Super‐Tough,Self‐Healing Polyurethane Based on Diels‐Alder Bonds and Dynamic Zinc–Ligand Interactions

Self‐healing polymer materials have attracted extensive attention and have been explored due to their ability of crack repairing in materials. This paper aims to develop a novel polyurethane‐based material with high self‐healing efficiency and excellent mechanical properties under 80 °C on the basis of reversible Diels–Alder bonds as well as zinc–ligand structure (DA‐ZN‐PU). By integrating DA bonds and zinc–ligand structure, as‐prepared DA‐ZN‐PU samples reach the maximum tensile strength as much as 28.45 MPa. After self‐healing, the tensile strength is 25.85 MPa, leading to the high self‐healing efficiency of 90.8%. In addition, by introducing carbonyl iron powder (CIP), a new polyurethane containing carbonyl iron powder (DA‐ZN‐CIP‐PU) can be achieved, exhibiting microwave‐assisted self‐healing property. And the self‐healing efficiency can be reached to 92.6% in 3 min. Due to high self‐healing efficiency and excellent mechanical properties of the prepared novel polyurethane, it has application attributes in crack repair of functional composite materials.     

High‐temperature Bending Strength of Self‐Healing Ni/Al2O3 Nanocomposites

Bending strength of 5 vol.% Ni/Al₂O₃ composites as a function of testing temperature is investigated at temperatures ranging from room temperature to 1200°C. Self‐healing performance at high temperatures of the composites is evaluated by conducting high‐temperature bending tests for as‐sintered, as‐cracked, and as‐healed specimens. Bending strength of as‐sintered specimens dramatically decreases from 995 MPa at room temperature to 205 MPa at 1200°C. Additionally, the plastic deformation of the as‐sintered specimens occurs when the testing temperature reaches to 1200°C. The values of high‐temperature bending strength of as‐healed specimens are comparable with those of as‐sintered specimens. Similar to that of as‐sintered specimens, bending strength of as‐healed specimens degrades when the testing temperature increases. Results of the present study indicate that the recovery of bending strength by the self‐healing function is able to achieve at temperatures as high as 1200°C. Unlike the mechanical behaviors at high temperatures of as‐sintered and as‐healed specimens, the bending strength of as‐cracked specimens slightly increases with the increase of testing temperature. This phenomenon is attributed to the effect of the self‐healing mechanism during high‐temperature bending tests.     

Self‐healing supramolecular elastomers based on the multi‐hydrogen bonding of low‐molecular polydimethylsiloxanes: Synthesis and characterization

Novel self‐healing supramolecular elastomers based on polydimethylsiloxanes (SESi) were synthesized from a mixture of polydimethylsiloxanes derivers with single, di‐, or tri‐carboxylic acid groups (PDMS–COOH_x, where x = 1, 2, and 3, respectively), diethylene triamine, and urea with a two‐stage procedure. The reactions and the final products were tracked, characterized, and confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, differential scanning calorimetry, dynamic mechanical analysis, and gel permeation chromatography. Compared with a supramolecular rubber based on dimer acid (reported previously) with a similar synthesis procedure, the SESi showed a lower glass‐transition temperature of about ?113°C for the softer chain of polydimethylsiloxane and showed real rubberlike elastic behavior and self‐healing properties at room temperature or even lower temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polyether–maleimide‐based crosslinked self‐healing polyurethane with Diels–Alder bonds

The Diels–Alder (DA) reaction is particularly desirable for the preparation of heat‐stimuli self‐healing polymeric materials because of its thermal reversibility, high yield, and minimal side reactions. Some attempts were conducted to synthesize polyether–maleimide‐based crosslinked self‐healing polyurethane with DA bonds (C‐PEMIPU–DA) through the reactions of the prepolymer (polymeric MDI/PBA‐1000) functionalized by furfuryl amine and polyether–maleimide without benzene in this study. The structures of intermediates and C‐PEMIPU–DA were first confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Next, the thermal reversibility and the self‐healing performance of C‐PEMIPU–DA were studied by ¹H‐NMR, polarizing optical microscopy, tensile testing, and a sol–gel process. The results show that C‐PEMIPU–DA exhibited interesting properties of thermal reversibility and self‐healing. The polymers could be applied to self‐healing materials or recyclable materials in the fields of the repair of composite structures and aging parts because of their thermosetting properties at room temperature and thermoplasticity at higher temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41944.     

Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry

The modified novolac epoxy resins with furan pendant groups were prepared by novolac epoxy resin and furfuryl alcohol and then crosslinked by bifunctional maleimide via Diels–Alder (DA) chemistry to obtain the thermally reversible and self‐healing novolac epoxy resins. The as‐prepared crosslinked novolac epoxy resins were characterized by FT‐IR, NMR, TGA, and DMA. The results indicate that the novel crosslinked novolac epoxy resins present higher storage modulus (2.37 GPa at 30°C) and excellent thermal stability (348°C at 5% mass loss). Furthermore, the thermal reversible and self‐healing properties were studied in detail by DSC, SEM, thermal re‐solution, and gel–solution–gel transition experiments. All the results reveal that the crosslinked novolac epoxy resins based on DA reaction can be used as smart material for the practical application of electronic packaging and structural materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42167.     

Diels–Alder‐based crosslinked self‐healing polyurethane/urea from polymeric methylene diphenyl diisocyanate

Crosslinked self‐healing polyurethane/urea based on a Diels–Alder reaction (C‐PMPU–DA) was synthesized from a multiple‐furan monomer and a commercial bismaleimide. The multiple‐furan monomer (PMPU–furan) was obtained from a functionalized prepolymer (polymeric MDI: PBA‐2000 = 2:1) by furfuryl amine. The structures of both the PMPU–furan and C‐PMPU–DA were characterized by attenuated total reflectance (ATR)–Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and ¹H‐NMR. The Diels–Alder bonds enabled C‐PMPU–DA thermal reversibility, which was investigated by ATR–FTIR spectroscopy, ¹H‐NMR, gel–solution–gel experiments, and viscosity tests. Meanwhile, the self‐healing properties of C‐PMPU–DA were also investigated by the recovery of the mechanical properties. The results showed that C‐PMPU–DA exhibited good thermal reversibility and self‐healing properties. C‐PMPU–DA exhibited thermosetting properties at room temperature, although it exhibited thermoplastic properties at higher temperatures and may find applications in self‐healing materials, recyclable materials, or removable materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40234.     

Heat‐triggered poly(siloxane‐urethane)s based on disulfide bonds for self‐healing application

Polydimethylsiloxane (PDMS) is one of the most widely employed silicon‐based polymers for its high flexibility, low usage temperature, excellent water resistance, outstanding electrical insulting property, and physiological inert, etc. However, the covalent‐bonded Si? O bonds are unable to heal automatically when damaged, which would result in the failure of the materials and devices. Disulfide bond based polymers show high healing efficiency at moderate temperature and have been investigated intensively. Herein, we report a PDMS‐based polyurethane self‐healing polymer (PDMS‐PU) modified with disulfide bonds, which exhibited a reinforced thermal stability, excellent stretchability, and satisfactory self‐healing ability. The effect of different ratio of PDMS and disulfide bond contents on the elastomer properties was investigated. With the increase of PDMS content, the decomposition temperature of the PDMS‐PU‐3 (332 °C) elastomer with highest content of PDMS was increased by 34 °C compared to PDMS‐PU‐1 (298 °C) with lowest content of PDMS and exhibited a largest elongation at break of 1204%. PDMS‐PU‐1 with highest content of disulfide bond possessed a highest healing efficiency of 97%. The results indicated the PDMS‐PU elastomers can be used as self‐healing flexible substrate for flexible electronics. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46532.     

Self‐catalyzed silicon‐containing phthalonitrile resins with low melting point,excellent solubility and thermal stability

A series of silicon‐containing self‐catalyzed phthalonitrile derivatives (SiPNs) have been successfully synthesized from reaction of 4‐(4‐aminophenoxy)phthalonitrile (APN) with corresponding chlorosilanes. The chemical structures of the SiPNs were confirmed by spectroscopic techniques. The introduction of silicon‐containing unit into the phthalonitrile structure has dramatically decreased the melting point from 143°C for APN to 40–60°C for the new SiPNs, which also exhibit improved solubility and are soluble in many common solvents. Differential scanning calorimetry analysis showed that they possess the self‐catalyzed behavior with the temperature of exothermic peak due to the self‐catalyzed reaction between 255 and 281°C. The cured SiPNs exhibit excellent thermal stability with glass transition temperature above 450°C, the temperature of 5% weight loss in range of 535–570°C under nitrogen, and 543–562°C under air. Their char yields at 1000°C are in the range of 80.2–82.6% in nitrogen, and 10.1–12.5% in air, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40919.     

