3D printable elastomers capable of
self-healing are attractive
for fabricating complex biomimetic and soft-robotic devices. While
polymer network reorganization can be enabled with dynamic bond exchange,
this strategy typically faces intrinsic trade-offs between healability,
processability, and mechanical performance. Thus, new material design
strategies that can overcome these trade-offs are needed. Here, we
report the use of multivalent polymer-grafted nanoparticles (PGNPs)
as reinforcing fillers for self-healing photoresins. As each nanoparticle
is functionalized with thousands of polymer chains engaging in multivalent
interactions with the surrounding elastomeric matrix, the bulk modulus
of the composite can be increased without impairing the local segmental
motion of polymer chains necessary for self-healing. We also examine
PGNP structural parameters to establish structure–property
relationships that permit fine-tuning of composite mechanical performance.
Finally, these enhancements do not impair the materials’ manufacturability,
as they can be used as feedstocks for digital light printing to produce
complex and high-resolution 3D objects.