Lightweight structures are often used for applications requiring higher strength-to-weight ratios and lower densities, such as in aircraft, vehicles, and various engine components. Three-dimensional (3D) printing technology has been widely used for lightweight polymer structures because of the superior flexibility, personalized design, and ease of operation offered by it. However, synthesis of lightweight polymeric structures that possess both high specific strength and glass transfer temperature (T g ) remains an elusive goal, because 3D printed polymers with these properties are still very few in the market. For example, 3,3′,4,4'-biphenyl tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA)-type (UPILEX-S type) polyimides show exceptional thermal stability (T g up to ≈400 °C) and mechanical properties (tensile strength exceeding 500 MPa) and are the first choice if extremely high temperatures of 400 °C or even higher (depending on the duration) are required, which hampers their processing using existing 3D printing techniques. However, their processing using existing 3D printing techniques is hampered due to their thermal resistance. Herein, a 3D printing approach was demonstrated for generating complex lightweight BPDA-PDA polyimide geometries with unprecedented specific strength and thermal resistance. The simple aqueous polymerization reaction of BPDA with water-soluble PDA and triethylamine (TEA) afforded the poly(amic acid) ammonium salt (PAAS) hydrogels. These PAAS solutions showed clear shear thinning and thermo-reversibility, along with high G′ gel-state moduli, which ensured selfsupporting features and shape fidelity in the gel state. Postprinting thermal treatment transformed the PAAS precursor to BPDA− PDA polyimide (UPILEX-S type). The resulting layer-by-layer deposition onto lightweight polyimide honeycombs in the form of triangular, square, and hexagonal structures showed tailorable mechanical strength, exceptional compressive strength-to-weight ratio (highest up to 0.127 MPa (kg m −3 ) −1 ), and remarkable thermoresistance (T g approximately 380 °C). These high-performance 3D printed polyimide honeycombs and unique synthetic techniques with general structures are potentially useful in fields ranging from automotive to aerospace technologies.
In response to the theme of environmental protection and green development in the world in the recent years, waterborne epoxy resin has received more and more attention. Waterborne epoxy resin has lower toxicity, but its low toughness limits the application range of waterborne epoxy resin. Here, we first proposed a method of toughening waterborne epoxy resin with aqueous polyamide salt solution. In this article, a series of waterborne polyamic acid salts is used as modification polymer to improve the high‐temperature resistance and other properties of waterborne epoxy resins by copolymerization modification. Waterborne polyamic acid salt is dispersed uniformly in the epoxy resin. After curing, by compared with the pure epoxy resin, a semi‐interpenetrating network is formed, the cross‐linking density and the high‐temperature resistance of the material are increased, and the glass transition temperature increases from 105°C to 116°C. The storage modulus at 300°C increases from 6.15 to 15.76 MPa. Thermogravimetric Analysis results reveal that the corresponding temperatures of 5% and 10% weight loss increase from 403°C and 419°C to 415°C and 435°C, respectively. At the same time, the toughness of the imide chain segment and polar groups lead to the improved adhesion of the epoxy system, the peeling strength increase from 0.51 to 1.24 N cm−1, and the lap shear strength at high temperature (100°C) increase from 0.58 to 16.97 MPa. The water absorption decreases from 1.51% to 0.66%. The developed waterborne epoxy resin is expected to be used as a high‐temperature waterborne epoxy coating in high‐temperature coatings and other applications.
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