Sintering‐induced aromatization during n‐heptane reforming on Pt/Al2O3 catalysts

A platinum/alumina catalyst was sintered in oxygen and hydrogen atmospheres using two metal loadings of the catalyst: 0.3% Pt and 0.6% Pt. After sintering, the aromatization selectivity was investigated with the reforming of n‐heptane as the model reaction at a temperature of 500 °C and a pressure of 391.8 kPa. The primary products of n‐heptane reforming on the fresh platinum catalysts were methane and toluene, with subsequent conversion of benzene from toluene demethylation. To induce sintering, the catalysts were treated with oxygen at a flow rate of 60 mL min^?1, pressure of 195.9 kPa and temperatures between 500 and 800 °C. The 0.3% Pt/Al₂O₃ catalyst exhibited enhanced aromatization selectivity at various sintering temperatures while the 0.6% Pt/Al₂O₃ catalyst was inherently hydrogenolytic. The fact that aromatization was absent on the 0.6% Pt/Al₂O₃ catalyst was attributed to the presence of surface structures with dimensionality between two and three as opposed to essentially 2‐D structures on the 0.3% Pt/Al₂O₃ catalyst surface. On the 0.3% Pt/Al₂O₃ catalyst, the reaction product ranged from only toluene at a 500 °C sintering temperature to predominantly cracked product at a sintering temperature of 650 °C and no reaction at 800 °C. For sintering at about 650 °C, subsequent conversion of n‐heptane was complete and dropped thereafter. The turnover number was observed to change from 0.07 to 2.26 s^?1 as the dispersion changed from 0.33 to 0.09. The Koros–Nowark (K–N) test was used to check for the presence of internal diffusional incursions and Boudart's criterion was used for structural sensitivity determination. The K–N test indicated the absence of diffusional resistances while n‐heptane reforming was found to be structure sensitive on the Pt/Al₂O₃ catalyst. Copyright © 2006 Society of Chemical Industry     

Synthesis and self‐healing behavior of thermoreversible epoxy resins modified with nitrile butadiene rubber

Cracks may generate in epoxy resins, which can affect the comprehensive property and shorten service life. The problem is expected to be resolved by endowing epoxy resin with self‐healing performance. Herein, a new kind of self‐healing epoxy resin containing both Diels–Alder (DA) bonds and nitrile butadiene rubber (NBR) has been developed. The self‐healing performance and mechanical properties of as‐prepared epoxy resins are investigated by qualitative observation and quantitative measuring. Results reveal that the as‐prepared epoxy resins exhibit excellent self‐healing performance and multiple repair ability, and the self‐healing behavior is based on dual actions of thermal reversibility of DA reaction and thermal movement of molecular chains. Furthermore, the thermoreversible DA bonds contribute much to the recovery of mechanical property, while the incorporated thermoplastic NBR accelerates the whole healing process. The self‐healing efficiency of epoxy resins can be enhanced markedly by introducing thermoplastic NBR. In addition, the self‐healing epoxy resins also exhibit outstanding reprocessing performance, which makes it possible of recycling waste epoxy resin. POLYM. ENG. SCI., 59:1603–1610 2019. © 2019 Society of Plastics Engineers     

Thermoplastic acrylic resin with self‐healing properties

This article presents a novel processing method of a self‐healing acrylic thermoplastic material starting from a healing agent in solution form. The self‐healing system consisted of a solution of the healing agent dicyclopentadiene (DCPD) in dimethylformamide (DMF) and a solution of the catalyst bis(tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (called Grubbs' catalyst) in dichloromethane (DCM). Hollow glass tubes filled with the self‐healing components were incorporated into autopolymerizing acrylic resins. The one set of tubes was filled with a solution of DCPD (containing the dye Rhodamine B as a marker) and the other set with a solution of Grubbs' catalyst in dichloromethane. FTIR and DSC analyses revealed that a poly(DCPD) film formed at the healed interface. The low energy impact tests of the samples showed a recovery of 83% after 4 days. The benefits of the Grubb's catalyst solution are twofold; besides the repair of the cracks, which is common for such a system, the reaction could decrease the content of residual monomer in the acrylic resin, which could reduce diffusion of residual monomer out of the resins. POLYM. ENG. SCI., 56:251–257, 2016. © 2015 Society of Plastics Engineers     

Ultraporous poly(lactic acid) scaffolds with improved mechanical performance using high‐pressure molding and salt leaching

