Abstract
Tooth enamel, and especially the outer tooth enamel, is a load-resistant shell that benefits mastication but is easily damaged, driving the need for enamel-restorative materials with comparable properties to restore the mastication function and protect the teeth. Synthesizing an enamel analog that mimics the components and hierarchical structure of natural tooth enamel is a promising way to achieve these comparable mechanical properties, but it is still challenging to realize. Herein, we fabricate a hierarchical enamel analog with comparable stiffness, hardness, and viscoelasticity as natural enamel by incorporating three hierarchies of outer tooth enamel based on hierarchical assembly of enamel-like hydroxyapatite hybrid nanowires with polyvinyl alcohol as a matrix. This enamel analog possesses enamel-similar inorganic components and a nanowire-microbundle-macroarray hierarchical structure. It exhibits toughness of 19.80 MPa m1/2, which is 3.4 times higher than natural tooth enamel, giving it long-term fatigue durability. This hierarchical design is promising for scalable production of enamel-restorative materials and for optimizing the mechanical performance of engineering composites.