环氧树脂修复水泥基材料微裂缝的渗透机理

为了探明微胶囊芯材(环氧树脂)修复水泥基材料微裂缝的毛细渗透机理,采用光学接触角测量仪测量环氧树脂的接触角及表面张力,并用环境扫描电镜观察环氧树脂在水泥基材料裂缝表面的润湿效果,研究温度、裂缝宽度、环氧树脂种类等因素对环氧树脂渗透能力的影响,建立了毛细渗透理论模型,进行模拟渗透试验.结果表明:在20～50℃范围内,升高温度能降低环氧树脂黏度,增强环氧树脂在水泥基材料微裂缝中的毛细渗透能力;环氧树脂在窄裂缝(一般小于200μm)中渗透时,初期可忽略其自身重力影响,渗透驱动力主要来源于毛细作用;在裂缝宽度为50～200μm时,环氧树脂的毛细渗透能力与裂缝宽度成反比,宽度越小毛细作用越明显,毛细渗透能力越强;环氧树脂E?51的毛细渗透能力相比环氧树脂E?44增强约17.4％,荧光环氧树脂相比普通环氧树脂的毛细渗透能力降低5％～8％.     

A Novel Polyvinyl Alcohol-Based Hydrogel with Ultra-Fast Self-Healing Ability and Excellent Stretchability Based on Multi Dynamic Covalent Bond Cross-Linking

A novel self-healing poly(vinyl alcohol) (PVA)-based hydrogel is developed by cross-linking PVA chains through multi dynamic covalent bonds by use of a small cross-linker composed by 4-formylphenylboric acid (FPBA) and lysine (Lys). The dynamic borate-imine-imine-borate bond structure between PVA chains endows the hydrogel excellent stretchability and ultra-fast self-healing ability without external stimulation. The self-healing efficiency can attain 94% and the elongation at break can reach up to near 1000% after only 3 min healing. Moreover, the self-healing of the hydrogel through the contact of two faces from both the same cut position and different cut positions has similar excellent efficiency. The hydrogel with the unusual self-healing performance and stretchability is used as an ideal material in strain sensors monitoring human movement and tiny vibrations caused by human voice. Interestingly, the sensor can continue to function normally after self-healing for only ≈3 s. It is expected that this simple strategy of fabricating self-healing hydrogels with multi dynamic bonds will provide new opportunities in the design and preparation of PVA-based hydrogels to expand their potential applications in sensors and other various fields.     

Fully Recyclable,Healable, Soft,and Stretchable Dynamic Polymers for Magnetic Soft Robots

Magnetic soft robots capable of wirelessly controlled programmable deformation and locomotion are desirable for diverse applications. Such multi-variable actuation ideally requires a polymer matrix with a well-defined range of softness and stretchability (Young's modulus of 0.1–10 MPa, high stretchability >200%). However, this defined mechanical range excludes most polymer candidates, leaving only a limited number of available polymers (e.g., PDMS, Ecoflex) with covalently cross-linked networks that may lead to non-recyclable robots and further potential threats to environment. Herein, based on the synergistic effects of reduced cross-linking density and intermolecular hydrogen bonding, a dynamic covalent polyimine is newly designed as polymer matrix and magnetic microparticles as fillers, and integrate defined softness and stretchability, full chemical recyclability, rapid room-temperature healability and multimodal actuation into a single magnetic soft robot. The polyimine is soft and stretchable enough to process soft robots in various geometries by simple laser cutting, without the need to pre-design the geometry to suit target scenarios. Through a cyclic depolymerization/repolymerization, this full recycling restores 100% of the robots’ mechanical properties and rapid deformability/mobility to their original level within seconds and heals quickly within minutes when damaged, facilitating ideal cyclic material economy for soft robots in diverse scenarios.     

Self-Healing,Photothermal-Responsive,and Shape Memory Polyurethanes for Enhanced Mechanical Properties of 3D/4D Printed Objects

Additive manufacturing is a promising technology that can directly fabricate structures with complex internal geometries, which is barely achieved by traditional manufacturing. However, the mechanical properties of fused deposition modeling (FDM)-printed objects are inferior to those of conventionally manufactured products. To improve the mechanical properties of the printed products, a series of novel thermoplastic polyurethanes with self-healing properties, intrinsic photothermal effects, and excellent printability are designed and synthesized by introducing dynamic oxime–carbamate bonds and hydrogen bonds into the polymer chains. On-demand introduction of near-infrared (NIR) irradiation, direct heating, and sunlight irradiation enhances interfacial bonding strength and thus improve the mechanical properties of the printed product. Additionally, mechanical anisotropy of the printed products can be sophistically manipulated by regulating the self-healing conditions. Support-free printing and healing of damaged printed products are also achieved owing to the self-healing properties of the material. Moreover, the as-prepared materials exhibit shape-memory properties NIR irradiation or direct heating effectively triggers shape-memory recovery and demonstrates their potential in 4D printing by printing a man-like robot. This study not only provides a facile strategy for obtaining high-performance printed products but also broadens the potential applications of FDM technology in intelligent devices.     