A novel processing technique, i.e. high‐pressure compression molding/salt leaching, was developed to fabricate ultraporous poly(lactic acid) (PLA) scaffolds. The optimized composition was studied in relation to the porosity, pore morphology, thermal property, and mechanical performance of the PLA scaffolds. At a porogen (CaCO₃) content of 90 wt %, the scaffolds have an interconnected open pore structure and a porosity above 80%. It was truly interesting that the structural stability of high‐pressure molded scaffolds was remarkably improved based on the fact that its glass transition temperature (83.5°C) increased about 20°C, as compared to that of the conventional compression‐molded PLA (60°C), which is not far from physiological temperature (～37°C) at the risk of structural relaxation or physical aging. More importantly, the mechanical performance of PLA scaffolds was drastically enhanced under optimized processing conditions. At pressure and temperature of 1000 MPa and 190°C, the porous PLA scaffolds attained a storage modulus of 283.7 MPa, comparable to the high‐end value of trabecular bone (250 MPa) ever reported. In addition, our prepared PLA scaffolds showed excellent cellular compatibility and biocompatibility in vitro tests, further suggesting that the high‐pressure molded PLA scaffolds have high potential for bone tissue engineering applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3509–3520, 2013     

The effect of modification on structure and dynamic mechanical behavior during the processing of acrylic fiber to stabilized fiber

Polyacrylonitrile (PAN) fibers pretreated with potassium permanganate have reduced the time required for stabilization, and also improved mechanical properties of the resultant carbon fibers. In this study, the effect of modification on the stabilization process and the dynamic mechanical properties of PAN fibers have been examined. The beta peak appeared at about 125°C on the loss tangent curves caused by molecular motion in the PAN fiber. Appearing at about 254°C, the alpha peak is attributed to chemical reactions and molecular motion in the formation of the crystalline phase of stabilized fibers. The alpha peak of the modified PAN fiber had lower absorption and had a smaller peak in the temperature range of 212–239°C. This indicated that potassium permanganate acts as a catalyst to lower the reaction temperature by about 20°C of the initial cyclization reaction. The dynamic storage modulus analysis indicated that modified PAN fibers have a lower initial transition temperature and that formation of the ladder polymer is gradual and steady.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Highly stretchable,tough, and self‐recoverable and self‐healable dual physically crosslinked hydrogels with synergistic “soft and hard” networks

Strength, toughness and self‐recoverability are among the most important properties of hydrogels for tissue‐engineering applications. Yet, it remains a challenge to achieve these desired properties from the synthesis of a single‐polymer hydrogel. Here, we report our one‐pot, a monomer‐polymerization approach to addressing the challenge by creating dual physically crosslinked hybrid networks, in particular, synergistic “soft and hard” polyacrylic acid‐Fe³⁺ hydrogels (SHPAAc‐Fe³⁺). Favorable mechanical properties achieved from such SHPAAc‐Fe³⁺ hydrogels included high tensile strength (about 1.08 MPa), large elongation at break (about 38 times), excellent work of extension (about 19 MJ m^?3), and full self‐recoverability (100% recovery of initial properties within 15 min at 50°C and within 60 min in ambient conditions, respectively). In addition, the hydrogels exhibited good self‐healing capabilities at ambient conditions (about 40% tensile strength recovery without any external stimuli). This work demonstrates that dual physical crosslinking combining hydrophobic interaction and ionic association can be achieved in single‐polymer hydrogels with significantly improved mechanical performance but without sacrificing favorable properties. POLYM. ENG. SCI., 59:145–154, 2019. © 2018 Society of Plastics Engineers     

Study of Screen‐Printed PZT Cantilevers Both Self‐Actuated and Self‐Read‐Out

Usually, resonating cantilevers come from silicon technology and are activated with pure bending mode. In this work, we suggest to combine high‐sensitive cantilever structure with both self‐actuated and self‐read‐out piezoelectric thick‐film for high electrical–mechanical coupling. This cantilever is realized through screen‐printing deposition associated with a sacrificial layer. It is composed of a PZT layer between two gold electrodes. Optimum performances of piezoelectric ceramics generally imply the use of mechanical pressure and very high sintering temperature that are not compatible with the screen‐printing process. Addition of eutectic composition Li₂CO₃‐Bi₂O₃‐CuO or borosilicate glass‐frit to PZT powder and application of isostatic pressure improve the sintering at a given temperature. Firing temperature of 850°C, 900°C, and 950°C is tested. Microstructural, electrical and mechanical characterizations are achieved. In addition to the bending mode, the in‐plane 31‐longitudinal vibration mode and the out‐of‐plane 33‐thickness resonance mode are revealed. Correlations between experimental results and modeling of the different vibration modes are established. The piezoelectric parameters of PZT cantilevers approach those of ceramics. Quality factors between 300 and 400 associated with the unusual 31‐longitudinal mode make screen‐printed PZT cantilevers good candidates for detection in liquid and gaseous media.     

