Synthesis of calcium-deficient hydroxyapatite nanowires and nanotubes performed by template-assisted electrodeposition

• Published in: Materials Science & Engineering C 2019-05, Vol.98, p.333-346
• Main Authors: Beaufils, Sylvie, Rouillon, Thierry, Millet, Pierre, Le Bideau, Jean, Weiss, Pierre, Chopart, Jean-Paul, Daltin, Anne-Lise
• Format: Article
• Language: English
• Subjects: Baths; Biological effects; Biological properties; Biomedical materials; Bone biomaterials; Bone healing; Calcium; Calcium deficient hydroxyapatite; Electrodeposition; Energy dispersive X ray spectroscopy; Geriatry and gerontology; Gold; High aspect ratio; Human health and pathology; Hydrogen peroxide; Hydroxyapatite; Life Sciences; Materials science; Mechanical properties; Membranes; Microscopy; Morphology; Nanotechnology; Nanotubes; Nanowires; Nucleation; Particle size distribution; Polycarbonate; Porosity; Rhumatology and musculoskeletal system; Scanning electron microscopy; Size distribution; Substrates; Surgical implants; Synthesis; Template synthesis; Thin films; Transmission electron microscopy; X-ray diffraction; X-ray spectroscopy
• ISSN: 0928-4931; 1873-0191
• DOI: 10.1016/j.msec.2018.12.071

Hydroxyapatite (HA) has received much interest for being used as bone substitutes because of its similarity with bioapatites. In form of nanowires or nanotubes, HA would offer more advantages such as better biological and mechanical properties than conventional particles (spherical). To date, no study had allowed the isolated nanowires production with simultaneously well-controlled morphology and size, narrow size distribution and high aspect ratio (length on diameter ratio). So, it is impossible to determine exactly the real impact of particles' size and aspect ratio on healing responses of bone substitutes and characteristics of these ones; their biological and mechanical effects can never be reproducible. By the template-assisted pulsed electrodeposition method, we have for the first time succeeded to obtain such calcium-deficient hydroxyapatite (CDHA) particles in aqueous baths with hydrogen peroxide by both applying pulsed current density and pulsed potential in cathodic electrodeposition. After determining the best conditions for CDHA synthesis on gold substrate in thin films by X-ray diffraction (XRD) and Energy dispersive X-ray spectroscopy (EDX), we have transferred those conditions to the nanowires and nanotubes synthesis with high aspect ratio going until 71 and 25 respectively. Polycrystalline CDHA nanowires and nanotubes were characterized by Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). At the same time, this study enabled to understand the mechanism of nanopores filling in gold covered polycarbonate membrane: here a preferential nucleation on gold in membranes with 100 and 200 nm nanopores diameters forming nanowires whereas a preferential and randomly nucleation on nanopores walls in membranes with 400 nm nanopores diameter forming nanotubes. •Ca-deficient hydroxyapatite confirmed by electrodeposition in thin films on gold•High aspect ratio polycrystalline nanowires by a template-assisted electrodeposition•Nanopores diameter (100, 200 or 400 nm) controls the nanotubes/nanowires morphology•Deposition parameters (duration and current density) control length and morphology•Mechanism of nanostructures (nanowires or nanotubes) growth has been explained