Mesoscale bicontinuous networks in self-healing hydrogels delay fatigue fracture

Load-bearing biological tissues, such as muscles, are highly fatigue-resistant, but how the exquisite hierarchical structures of biological tissues contribute to their excellent fatigue resistance is not well understood. In this work, we study antifatigue properties of soft materials with hierarchical structures using polyampholyte hydrogels (PA gels) as a simple model system. PA gels are tough and self-ealing, consisting of reversible ionic bonds at the 1-nm scale, a cross-linked polymer network at the 10-nm scale, and bicontinuous hard/soft phase networks at the 100-nm scale. We find that the polymer network at the 10-nm scale determines the threshold of energy release rate G(0) above which the crack grows, while the bicontinuous phase networks at the 100-nm scale significantly decelerate the crack advance until a transition G(tran) far above G(0). In situ small-angle X-ray scattering analysis reveals that the hard phase network suppresses the crack advance to show decelerated fatigue fracture, and G(tran) corresponds to the rupture of the hard phase network

Preparation of Polyethylene and Ethylene/Methacrylic Acid Copolymer Blend Films with Tunable Surface Properties through Manipulating Processing Parameters during Film Blowing

Polymer films based on polyethylene (PE) and ionomer ethylene/methacrylic acid (EMAA) copolymer blend were prepared by film blowing, whose surface properties were tuned by varying processing parameters, i.e., take up ratio (TUR). Blends of PE/EMAA copolymer were firstly prepared by the melt-mixing method, before being further blown to films. The wettability of the film was investigated by measuring the contact angle/water-film encounter time, and optical properties, i.e., the haze and transmittance. The wettability was found to be enhanced with the increase of TUR. So too was the haze, while the transmittance was found to be almost independent of TUR. The XPS and AFM results directly show the increasing polar functional groups (–COO−) on the surface and roughness with increasing TUR. Further analysis of the 2D SAXS and WAXS unveiled the origin of the invariant transmittance, which resulted from the minor change of the crystallinity and the monotonic increase of the haze, with TUR resulting from the evolution of crystal orientation. In addition to other post-modification methods, the current study provides an alternative route to prepare large-scale PE films as the template for the advanced potential applications, i.e., covering in the layer of roof, the privacy of protective windows, and multitudes of packaging

Counterion-Induced Nanosheet-to-Nanofilament Transition of Lyotropic Bent-Core Liquid Crystals

The smart flexibility of phase transitions in liquid crystals (LCs) makes them suitable for various applications and is an important research field in contemporary science, engineering, and technology. Unlike most reports focused on bent-core LCs in the thermotropic situation, in our present study, we designed and synthesized a fully rigid bent-core molecule with the sulfonic acid group replacing conventional flexible chains. A rich variety of counterion-induced supramolecular LC phase behaviors have been systematically investigated. It was found that the smectic phase with nanosheets tends to transform to the hexagonal phase with nanofilaments when the protons of the sulfonic acid group are partially replaced by alkali metal ions. The experimental results show that the nanoaggregate and phase transition are controlled by the displacing ratio of alkali metal ions rather than the molecular concentration. Another interesting feature is that the achiral bent-core molecules self-assemble into columns by helical stacking and present macroscopic chirality, indicating that spontaneous chiral symmetry breaking occurs in the columnar phase. The fully rigid bent-core molecules reveal surprisingly hierarchical molecular self-assemblies with the smectic-to-hexagonal phase transition, which was not previously observed in supramolecular complexes. The findings will provide new possibilities for applications in LC-based photonic devices, biosystem switches, and supramolecular actuators

Stretch-induced crystal-crystal transition of polybutene-1: An in situ synchrotron radiation wide-angle X-ray scattering study

Deformation induced crystal-crystal transition of polybutene-1 (PB-1) from forms II to I at different temperatures is studied with in situ synchrotron radiation wide-angle X-ray scattering (WAXS). Analyses on the evolution of crystallinity and orientations of forms II and I during tensile deformation show that stretch accelerates the transformation from forms II to I, which is interpreted based on either a direct crystal-crystal transition or an indirect approach via an intermediate state of melt, namely a melting recrystallization process. A three-stage mechanical deformation including linear deformation, stress plateau, and strain hardening is observed in the engineering stress-strain curves, which corresponds to a process of incubation, nucleation, and gelation of form I crystals. It establishes a nice correlation between phase transition and mechanical behavior in this study

From Molecular Entanglement Network to Crystal-Cross-Linked Network and Crystal Scaffold during Film Blowing of Polyethylene: An in Situ Synchrotron Radiation Small- and Wide-Angle X‑ray Scattering Study

