Basam A.E. Ben-Arfa

Novel route for rapid sol-gel synthesis of hydroxyapatite, avoiding ageing and using fast drying with a 50-fold to 200-fold reduction in process time

We have developed an innovative, rapid sol-gel method of producing hydroxyapatite nanopowders that avoids the conventional lengthy ageing and drying processes (over a week), being 200 times quicker in comparison to conventional aqueous sol-gel preparation, and 50 times quicker than ethanol based sol-gel synthesis. Two different sets of experimental conditions, in terms of pH value (5.5 and 7.5), synthesis temperature (45 and 90°C), drying temperature (60 and 80°C) and calcination temperature (400 and 700°C) were explored. The products were characterised by X-ray diffraction (XRD) Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and specific surface area (SSA) measurements. Pure hydroxyapatite (Ca10(PO4)6(OH)2, HAp) was obtained for the powders synthesised at pH7.5 and calcined at 400°C, while biphasic mixtures of HAp/β-tricalcium phosphate (β-Ca3(PO4)2, TCP) were produced at pH5.5 and (pH7.5 at elevated temperature). The novel rapid drying was up to 200 times faster than conventional drying, only needing 1h with no prior ageing step, and favoured the formation of smaller/finer nanopowders, while producing pure HAp or phase mixtures virtually identical to those obtained from the slow conventional drying method, despite the absence of a slow ageing process. The products of this novel rapid process were actually shown to have smaller crystallite sizes and larger SSA, which should result in increased bioactivity.

Synthesis and bioactivity assessment of high silica content quaternary glasses with Ca:P ratios of 1.5 and 1.67, made by a rapid sol-gel process

Sol-gel glasses in quaternary silica-sodium-calcium-phosphorous systems have been synthesized using a rotary evaporator for rapid drying without ageing. This novel fast drying method drastically decreases the total drying and ageing time from several weeks to only 1 hour, thus overcoming a serious drawback in sol-gel preparation procedures for bioglasses. This work investigates the bioactivity behavior of two glasses synthesized by this fast method, with Ca:P ratios of 1.5, and 1.67. X-ray diffraction (XRD), Inductive coupled plasma, Fourier-transform infrared, and Raman spectroscopy were used to confirm the bioactivity of the synthesized powders. MAS-NMR was also used to assess the degree of silica polymerization. The composition with a higher Ca:P = 1.67 ratio showed better bioactivity in comparison to the one with Ca:P = 1.5, which exhibited little bio-response with up to 4 weeks of immersion in SBF (simulated body fluid). It was also found that an orbital agitation rate of 120 rpm favors the interfacial bio-mineralization reactions, promoting the formation of a crystalline hydroxyapatite (HAp) layer at the surface of the (Ca:P = 1.67) composition after 2 weeks immersion in SBF.

Enhanced bioactivity of a rapidly-dried sol-gel derived quaternary bioglass

Novel quaternary (67Si-24Ca-10Na-8P) glass powders were successfully synthesised by sol-gel followed by two alternative drying schedules, conventional drying (CD) and an innovative fast drying (FD) process (200 times quicker). The glasses were thermally stabilised at 550 °C, and then characterised by different complementary techniques. The samples showed very similar silica network structures, with the FD one having slightly lower degree of polymerisation than the CD sample. This less polymerised, more open, network structure exhibited an improved bioactivity in simulated body fluid (SBF), probably also due to the apparent presence of poorly crystalline HAp in the stabilised glass powder. In contrast, the CD glass exhibited an unwanted secondary crystalline silica phase. Both glasses showed excellent biomineralisation upon immersion in SBF, being more pronounced in the case of FD with clear evidence of HAp formation after 4 h, while equivalent signs in the CD samples were only noticed after longer immersion periods between 8 h and 1 week.