Multi-Gradient Bone-Like Nanocomposites Induced by Strain Distribution

The heterogeneity of bones is elegantly adapted to the local strain environment, which is critical for maintaining mechanical functions. Such an adaptation enables the strong correlation between strain distributions and multiple gradients, underlying a promising pathway for creating complex gradient structures. However, this potential remains largely unexplored for the synthesis of functional gradient materials. In this work, heterogeneous bone-like nanocomposites with complex structural and compositional gradients comparable to bones are synthesized by inducing strain distributions within the polymer matrix containing amorphous calcium phosphate (ACP). Uniaxial stretching of composite films exerts the highest strain in the center, which ceases gradually toward the sides, resulting in the gradual decrease of polymer alignment and crystallinity. Simultaneously, the center with high orientation traps most ACP during stretching due to the nanoconfinement effect, which in turn promotes the formation of aligned nanofibrous structures. The sides experiencing the least strain have the smallest amounts of ACP, characteristic of porous architectures. Further crystallization of ACP produces oriented apatite nanorods in the center with a larger crystalline/amorphous ratio than the sides because of template-induced crystallization. The combination of structural and compositional gradients leads to gradient mechanical properties, and the gradient span and magnitude correlate nicely with strain distributions. Accompanying bone-like mechanical gradients, the center is less adhesive and self-healable than the sides, which allows a better recovery after a complete cutting. Our work may represent a general strategy for the synthesis of biomimetic materials with complex gradients thanks to the ubiquitous presence of strain distributions in load-bearing structures.