Manipulating Cis-Trans Copolymer Chain Conformation to Simultaneously Improve Permittivity and DC Breakdown Strength in Polythiourea.

Polythioureas (PTUs) show great potentials for applications in the new generation of film capacitors due to their excellent dielectric properties. Herein, the cis-trans copolymer chain of PTU is successfully tailored by employing cis and trans cyclohexyl spacers. The relationship between the copolymer chain conformation, microstructure, and dielectric properties is carefully explored by a series of analysis. Compared with cis conformation, the trans with less steric hindrance can promote the formation of H-bonds. The enhanced H-bonding interactions not only reduce the molecular inter-chain spacing, but also drive the self-assembly of molecular chains to form cylindrical and droplet nano-morphologies. The phase separation between cis and trans PTUs is confirmed by combining the experimental results of TEM and DSC, and the CT64-PTU with the most two-phase interface thus obtains the highest permittivity of 5.5 (@10 Hz). The reduced molecular inter-chain spacing is accompanied by a decreased hopping distance of charges, which improves breakdown strength by 17% from 498 MV/m to 580 MV/m. Therefore, the cis-trans copolymer chain conformation in PTU provides a simultaneous high permittivity and breakdown strength. This research offers a strategy to further design high-performance dielectrics via regulation of copolymer chain conformation.

Surprising Hydrophobic Polymer Surface with a High Content of Hydrophilic Polar Groups.

The wetting property of a solid surface has been a hotspot for centuries, and many studies suggest that the hydrophobicity is highly related to the polar components. However, the underlying mechanism of polar moieties on the hydrophobicity remains unclear. Here, we tailor the surface polar moieties of epoxy resin (EP) by ozone modification and assess their wetting properties. Our results show that, for the modified EP with more (60.54%) polar moieties, the polar effect on hydrophobicity cannot be empirically observed. To reveal the underlying mechanism, the absorption parameters, including equilibrium distance, adsorption radius, and effective adsorption sites for water on EP before and after ozone treatment, are calculated on the basis of molecular simulations. After ozone modification, the equilibrium distance (from 1.95 to 1.70 Å), adsorption radius (from 3.80 to 4.50 Å), and effective adsorption sites (from 1 to 2) change slightly and the EP surface remains hydrophobic, although the polar groups significantly increase. Therefore, it is concluded that the wetting properties of solid surfaces are dominated by the equilibrium distance, adsorption radius, and effective adsorption sites for water on solids, and the nonlinear relationship between polar groups and hydrophilicity is clarified.

Interfacial Effect on Dielectric Properties of Self-Assembled Polythiourea-Based Copolymers for Ultrahigh Energy Storage.

Polymer dielectrics are highly desirable in capacitor applications due to their low cost, high stability, and reliability. However, there still remains a lack of feasible methods to prepare polymer dielectrics with high energy density and low dielectric loss, which severely hampers the development of compact and efficient power electronics. Here, an amphiphilic block copolymer, polythiourea-b-polydimethylsiloxane (PTU-b-PDMS), with an extraordinarily high energy density of 29.8 J cm-3 and a low loss is synthesized via polyaddition polymerization. This is highly relevant to the block molecule conformation in the interfacial region of the self-assembled PTU-b-PDMS. The block molecule in the interface adopts an extended conformation when the PTU forms nanodots, whereas the block molecule adopts a coiled conformation when the PTU forms nanostrands. The observation and characterization have proved that the coiled block molecule in the interfacial region can simultaneously induce extra strong charge trapping sites and dipolar polarization. It substantially improves the breakdown strength from 652 to 1166 MV m-1 , while maintaining a high dielectric constant of 5 and a low loss of <0.01. This work offers unprecedented structural insights into the conformation-induced interfacial effect and enables rational design of self-assembled copolymers to boost their dielectric properties and energy density.