Catalytic effect of 2,2′‐diallyl bisphenol A on thermal curing of cyanate esters

Cyanate esters are a class of thermal resistant polymers widely used as thermal resistant and electrical insulating materials for electric devices and structural composite applications. In this article, the effect of 2,2′‐diallyl bisphenol A (DBA) on catalyzing the thermal curing of cyanate ester resins was studied. The curing behavior, thermal resistance, and thermal mechanical properties of these DBA catalyzed cyanate ester resins were characterized. The results show that DBA is especially suitable for catalyzing the polymerization of the novolac cyanate ester resin (HF‐5), as it acts as both the curing catalyst through depressing the exothermic peak temperature (T_exo) by nearly 100°C and the toughening agent of the novolac cyanate ester resin by slightly reducing the elastic modulus at the glassy state. The thermogravimetric analysis and dynamic mechanical thermal analysis show that the 5 wt % DBA‐catalyzed novolac cyanate ester resin exhibits good thermal resistance with T_d⁵ of 410°C and the char yield at 900°C of 58% and can retain its mechanical strength up to 250°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1775–1786, 2006     

Physical characterization of a self‐healing dental restorative material

The objectives of this study were to determine the efficacy of self‐healing a highly filled composite and to investigate the physical properties of a model dental compound formulated to autonomically heal cracks. A visible light cured model resin consisting of TEGMA : UDMA : BisGMA (1 : 1 : 1) at 45% w/w with silane 0.7 μ glass was formulated with a self‐healing system consisting of encapsulated dicyclopentadiene and Grubbs' catalyst. The base resin was also formulated and characterized with the microcapsules alone, Grubbs' catalyst alone, and no healing additives. Fracture toughness (K_Ic) was assessed using single edge notch specimens in three‐point bend (n = 12). Data was analyzed with ANOVA/Tukey's at p ≤ 0.05. DMA was performed from ?140 to 250°C at 2°/min and 1 Hz. Storage and loss modulus, T_g and tan δ, was recorded for each material. The self‐healing material was loaded to failure, was left to sit for 7 days and then loaded a second time to failure to determine healing in the material. These specimens had a K_Ic = 0.69 ± 0.072 for a 57% average recovery rate of the original fracture toughness. The fracture toughness of the self‐healing material was statistically similar to the control. The modulus decreased in the composites with encapsulated dicyclopentadiene. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

2D‐ and 3D Observation and Mechanism of Self‐Healing in Glass–Boron Composites

The self‐healing of a crack in a glass–boron composite has been observed by X‐ray nanotomography. It shows the occurrence of a healing effect within the bulk of the composite, despite of a limited oxygen access in the crack. This 3D tomographic observation offers new insights in the mechanism of healing, complementary to in situ high‐temperature environmental scanning electron microscopy. In addition, nano‐X‐ray fluorescence imaging, electron microprobe and solid‐state NMR gave evidence that the molten B₂O₃, produced by the oxidation of boron particles at 700°C, reacts with the glass matrix to form borosilicate compounds that also contribute to heal the crack. The high viscosity of B₂O₃ at 700°C leads to the formation of bridges between the walls of the crack, which limit oxygen diffusion. Thus, the B particle oxidation is not completed after a single healing cycle, meaning that several healing cycles can be obtained in a composite.     

Performance of long glass fiber‐reinforced polypropylene composites at different injection temperature

Long glass fiber‐reinforced polypropylene composites were prepared using self‐designed impregnation device. Effects of the different injection temperature on mechanical properties, crystallization, thermal, and dynamic mechanical properties of long glass fiber‐reinforced polypropylene composites were discussed. The differential scanning calorimetry (DSC) results indicate that the melting peak temperature of PP/LGF composites gradually reduced, however, the crystallinity of PP/LGF composites gradually increased with increasing injection temperature. Thermo‐gravimetric analyzer (TGA) results demonstrate that with increasing injection temperature, the temperature of the PP/LGF composites melt increased, the viscosity of the PP/LGF composites melt lowered, the mold filling of the PP/LGF composites melt was easy, the shear force of glass fiber was relatively low, which made the residual length of glass fiber in products increase. Dynamic thermal mechanical analyzer (DMA) results show that the storage modulus of PP/LGF composites is the highest while the injection temperature is at 290°C, and the peak value of tan σ of PP /LGF composites at 290°C is minimal, which indicates that the mechanical properties of PP /LGF composites at 290°C is the best. What' more, the injection temperature at 290°C significantly ameliorated “glass fiber rich skin” of products of glass fiber‐reinforced composites. J. VINYL ADDIT. TECHNOL., 24:233–238, 2018. © 2016 Society of Plastics Engineers