SiC modified self-healing ytterbium disilicate materials for potential environmental barrier coating application

Environmental barrier coatings (EBCs) are crucial to the reliability and durability of SiC_f/SiC composite components seeking applications in hot sections of next-generation advanced aero-engines. The cracks initiated and developed in EBCs owing to various reasons during service greatly undermine their lifespans. To address this problem, in this work, silicon carbide (SiC) in the forms of particles and whiskers with various amounts have been introduced to ytterbium disilicate (Yb₂Si₂O₇), the mainstream EBC topcoat materials, so as to gain some self-healing potential. The results reveal that, the SiC inclusions in Yb₂Si₂O₇ in the presence of ytterbium monosilicate (Yb₂SiO₅) can trigger the following reactions. Specifically, SiC self-healing agents are oxidized to form viscous SiO₂, which actively reacts with Yb₂SiO₅ upon encountering it, forming Yb₂Si₂O₇. This has brought twofold beneficial effects including ① silicon supplementation of disilicate topcoat, whose silicon element tends to be “dragged out” by water vapor, leading to the deterioration of thermal mismatch; as well as ② crack self-healing resulting from the volume expansion induced by the above reactions. Then the two aspects of self-healing agents, namely the “promptness” and “sustainability,” have been discussed in detail. The former is unveiled to be more pertinent to the repairing of large cracks, whilst the latter is more relevant to the self-healing of tiny cracks at initiation or early stage of propagation. The current work sheds some lights on the design and development of more durable and robust EBCs with self-healing capability.     

Self-Healing Ability of Poly(PEGMA-5-UPy) Evaluated by Thermomechanical Analysis

The synthesis and characterization of polyethylene glycol monomethyl ether methacrylate (PEGMA) based copolymers incorporating three different percentages (2.5 wt%, 5.0 wt%, and 7.8 wt%) of urea-N-2-amino-4-hydroxy-6-methylpyrimidine-N’-(hexametylen-n-carboxyethyl methacrylate) (HEMA-UPy) are reported. Nuclear magnetic resonance (NMR) and infrared spectroscopy (IR) confirm the synthesis procedure. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are employed to evaluate the thermal properties of the samples. DSC measurements evidence a slight increase in glass transition temperature (T_g), a consistent increase in crystallization and melting temperatures (T_c and T_m), and a reduction in the crystallization degree (X_c) with increasing the amount of HEMA-UPy moiety. Dynamic mechanical analysis (DMA) is carried out at different values of temperature and oscillation frequency. It highlights the ability of the healed copolymer to recover the pristine values of storage modulus. The healing efficiency depends on the temperature history of the sample. For the sample healed at room temperature, the value of healing efficiency is 64%. DMA tests performed at higher temperatures, after some permanence at room temperature, evidence higher values in the healing efficiency. This demonstrates that the higher value of the temperature employed during DMA tests determines greater mobility of the chains causing an enhancement in the healing efficiency.     

热老化下沥青胶浆微观结构及自愈合性能评价

为研究热老化作用下沥青胶浆的自愈合特性,针对3种沥青胶浆,利用原子力显微镜(AFM)、动态剪切流变仪(DSR)、弯曲梁流变仪(BBR)进行微观结构、疲劳—愈合—再疲劳、蠕变—愈合—再蠕变测试,通过2个愈合指数(H I1和H I2)研究了愈合温度、沥青种类、粉胶比、老化程度、破坏程度及愈合时间对沥青胶浆自愈合性能的影响.结果表明:老化后基质沥青胶浆中"蜂形结构"变化显著,而老化后SBS改性沥青胶浆和胶粉改性沥青胶浆的微观结构较为稳定,微观结构的改变潜在影响沥青胶浆的自愈合性能;基于累计耗散能建立的愈合指数H I1和基于时间轴与劲度模量主曲线在双对数坐标下所围面积SA而建立的愈合指数HI2能很好地反映沥青胶浆的自愈合性能;低粉胶比沥青胶浆的自愈合能力更好,老化程度的加深导致沥青胶浆的自愈合能力降低,经历低温后改性沥青胶浆的愈合能力较好.     