Combining a homemade film blowing machine and an in situ synchrotron radiation source with small- and wide-angle X-ray scattering (SAXS and WAXS) capability, an investigation of film blowing of polyethylene (PE) has been studied. From the die exit to the positions above the frost line, four zones defined with different structural features are observed with SAXS and WAXS measurements. In zone I, precursor and crystal structures emerge from the polymer entanglement network during cooling and extension, which lead to the formation of a deformable crystal-cross-linked network at the boundary between zones I and II. The occurrence of the crystal-cross-linked network enhances the effective chain stretching during further deformation in zone II. Crystallization is largely accelerated, which generates crystals with high orientation. Further increasing the crystallinity results in the deformable crystal-cross-linked network transforming into a nondeformable crystal scaffold at the frost line (the boundary between zones II and III), which stabilizes the bubble and prevents further deformation. In zones III and IV, the scaffold and the entire sample are gradually filled up by crystals, respectively. Interestingly, increasing the take-up ratio (TUR) does not influence the critical crystallinity (χ_I–II) for the formation of the deformable crystal-cross-linked network, while the crystallinity (χ_f) at the frost line or for the formation of nondeformable scaffold does vary with TUR. This suggests that the former (χ_I–II) is mainly controlled by molecular parameters, while the latter (χ_f) is determined by both processing and molecular parameters of PE material

Structural Evolution of Hard-Elastic Isotactic Polypropylene Film during Uniaxial Tensile Deformation: The Effect of Temperature

The effects of temperature on the nonlinear mechanical behaviors of hard-elastic isotactic polypropylene films are systematically studied with in-situ ultrafast synchrotron radiation small- and wide-angle X-ray scattering techniques (SAXS/WAXS) during uniaxial tensile deformation at temperatures from 30 to 160 °C. Based on the mechanical behaviors and structural evolutions in strain–temperature two-dimensional space, three temperature regions (I, II, and III) are clearly defined with the α relaxation temperature (<i>T</i>_α ≈ 80 °C) and the onset of melting temperature (<i>T</i>_onset ≈ 135 °C) as boundaries, where different mechanisms dominate the nonlinear deformations after yield. In region I, microstrain in lamellar stacks ε_m obtains an accelerated increase after yield and reaches a value significantly larger than corresponding macrostrain ε, during which neither slipping, melting, nor cavitation occurs. We propose stress-induced microphase separation of interlamellar amorphous to be responsible to the hyperelastic behavior in region I. Above <i>T</i>_α in region II, due to reduced cohesive strength and enhanced chain mobility, the irreversible reduction of crystallinity and the formation of slender cavities suggest that crystal slipping overwhelms microphase separation and plays the major role in nonlinear deformation, during which chains in lamellar crystals are pulled out and recrystallize into nanofibrillar bridges. In region III above <i>T</i>_onset, melting–recrystallization dictates the nonlinear deformation. A schematic roadmap for structural evolution is constructed in strain–temperature space, which may guide the processing of microporous membranes for lithium battery separators as well as other high performance polymer fibers and films

Coupling of Multiscale Orderings during Flow-Induced Crystallization of Isotactic Polypropylene

The sequence and coupling of intra- and interchain orderings in flow-induced crystallization (FIC) of partially cross-linked isotactic polypropylene (iPP) is studied with <i>in situ</i> Fourier transform infrared spectroscopy (FTIR) and synchrotron radiation X-ray scattering techniques, which reveal that multiscale structural intermediates emerge prior to the onset of crystallization. Upon imposing flow, intrachain conformational ordering or coil–helix transition (CHT) occurs first, which is directly correlated with external stress. As helical content is built up at large strain, density fluctuation happens, and sufficient long helices may result in orientation ordering before FIC. The results demonstrate that stress induced intrachain CHT is the essential structural intermediate in FIC, which can be further coupled with interchain orientation and density providing either helical content or length meets the criterions for the phase transitions. We propose that coupling among external stress, intrachain conformational, and interchain orientation and density orderings to be the molecular mechanism for FIC of polymer forming helical structures

Extension-Induced Crystallization of Poly(ethylene oxide) Bidisperse Blends: An Entanglement Network Perspective

The role of long chains in extension flow-induced crystallization was studied with a combination of extension rheological and <i>in situ</i> small-angle X-ray scattering (SAXS) measurements at 52 °C. To elucidate the effects of long chains, bidisperse blends of poly­(ethylene oxide) (PEO) with the long-chain concentration above the overlap concentration were prepared, constructing long-chain entanglement network in short-chain matrix. Rheological data of step extension on PEO melt are divided into two regions with fracture strain of pure short-chain sample as a boundary. Distinctly different features of crystallization kinetics and crystal morphologies are observed in these two regions, exactly corresponding to rheological behavior. A new mechanism based on entanglement network perspective is proposed, in which the second entanglement network constructed by long chains has three effects: (i) helping flow to change the free energy of polymer melt more effectively; (ii) ensuring the specific work can impose on the system; (iii) favoring the formation of precursors. This mechanism captures both rheological observation and crystallization behavior successfully and offers a new viewpoint for FIC study