nanotubes-with-thermo

Functionalization of Single-walled Carbon Nanotubes with Thermo-reversible Block Copolymers and Characterization by Small-angle Neutron Scattering

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous ...

Oak Ridge National Laboratory

Pusan National University

Herein, we investigate the influence of nanoscale smectic polymorphism within end-on fixed side-chain liquid crystalline polymer networks (SCLCNs) on macroscopic shape-memory and actuation properties. We have synthesized a series of SCLC-type linear (TP-n) and cross-linked random terpolymers (XL-TP-n) with varying length of flexible methylene spacers (n = 5, 10, and 15) between polynorbornene main-chain and cholesteryl ester side-chains. Thermal and mechanical analyses by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) confirm a glass transition (T(g)), a clearing temperature (T(cl)), and a network structure in the XL-TP-n. Detailed structural investigation conducted using wide-angle and small-angle X-ray scattering (WAXS and SAXS) at room temperature proves self-assembled smectic A (SmA) polymorphism of the XL-TP-n which evolves from non-interdigitated bilayer (SmA(2)) for n = 5 to mixed layers of monolayer-like highly interdigitated layer (SmA(1)) and SmA(2) for n = 10 and to SmA(1) for n = 15. In addition, TP10 at temperatures above 60 °C interestingly shows transformation of SmA structure from mixed layer (SmA(1) + SmA(2)) to interdigitated structure (SmA(d)). The SmA polymorphism developed in TP-n during shape-memory cycles (SMCs) significantly impacts the ultimate strain responses. A mechanism for the unique interdigitation-based thermostrictive behavior is proposed. More importantly, this new actuation mechanism observed in these XL-TP-n can be exploited to develop intelligent thermal actuators.

Side-chain liquid crystalline polymer networks: exploiting nanoscale smectic polymorphism to design shape-memory polymers.

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Article	Year
Side-chain liquid crystalline polymer networks: exploiting nanoscale smectic polymorphism to design shape-memory polymers. ACS nano\| PubMed ID: 21401122	2011
Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes. Physical chemistry chemical physics : PCCP\| PubMed ID: 25733054	2015

Suk-kyun Ahn

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