Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy

We study the effect of chain rigidity on tailoring the nanoparticle locations for neutral and selective particles embedded in the lamellar morphology formed by semiflexible diblock copolymer chains using self-consistent field calculations. The nanoparticles are modeled through a cavity function, and the semiflexible chains are represented by the continuous Kratsky-Porod chain model. In general situation, the nanoparticles prefer to stay at the interface in order to reduce the interface areas and thus the system free energy. However, the particle distribution at the domain center is subtle, and the underlying physics is intrinsically different depending on the polymer flexibility. In the case of flexible chains, the entropy just contributes a constant shift to the free energy when the nanoparticles move around the domain center indicating that the local metastable state if appears at the domain center is wholly attributed to the local minimum in the enthalpy. If the polymers are rigid, the variation of the particle distribution at the domain center has a close relation with the polymer rigidity and nanoparticle size. In the case of strongly rigid polymers with small nanoparticles, a nearly uniform particle distribution at the domain center is observed, while in other cases, a local enhancement of particle distribution there is found. In contrast to the case of flexible chains, further analysis reveals the crucial role of entropy in controlling the shape of particle distributions at the phase domain. Specifically, the local metastable state appears in the domain center is determined by the large entropy there which arises from the weak coupling of bond orientations that allows the polymer chains to be relatively relaxed. When the particle becomes selective, its distribution in the phase domain exhibits a shift almost uniformly rather than changes its profile, and the underlying physics still holds. In all, our study establishes a strong coupling between the chain rigidity and effect of entropy.

Super-tough and strong nanocomposite fibers by flow-induced alignment of carbon nanotubes on grooved hydrogel surfaces

Nanocomposite fibers have attracted intensive attentions owing to their promising applications in various fields. However, the fabrication of nanocomposite fibers with super toughness and strong strength under mild conditions remains a great challenge. Here we present a facile flow-induced assembly strategy for the development of super-tough and strong nanocomposite fibers with highly ordered carbon nanotubes (CNTs), which can be induced by directional and fast flow on a grooved hydrogel surface. The prepared nanocomposite fibers show excellent mechanical properties, with a tensile strength up to 643±27 MPa and toughness as high as 77.3±3.4 MJ m^-3 at ultimate strain of 14.8±1.5%. This versatile and efficient flow-induced alignment strategy represents a promising direction for the development of high-performance nanocomposites for practical applications.