A novel low-temperature densification method of nanocrystalline calcium hydroxyapatite (HAp) at a temperature as low as 200 degrees C with no liquid additives is investigated. To understand the underlying mechanism of the low-temperature sintering of hydroxyapatite, two types of lab-synthesized nanocrystalline HAp, dried (110 degrees C, 12 h) and calcined (1000 degrees C, 2 h), were subjected to cold sintering conditions (200 degrees C, 500 MPa) and compared thoroughly. The dried samples were found to be nanocrystalline, enveloped by an amorphous shell, whereas the calcined samples were fully crystalline, as confirmed by X-ray diffraction, transmission electron microscopy, and solid-state nuclear magnetic resonance techniques. A relative density of 98.8% was achieved for the dried samples; however, the calcined samples could not be sintered. This indicates a clear dependence of densification on the surface chemistry of the nanocrystals involving rearrangement and dehydration of the amorphous layer present on the surface of the nanocrystals under the influence of applied pressure and temperature. Moreover, the calcined sample, which had a fully developed crystalline structure, did not undergo sintering, even with the use of added water. Therefore, it is demonstrated that wet-precipitated and dried nanocrystalline HAp can be cold-sintered to full densification for applications in biomedical materials or radioactive waste immobilization of volatile radionuclides at a considerably low temperature, without the addition of sintering aids. (c) 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).