Thickness-Dependent Photo-Aligned Thin-Film Morphologies of a Block Copolymer Containing an Azobenzene-Based Liquid Crystalline Polymer and a Poly(ionic liquid).

Photo-induced alignment of the thin-film morphologies of azobenzene-containing block copolymers (BCPs) is an effective method to obtain a uniaxial pattern of nanocylinders. Although film thickness is an important factor affecting the self-assembly of BCP thin films, the influence of film thickness on the photo-induced alignment of BCP thin-film morphology has never been systematically studied. Herein, we report the thickness-dependent photo-aligned film morphologies of the BCP containing an azobenzene-based liquid crystalline polymer and a poly(ionic liquid) (PIL), with a perfect uniaxial pattern of PIL nanocylinders. For films aligned with the unpolarized light (UPL), the out-of-plane PIL nanocylinders can be obtained in the film with a thickness of only 1L0 (∼30 nm, where L0 is the layer spacing of the hexagonally packed cylinder array), which is far lower than the thickness (more than 4L0) of the thermally annealed film needed to obtain the same morphology. This change is attributed to the orientation effect of UPL on azobenzene mesogens that suppresses the excluded volume effect. For the films aligned with linearly polarized light (LPL), to take advantage of the excluded volume effect to obtain the planar orientation of azobenzene mesogens, the thickness should be controlled to be no more than 3L0 to achieve an in-plane uniaxial alignment of PIL nanocylinders. The above relationship between the morphology and thickness of photo-aligned film eliminates the obstacles encountered in preparing films with well-ordered photo-aligned morphologies.

Self-Healing Solid Polymer Electrolyte with High Ion Conductivity and Super Stretchability for All-Solid Zinc-Ion Batteries.

The zinc-ion battery (ZIB) is a novel energy storage device, an attractive alternative to the lithium-ion battery. The frequently used aqueous electrolyte suffers from many problems such as zinc dendrites and leakage, which prompts hydrogel electrolytes and solid electrolytes as good replacements. However, hydrogel electrolytes are usually unstable, owing to water volatilization. Herein, a novel solid polymer electrolyte (SPE) utilizing coordination of zinc ions is designed and then introduced into an all-solid ZIB. Benefiting from the unique coordination structure between the polymer and zinc ions, the SPE shows outstanding flexibility, high ion conductivity, and self-healing properties. In addition, the imine bonds in the polymer allow the electrolyte to degrade in acid environments, endowing its recyclability. More importantly, solid-state ZIBs based on the polymer electrolytes exhibit an impressive cycling stability (125% capacity retention after 300 cycles) and a high coulombic efficiency (94% after 300 cycles). The results demonstrate the promising potentials of the developed SPEs that can be used in all-solid ZIBs.

Efficient Access to 3D Mesoscopic Prisms in Polymeric Soft Materials.

The preparation of 3D functional isolated mesoscopic assemblies remains a challenge in the self-assembly of polymers. Here, well-defined 3D hexagonal and hexagram prisms with uniform dimensions are acquired by the crystallization of the inclusion complex composed of a crystalline molecule tris-o-phenylenedioxycyclotriphosphazene (TPP) and a block copolymer. The crystalline TPP plays an important role in the self-assembling process. The faceted morphologies of the hexagonal and hexagram prisms are infrequent in the self-assembly field of soft materials. The formation of the prisms experiences a 3D growth mechanism. The epitaxial growth, accompanied by the heterogeneous nucleation in the edges, yields the growth of inclusion crystals. This study provides a path to construct well-defined polymeric soft materials with broad utility based on numerous supramolecular complexes.

Tailored Polymer Particles with Ordered Network Structures in Emulsion Droplets.

The structural control of block copolymer (BCP) particles, which determines their properties and utilities, is quite important. Understanding the structural relationship between solution-cast samples and polymer particles in a confined space is necessary to precisely regulate the internal structure of polymer particles. Therefore, a facile method by choosing an appropriate selective solvent is reported to prepare spherical polymer particles with ordered network structures. The rod-coil BCP, poly(dimethylsiloxane)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS), was chosen as a model polymer because of its strong phase segregation ability. First, the structures of the BCP with a thermodynamically stable lamellar structure cast from different selective solvents were systematically studied. Then, a polymer particle with the same internal structure as that of the solution-cast sample can be easily prepared by self-assembling in an emulsion confined space. The relatively large particle size is of importance in this process because the large value of the particle size to periodicity ratio can provide a weak confined environment. This method helps us understand the inherent self-assembling mechanism of polymer particles in an emulsion confined space and accurately control the internal structure of the polymer particle obtained.

White-Light-Emitting AIE/Eu3+-Doped Ion Gel with Multistimuli-Responsive Properties.

A white-light-emitting ion gel composed of a poly[(2-(4-vinylphenyl)ethene-1,1,2-triyl)tribenzene-b-ethylene glycol-b-(2-(4-vinylphenyl)ethene-1,1,2-triyl)tribenzene] aggregation-induced emission (AIE) network and a poly([2,2':6',2″-terpyridin]-4'-yl methacrylate-co-methyl methacrylate) Eu3+-doped network was fabricated via a solution mixing process. This ion gel exhibits special multistimuli-responsive properties, and it can change its luminescent color by changing pH, temperature, or the solvent. The unique color-changing property is attributed to the different luminescent mechanisms of the AIE/Eu3+-doped polymer networks. The former is affected by changes in its aggregation state, while the latter is controlled by the dynamic metal-ligand cross-linking bonds. Furthermore, owing to the interpenetrating networks formed by the two polymers, the hybrid gel has both good mechanical strength and flexibility. It may be used in the fields of sensors, probes, and light-emitting materials.

Head-Tail Asymmetry as the Determining Factor in the Formation of Polymer Cubosomes or Hexasomes in a Rod-Coil Amphiphilic Block Copolymer.

The self-assembly of a rod-coil amphiphilic block copolymer (ABCP) led to Im3‾ m and Pn3‾ m polymer cubosomes and p6mm polymer hexasomes. This is the first time that these structures are observed in a rod-coil system. By varying the hydrophobic chain length, the initial concentration of the polymer solution, or the solubility parameter of the mixed solvent, head-tail asymmetry is adjusted to control the formation of polymer cubosomes or hexasomes. The formation mechanism of the polymer cubosomes was also studied. This research opens up a new way for further study of the bicontinuous and inverse phases in different ABCP systems.