Solvothermal Transformation of a Calcium Oleate Precursor into Large‐Sized Highly Ordered Arrays of Ultralong Hydroxyapatite Microtubes

Hydroxyapatite (HAP), a well‐known member of the calcium phosphate family, is the major inorganic component of bones and teeth in vertebrates. The highly ordered arrays of HAP structures are of great significance for hard tissue repair and for understanding the formation mechanisms of bones and teeth. However, the synthesis of highly ordered HAP structure arrays remains a great challenge. In this work, inspired by the ordered structure of tooth enamel, we have successfully synthesized three‐dimensional bulk materials with large sizes (millimeter scale) that are made of highly ordered arrays of ultralong HAP microtubes (HOAUHMs) by solvothermal transformation of calcium oleate precursor. The core–shell‐structured oblate sphere consists of a core that is composed of HAP nanorods and a shell that consists of highly ordered HAP microtube arrays. The prepared HOAUHMs are large: 6.0 mm in diameter and up to 1.4 mm in thickness. With increasing solvothermal reaction time, the HOAUHMs grow larger; the microtubes become more uniform and more ordered. This work provides a new synthetic method for synthesizing highly ordered arrays of uniform HAP ultralong microtubes that are promising for biomedical applications.