Radiation stability of nanostructured hydroxyapatite Ca10(PO4)6(OH)2 under ion irradiations

Abstract

Radiation stability of nanostructured hydroxyapatite with different interfacial structure is studied. Hydroxyapatite nanoparticle (HAp-np) is fabricated by calcination in muffle furnace and densified nanocrystalline hydroxyapatite (HAp-nc) is synthesized by spark plasma sintering . X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterizations show the hexagonal structure for both HAp-np and HAp-nc. Irradiation responses of HAp-np and HAp-nc are studied via in situ TEM techniques. The samples are irradiated with 1 MeV Kr 2+ ions over the temperature range of 150 K to 523 K. In situ TEM observations reveal a higher critical amorphization dose of HAp-nc (0.075 dpa) compared to 0.05 dpa of HAp-np at room temperature, indicating enhanced amorphization resistance. The radiation tolerance shows a great dependence on temperature, and a higher critical dose can be observed at elevated temperatures. A lower critical amorphization temperature ( T c ) of HAp-nc (∼437 K) than HAp-np (∼545 K) indicates better radiation tolerance since the lower T c shows better defect annealing ability. This better radiation tolerance of HAp-nc is attributed to the higher sink strength and lower interface energy carried by densified grain boundaries as free-standing open surfaces of HAp-np can carry more isolated dangling bonds that results in a higher interface energy. This excess interface energy can lower the energy difference between crystalline phase and amorphous state, leading to HAp-np to be less radiation resistant. Radiation-induced amorphization is attributed to the accumulation of oxygen vacancies and the glass-like structure rearranged by displaced oxygen and phosphorus atoms.