Bioactive Composite for Orbital Floor Repair and Regeneration.

In the maxillofacial area, specifically the orbital floor, injuries can cause bone deformities in the head and face that are difficult to repair or regenerate. Treatment methodologies include use of polymers, metal, ceramics on their own and in combinations mainly for repair purposes, but little attention has been paid to identify suitable materials for orbital floor regeneration. Polyurethane (PU) and hydroxyapatite (HA) micro- or nano- sized with different percentages (25%, 40% & 60%) were used to fabricate bioactive tissue engineering (TE) scaffolds using solvent casting and particulate leaching methods. Mechanical and physical characterisation of TE scaffolds was investigated by tensile tests and SEM respectively. Chemical and structural properties of PU and PU/HA scaffolds were evaluated by infrared (IR) spectroscopy and Surface properties of the bioactive scaffold were analysed using attenuated total reflectance (ATR) sampling accessory coupled with IR. Cell viability, collagen formed, VEGF protein amount and vascularisation of bioactive TE scaffold were studied. IR characterisation confirmed the integration of HA in composite scaffolds, while ATR confirmed the significant amount of HA present at the top surface of the scaffold, which was a primary objective. The SEM images confirmed the pores' interconnectivity. Increasing the content of HA up to 40% led to an improvement in mechanical properties, and the incorporation of nano-HA was more promising than that of micro-HA. Cell viability assays (using MG63) confirmed biocompatibility and CAM assays confirmed vascularization, demonstrating that HA enhances vascularization. These properties make the resulting biomaterials very useful for orbital floor repair and regeneration.

Microwave assisted synthesis and characterization of magnesium substituted calcium phosphate bioceramics.

Hydroxyapatite is used extensively in hard tissue repair due to its biocompatibility and similarity to biological apatite, the mineral component of bone. It differs subtly in composition from biological apatite which contains other ions such as magnesium, zinc, carbonate and silicon (believed to play biological roles). Traditional methods of hydroxyapatite synthesis are time consuming and require strict reaction parameter control. This paper outlines synthesis of magnesium substituted hydroxyapatite using simple microwave irradiation of precipitated suspensions. Microwave irradiation resulted in a drastic decrease in ageing times of amorphous apatitic phases. Time taken to synthesize hydroxyapatite (which remained stable upon heat treatment at 900°C for 1h) reduced twelve folds (to 2h) as compared to traditionally required times. The effects of increasing magnesium concentration in the precursors on particle size, surface area, phase-purity, agglomeration and thermal stability, were observed using scanning electron microscopy, BET surface area analysis, X-ray diffraction and photo acoustic Fourier transform infra-red spectroscopy. Porous agglomerates were obtained after a brief heat-treatment (1h) at 900°C.

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates.

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy.

Phase stability and rapid consolidation of hydroxyapatite-zirconia nano-coprecipitates made using continuous hydrothermal flow synthesis.

A rapid and continuous hydrothermal route for the synthesis of nano-sized hydroxyapatite rods co-precipitated with calcium-doped zirconia nanoparticles using a superheated water flow at 450°C and 24.1 MPa as a crystallizing medium is described. Hydroxyapatite and calcium-doped zirconia phases in the powder mixtures could be clearly identified based on particle size and morphology under transmission electron microscopy. Retention of a nanostructure after sintering is crucial to load-bearing applications of hydroxyapatite-based ceramics. Therefore, rapid consolidation of the co-precipitates was investigated using a spark plasma sintering furnace under a range of processing conditions. Samples nominally containing 5 and 10 wt% calcium-doped zirconia and hydroxyapatite made with Ca:P solution molar ratio 2.5 showed excellent thermal stability (investigated using in situ variable temperature X-ray diffraction) and were sintered via spark plasma sintering to >96% sintered densities at 1000°C resulting in hydroxyapatite and calcium-doped zirconia as the only two phases. Mechanical tests of spark plasma sintering sintered samples (containing 10 wt% calcium-doped zirconia) revealed a three-pt flexural strength of 107.7 MPa and Weibull modulus of 9.9. The complementary nature of the spark plasma sintering technique and continuous hydrothermal flow synthesis (which results in retention of a nanostructure even after sintering at elevated temperatures) was hence showcased.

High-strength nanograined and translucent hydroxyapatite monoliths via continuous hydrothermal synthesis and optimized spark plasma sintering.

The synthesis of high-strength, completely dense nanograined hydroxyapatite (bioceramic) monoliths is a challenge as high temperatures or long sintering times are often required. In this study, nanorods of hydroxyapatite (HA) and calcium-deficient HA (made using a novel continuous hydrothermal flow synthesis method) were consolidated using spark plasma sintering (SPS) up to full theoretical density in ∼5 min at temperatures up to 1000°C. After significant optimization of the SPS heating and loading cycles, fully dense HA discs were obtained which were translucent, suggesting very high densities. Significantly high three-point flexural strength values for such materials (up to 158 MPa) were measured. Freeze-fracturing of disks followed by scanning electron microscopy investigation revealed selected samples possessed sub-200 nm sized grains and no visible pores, suggesting they were fully dense.

Instant nano-hydroxyapatite: a continuous and rapid hydrothermal synthesis.

Nano-particle hydroxyapatite (HA) rods, were rapidly synthesised using a three pump continuous hydrothermal process (using a water feed at up to 400 degrees C and at 24 MPa): the product was obtained as a highly crystalline and phase pure material, without the need for an ageing step or subsequent heat treatment.