Introducing sacrificial bonds is a common method for increasing the toughness of hydrogels. Many sacrificial bonds have been extensively investigated, but the sacrifice efficiency has never been studied. In this study, polyacrylamide hydrogels with highly entangled polymer chains containing carboxyl-zirconium (-COO--Zr4+) sacrificial bonds are prepared to study the effect of polymer chain entanglement on the sacrificial bond efficiency. Unlike chemical crosslinking points, the dense physical entanglements do not affect the toughness (∼43 MJ/m3) of hydrogels but significantly improve the tensile strength (by two times) and Young\'s modulus (by six times). Physical entanglements enable the chains to slide and adjust the network structure under stress, which enables more polymer chains and sacrificial bonds to participate in the deformation process. Therefore, dense entanglements will greatly improve the sacrifice efficiency. However, a high density of chemical crosslinking points will limit the improvement in the sacrifice efficiency, which is attributed to the sliding limitations because of physical entanglement. The highly entangled polyacrylamide hydrogels toughened by -COO--Zr4+ have an excellent load-bearing capacity. This study provides a novel strategy for designing hydrogels with ultra-high strength and toughness, which paves the way for the development of many hydrogels used in engineering materials.

With the rapid development of new energy and the upgrading of electronic devices, structurally stable phase change materials (PCMs) have attracted widespread attentions from both academia and industries. Traditional cross-linking, composites, or microencapsulation methods for preparation of form stable PCMs usually sacrifice part of the phase change enthalpy and recyclability. Based on the basic polymer viscoelasticity and crystallization theories, here, a kind of novel recyclable polymeric PCM is developed by simple solution mixing ultrahigh molecular weight of polyethylene oxide (UHMWPEO) with its chemical identical oligomer polyethylene glycol (PEG). Rheological and leakage-proof experiments confirm that, even containing 90% of phase change fraction PEG oligomers, long-term of structure stability of PCMs can be achieved when the molecular weight of UHMWPEO is higher than 7000 kg mol-1 due to their ultralong terminal relaxation time and large number of entanglements per chain. Furthermore, because of the reduced overall entanglement concentration, phase change enthalpy of PCMs can be greatly promoted, even reaching to ≈185 J g-1, which is larger than any PEG-based form stable PCMs in literatures. This work provides a new strategy and mechanism for designing physical-entanglements-supported form stable PCMs with ultrahigh phase change enthalpies.

Ti-series oxide ceramics in the form of aerogels, such as TiO2, SrTiO3, BaTiO3, and CaCu3Ti4O12, hold tremendous potential as functional materials owing to their excellent optical, dielectric, and catalytic properties. Unfortunately, these inorganic aerogels are usually brittle and prone to pulverization owing to weak inter-particulate interactions, resulting in restricted application performance and serious health risks. Herein, a novel strategy is reported to synthesize an elastic form of an aerogel-like, highly porous structure, in which activity-switchable Ti-series oxide sols transform from the metastable state to the active state during electrospinning, resulting in condensation and solidification at the whipping stage to obtain curled nanofibers. These curled nanofibers are further entangled when flying in the air to form a physically interlocked, elastic network mimicking the microstructure of high-elasticity hydrogels. This strategy provides a library of Ti-series oxide nanofiber sponges with unprecedented stretchability, compressibility, and bendability, possessing extensive opportunities for greener, safer, and broader applications as integrated or wearable functional devices. As a proof-of-concept demonstration, a new, elastic form of TiO2, composed of both \"white\" and \"black\" TiO2 nanofiber sponges, is constructed as spontaneous air-conditioning textiles in smart clothing, buildings, and vehicles, with unique bidirectional regulation of radiative cooling in summer and solar heating in winter.

Crystallization of polymers from entangled melts generally leads to the formation of semicrystalline materials with a nanoscopic morphology consisting of stacks of alternating crystalline and amorphous layers. The factors controlling the thickness of the crystalline layers are well studied; however, there is no quantitative understanding of the thickness of the amorphous layers. We elucidate the effect of entanglements on the semicrystalline morphology by the use of a series of model blends of high-molecular-weight polymers with unentangled oligomers leading to a reduced entanglement density in the melt as characterized by rheological measurements. Small-angle X-ray scattering experiments after isothermal crystallization reveal a reduced thickness of the amorphous layers, while the crystal thickness remains largely unaffected. We introduce a simple, yet quantitative model without adjustable parameters, according to which the measured thickness of the amorphous layers adjusts itself in such a way that the entanglement concentration reaches a specific maximum value. Furthermore, our model suggests an explanation for the large supercooling that is typically required for crystallization of polymers if entanglements cannot be dissolved during crystallization.

Research on the rheological performance and mechanism of polymer nanocomposites (PNCs), mainly focuses on non-polar polymer matrices, but rarely on strongly polar ones. To fill this gap, this paper explores the influence of nanofillers on the rheological properties of poly (vinylidene difluoride) (PVDF). The effects of particle diameter and content on the microstructure, rheology, crystallization, and mechanical properties of PVDF/SiO2 were analyzed, by TEM, DLS, DMA, and DSC. The results show that nanoparticles can greatly reduce the entanglement degree and viscosity of PVDF (up to 76%), without affecting the hydrogen bonds of the matrix, which can be explained by selective adsorption theory. Moreover, uniformly dispersed nanoparticles can promote the crystallization and mechanical properties of PVDF. In summary, the viscosity regulation mechanism of nanoparticles for non-polar polymers, is also applicable to PVDF, with strong polarity, which is of great value for exploring the rheological behavior of PNCs and guiding the process of polymers.

Many high-strength hydrogels have been developed in recent years; however, few of them are both tough and resilient, and their intrinsic paradoxical nature makes designing a gel with both high toughness and high resilience a great challenge. To address this problem, we introduced both N,N,N,N-pentamethyldiethylenetriamine (PA) and N,N-methylenebisacrylamide (MBA) into polyacrylamide hydrogel networks to construct an entangled network that contains chemically cross-linked chains and branched chains simultaneously. The entanglements of branched chains can act as a physical cross-linking point to uniformly disperse stress on molecular chains, and chemical cross-linking ensures the stability of the hydrogel network. The increase in the number and length of branched chains is able to achieve an enhancement in strength while the slip of the entangled polymer chains can effectively achieve energy dissipation and can improve the toughness of the gel. Moreover, the resultant hydrogels exhibit an excellent resilience (>98%). Therefore, high toughness and resilience are achieved simultaneously. In addition, we also investigated the initiation mechanism of PA. This strategy creates a new way for the preparation of next-generation high toughness and high resilience hydrogel-based materials, which have promising applications in wearable, flexible strain/pressure sensors.