Although 3D printing allows the macroscopic structure of objects to be easily controlled, controlling the nanostructure of 3D printed materials has rarely been reported. Herein, we report an efficient and versatile process for fabricating 3D printed materials with controlled nanoscale structural features. This approach uses resins containing macromolecular chain transfer agents (macroCTAs) which microphase separate during the photoinduced 3D printing process to form nanostructured materials. By varying the chain length of the macroCTA, we demonstrate a high level of control over the microphase separation behavior, resulting in materials with controllable nanoscale sizes and morphologies. Importantly, the bulk mechanical properties of 3D printed objects are correlated with their morphologies; transitioning from discrete globular to interpenetrating domains results in a marked improvement in mechanical performance, which is ascribed to the increased interfacial interaction between soft and hard domains. Overall, the findings of this work enable the simplified production of materials with tightly controllable nanostructures for broad potential applications.

虽然 3D 打印可以轻松控制物体的宏观结构，但控制 3D 打印材料的纳米结构的报道很少。在这里，我们报告了一种高效且通用的工艺，用于制造具有受控纳米级结构特征的 3D 打印材料。这种方法使用含有大分子链转移剂 (macroCTAs) 的树脂，这些树脂在光诱导 3D 打印过程中会发生微相分离，从而形成纳米结构材料。通过改变macroCTA的链长，我们展示了对微相分离行为的高度控制，从而产生具有可控纳米级尺寸和形态的材料。重要的是，3D 打印物体的整体机械性能与其形态相关；从离散的球状域过渡到互穿域会导致机械性能显着提高，这归因于软域和硬域之间的界面相互作用增加。总体而言，这项工作的发现能够简化具有严格可控纳米结构的材料的生产，以实现广泛的潜在应用。