Vinyl ester (VE) resin is widely used as a thermosetting polymer for structural materials because of its high mechanical properties and excellent chemical resistance. Using additive manufacturing to produce high-performance VE structures with dimensional scalability and material efficiency has gained interest from both research and industry, however it is challenging due to the limitations of current techniques. In this work, a modified setup of direct ink writing (DIW) with ultraviolet (UV)-thermal dual curing is made compatible with commercially available VE resins thickened by 4 wt% fumed silica to fabricate three-dimensional structures with outstanding mechanical properties. The in-situ UV curing during DIW partially solidifies the resin to provide the structural shape, and subsequent thermal curing allows for a high degree of crosslinking. The printed and dual cured VE nanocomposites have a Young’s modulus of 3.7 GPa and a tensile strength of approximately 80 MPa, which outperforms conventionally molded neat VE cured with methyl ethyl ketone peroxide (MEKP) by about 10% and also indistinguishable from the tensile properties of molded VE nanocomposites with the same composition. The fracture toughness of the printed and dual cured VE nanocomposites is also 16% higher than the molded neat VE with MEKP curing due to the superior interfacial bonding between DIW infill paths and the additional 4 wt% fumed silica for toughening, and similar to the molded VE nanocomposites with the same composition. Along with the outstanding mechanical properties, the scalability and resolution of the DIW technique with dual curing is demonstrated by printing a 100 mm long wrench and a microscale lattice, thus showing the potential of this technique in additive manufacturing of high-performance VE structures.

乙烯基酯（VE）树脂因其高机械性能和优异的耐化学性而被广泛用作结构材料的热固性聚合物。使用增材制造生产具有尺寸可扩展性和材料效率的高性能 VE 结构引起了研究和工业界的兴趣，但由于当前技术的局限性，这具有挑战性。在这项工作中，采用紫外线 (UV)-热双重固化的直接墨水书写 (DIW) 的改进设置与由 4 wt% 气相二氧化硅增厚的市售 VE 树脂兼容，以制造具有出色机械性能的三维结构。DIW 过程中的原位 UV 固化使树脂部分固化以提供结构形状，随后的热固化允许高度交联。印刷和双重固化的 VE 纳米复合材料具有 3.7 GPa 的杨氏模量和约 80 MPa 的拉伸强度，比用过氧化甲乙酮 (MEKP) 固化的常规模塑纯 VE 高约 10%，并且与具有相同成分的模塑VE纳米复合材料。由于 DIW 填充路径和额外的 4 wt% 气相二氧化硅用于增韧，印刷和双重固化的 VE 纳米复合材料的断裂韧性也比使用 MEKP 固化的模制纯 VE 高 16%，并且类似于模制具有相同成分的VE纳米复合材料。除了出色的机械性能外，双固化 DIW 技术的可扩展性和分辨率通过打印 100 毫米长的扳手和微尺度晶格得到证明，