Nature excels in both self-healing and 3D shaping; for example, self-healable human organs feature functional geometries and microstructures. However, tailoring man-made self-healing materials into complex structures faces substantial challenges. Here, we report a paradigm of photopolymerization-based additive manufacturing of self-healable elastomer structures with free-form architectures. The paradigm relies on a molecularly designed photoelastomer ink with both thiol and disulfide groups, where the former facilitates a thiol-ene photopolymerization during the additive manufacturing process and the latter enables a disulfide metathesis reaction during the self-healing process. We find that the competition between the thiol and disulfide groups governs the photocuring rate and self-healing efficiency of the photoelastomer. The self-healing behavior of the photoelastomer is understood with a theoretical model that agrees well with the experimental results. With projection microstereolithography systems, we demonstrate rapid additive manufacturing of single- and multimaterial self-healable structures for 3D soft actuators, multiphase composites, and architected electronics. Compatible with various photopolymerization-based additive manufacturing systems, the photoelastomer is expected to open promising avenues for fabricating structures where free-form architectures and efficient self-healing are both desirable.

大自然在自我修复和3D塑造方面均表现出色；例如，可自我修复的人体器官具有功能性的几何结构和微观结构。然而，将人造的自我修复材料定制成复杂的结构面临着巨大的挑战。在这里，我们报告了一种基于光聚合的具有自由形式结构的可自修复弹性体结构的增材制造范例。该范例依赖于具有硫醇和二硫键基团的分子设计的光弹性油墨，前者在增材制造过程中促进硫醇-烯的光聚合，而后者在自修复过程中促进二硫化合物的易位反应。我们发现，硫醇基团和二硫键基团之间的竞争决定了光弹性体的光固化速率和自修复效率。可以通过与实验结果吻合的理论模型了解光弹性体的自我修复行为。使用投影微立体光刻系统，我们演示了用于3D软执行器，多相复合材料和体系结构电子产品的单材料和多材料自修复结构的快速增材制造。与各种基于光聚合的增材制造系统兼容，光弹性体有望为制造同时需要自由形式结构和有效自我修复的结构开辟前景广阔的途径。我们演示了用于3D软执行器，多相复合材料和体系结构电子产品的单材料和多材料自修复结构的快速增材制造。与各种基于光聚合的增材制造系统兼容，光弹性体有望为制造同时需要自由形式结构和有效自我修复的结构开辟前景广阔的途径。我们演示了用于3D软执行器，多相复合材料和体系结构电子产品的单材料和多材料自修复结构的快速增材制造。与各种基于光聚合的增材制造系统兼容，光弹性体有望为制造同时需要自由形式结构和有效自我修复的结构开辟前景广阔的途径。