Bottom‐Up Assembling Hierarchical Enamel‐Like Bulk Materials with Excellent Optical and Mechanical Properties for Tooth Restoration

Enamel has good optical and mechanical properties because of its multiscale hierarchical structure. Biomimetic construction of enamel-like 3D bulk materials at nano-, micro-, mesh- and macro-levels is a challenge. A novel facile, cost-effective, and easy large-scale bottom-up assembly strategy to align 1D hydroxyapatite (HA) nanowires bundles to 3D hierarchical enamel structure with the nanowires bundles layer-by-layer interweaving orientation, is reported. In the strategy, the surface of oleate templated ultralong HA nanowires with a large aspect ratio is functionalized with amphiphilic 10-methacryloyloxydecyl dihydrogen phosphate (MDP). Furtherly, the MDP functionalized HA nanowire bundles are assembled layer-by-layer with oriented fibers in a single layer and cross-locked between layers at a certain angle at mesoscale and macroscale in the viscous bisphenol A-glycidyl methacrylate (Bis-GMA) ethanol solution by shear force induced by simple agitation and high-speed centrifugation. Finally, the excessive Bis-GMA and ethanol are removed, and (Bis-GMA)-(MDP-HA nanowire bundle) matrix is densely packed under hot pressing and polymerized to form bulk enamel-like materials. The composite has superior optical properties and comparable comprehensive mechanic performances through a combination of strength, hardness, toughness, and friction. This method may open new avenues for controlling the nanowires assembly to develop hierarchical nanomaterials with superior properties for many different applications.