Interfacial Confinement in Semi-Crystalline Shape Memory Polymer Towards Sequentially Dynamic Relaxations

Sequential glass and melting transitions in semi-crystalline shape memory polymers (SMPs) provide great opportunities to design and generate multiple shape-memory effects (SMEs) for practical applications. However, the complexly dynamic confinements of coexisting amorphous and crystalline phases within the semi-crystalline SMPs are yet fully understood. In this study, an interfacial confinement model is formulated to describe dynamic relaxation and shape memory behavior in the semi-crystalline SMPs undergoing sequential phase/state transitions. A confinement entropy model is first established to describe the glass transition behavior of amorphous phase within the SMPs based on the free volume theory, where the free volume is critically confined by the crystalline phase. An extended Avrami model is then formulated using the frozen volume theory to characterize the melting and crystallization transitions of the crystalline phase in the SMPs, whose interfacial confinement with the amorphous phase has been identified as the driving force for the supercooled regime. Furthermore, an extended Maxwell model is formulated to describe the effect of dynamic confinement of two phases on the multiple SMEs and shape recovery behaviors in the semi-crystalline SMPs. Finally, the effectiveness of the newly proposed model is verified using the experimental data reported in the literature. This study aims to provide a new methodology for the dynamic confinements and cooperative principles in the semi-crystalline SMP towards multiple SMEs.

Water Formation Reaction under Interfacial Confinement: Al0.25Si0.75O2 on O-Ru(0001)

Confined nanosized spaces at the interface between a metal and a seemingly inert material, such as a silicate, have recently been shown to influence the chemistry at the metal surface. In prior work, we observed that a bilayer (BL) silica on Ru(0001) can change the reaction pathway of the water formation reaction (WFR) near room temperature when compared to the bare metal. In this work, we looked at the effect of doping the silicate with Al, resulting in a stoichiometry of Al0.25Si0.75O2. We investigated the kinetics of WFR at elevated H2 pressures and various temperatures under interfacial confinement using ambient pressure X-ray photoelectron spectroscopy. The apparent activation energy was lower than that on bare Ru(0001) but higher than that on the BL-silica/Ru(0001). The apparent reaction order with respect to H2 was also determined. The increased residence time of water at the surface, resulting from the presence of the BL-aluminosilicate (and its subsequent electrostatic stabilization), favors the so-called disproportionation reaction pathway (*H2O + *O ↔ 2 *OH), but with a higher energy barrier than for pure BL-silica.

Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions

Combining broadband dielectric spectroscopy and nuclear magnetic resonance studies, we analyze the reorientation dynamics and the translational diffusion associated with the glassy slowdown of the eutectic aqueous dimethyl sulfoxide solution in nano-sized confinements, explicitly, in silica pores with different diameters and in ficoll and lysozyme matrices at different concentrations. We observe that both rotational and diffusive dynamics are slower and more heterogeneous in the confinements than in the bulk but the degree of these effects depends on the properties of the confinement and differs for the components of the solution. For the hard and the soft matrices, the slowdown and the heterogeneity become more prominent when the size of the confinement is reduced. In addition, the dynamics are more retarded for dimethyl sulfoxide than for water, implying specific guest-host interactions. Moreover, we find that the temperature dependence of the reorientation dynamics and of the translational diffusion differs in severe confinements, indicating a breakdown of the Stokes–Einstein–Debye relation. It is discussed to what extent these confinement effects can be rationalized in the framework of core-shell models, which assume bulk-like and slowed-down motions in central and interfacial confinement regions, respectively.

Thermal-guided interfacial confinement to fabricate flexible structural color composites for durable applications

A novel strategy to fabricate flexible and mechanically robust composite films of noniridescent structural color patterns is proposed.