Electrochemical Self-Healing Nanocrystal Electrodes for Ultrastable Potassium-Ion Storage

The unique properties of self-healing materials hold great potential in battery systems, which can exhibit excellent deformability and return to its original shape after cycling. Herein, a Cu₃BiS₃ anode material with self-healing mechanisms is proposed for use in ultrastable potassium-ion battery (PIB) and potassium-ion hybrid capacitor (PIHC). Different from the binder design, Cu₃BiS₃ anode can exhibit the dual advantages of phase and morphological reversibility, further remaining original property after potassiation/depotassiation and exhibiting ultrastable cycling performance. The reversible electrochemical reconstruction during the continuous charge/discharge processes is beneficial to maintain the structure and function of the material. Furthermore, the conversion reactions during the charge and discharge process produce two advantages: i) suppressing the shuttle effect due to the formation of the heterostructure interface between Cu (111) and Bi (012); ii) Cu can avoid the agglomeration of Bi nanoparticles (NPs), further improving the electrochemical performance and long-cycle stability of the Cu₃BiS₃ electrode. As a result, the Cu₃BiS₃ electrode not only exhibits a long cycle life in half cells, but also 2000 cycles and 12000 cycles in PIB and PIHC full cells, respectively.     

Self-Adapting and Self-Healing Hydrogel Interface with Fast Zn2+ Transport Kinetics for Highly Reversible Zn Anodes

Construction of polymer-based artificial solid-electrolyte interphase films on Zn metal anode holds great potential in the suppression of both dendrite growth and side reaction in rechargeable aqueous Zn-ion batteries. However, the traditional polymer films suffer from the critical issues of sluggish Zn²⁺ transport kinetics and rigid interface. Herein, zinc alginate (ZA) hydrogel is designed and prepared as a dynamic interface and Zn²⁺ redistributor on Zn anode via in situ cross-linking reaction. The zincophilic and negatively charged carboxyl groups of ZA promote the transport of Zn²⁺ ions along a “Z-type” pathway, the repulsion of free SO₄^2- anions, and the desolvation of Zn²⁺ ions, consequently leading to the homogeneous deposition of Zn and the effective suppression of side reaction. Additionally, the dynamic flexibility of ZA hydrogel endows the Zn anode with self-adapting interface to accommodate the volume variation and repair the possible ruptures, thereby guaranteeing the long-term cycling stability. Assisted by the ZA layer, the Zn anode achieves a prolonged lifespan over 2200 h without the formation of Zn dendrites and by-products. Outstanding cycling stability is also demonstrated for the Zn anode when coupled with MnO₂ cathode, further demonstrating its prospects for practical application.     

Ionic Thermoelectric Properties of Reconstructed Lamellar Vanadium Pentoxide Membranes

In recent years, the application of ionic thermoelectric (TE) materials to convert low-grade waste heat into electricity has become a subject of intense scientific research. However, most of the efforts are focused on organic polyelectrolytes or ionic-liquids embedded in polymeric gels. Here, for the first time, it is demonstrated that nanofluidic membranes of reconstructed layered materials like vanadium pentoxide (V₂O₅) exhibit excellent ionic-TE characteristics. The high Seebeck coefficient (S = 14.5 ± 0.5 mV K^-1) of the V₂O₅ membrane (VO-M) is attributed to temperature gradient-induced unidirectional transport of protons through the percolated network of 2D nanofluidic channels. The TE characteristics of VO-M show nearly 80% improvement (S = 26.3 ± 0.7 mV K^-1) upon functionalizing its percolated network with ionic polymers like poly(4-styrenesulfonic acid) (PSS). Further, unlike organic polymer-based TE systems, VO-M not only sustains exposure to high temperatures (≈200 °C, 5 min) but also protects the PSS molecules intercalated into its interlayer space. Moreover, V₂O₅-based TE materials can self-repair any damage to their physical structure with the help of a tiny water droplet. Thus, nanofluidic membranes of reconstructed layered materials like VO-Ms demonstrate vast robustness and great ionic-TE performance, which can provide a novel platform for scientific studies and futuristic applications.