J P Gittings

Electrical characterization of hydroxyapatite-based bioceramics.

This paper studies the AC conductivity and permittivity of hydroxyapatite (HA)-based ceramics from 0.1 Hz-1 MHz at temperatures from room temperature to 1000 degrees C. HA-based ceramics were prepared either as dense ceramics or in porous form with interconnected porosity and were sintered in either air or water vapour. Samples were thermally cycled to examine the influence of water desorption on AC conductivity and permittivity. Surface-bound water was thought to contribute to conductivity for both dense and porous materials at temperatures below 200 degrees C. At temperatures below 700 degrees C the permittivity and AC conductivity of HA was also influenced by the degree of dehydration and thermal history. At higher temperatures (700-1000 degrees C), bulk ionic conduction was dominant and activation energies were of the order of approximately 2 eV, indicating that hydroxyl ions are responsible for conductivity.

Polarization of hydroxyapatite:Influence on osteoblast cell proliferation

Hydroxyapatite (HA) has been used clinically to treat bone defects. However, modifications of the surface properties of HA could improve and control bone matrix deposition and localized host tissue integration. The aim of this study was to investigate the effect of developing a surface charge on HA discs with respect to osteoblast activity in vitro. HA discs (12 mm x 2 mm) were sintered in either air or water vapour. The HA discs were then electrically polarized (positive and negative surfaces) or non-polarized (controls) and seeded with MC3T3-E1 cells. Polarized HA sintered in water vapour was shown to retain six times more charge than polarized HA sintered in air. Picogreen analysis demonstrated that at 4h cell number was significantly higher on the negatively and positively charged HA surface (water sintered) in comparison to the non-charged water and air-sintered HA controls. At 7 days there was a significant increase in cell number on the negatively charged HA (air sintered) sample in comparison to the negatively charged water vapour sintered HA sample and the non-charged water vapour sintered control sample. Also at 7 days, the picogreen data showed a significant increase in cell number on the positively charged water-treated HA sample in comparison to both the air- and water-treated HA non-charged control HA samples. An alamarBlue assay at 7 days demonstrated significant cell metabolic activity on the charged surfaces (both positive and negative) in comparison to the non-charged HA and the tissue culture plastic controls. This study demonstrated that all of the HA discs tested supported cell viability/attachment. However, cell attachment/proliferation/metabolic activity was significantly increased as a result of developing a charge on the HA surface.

Polarisation Behaviour of Calcium Phosphate Based Ceramics

This paper studies the effects of porosity, sintering atmosphere and composition on the polarisation behaviour of calcium phosphate (CaP) ceramics. Hydroxyapatite (HA) and α- tricalcium phosphate (α-TCP) materials were prepared as both dense discs and as porous samples with interconnecting porosity. Materials were sintered in either air or water vapour at 1300°C and poled at a variety of temperatures, applied electric fields and time periods to optimise the polarisation properties of the materials. Thermally Stimulated Depolarisation Current (TSDC) measurements were used to investigate the degree of polarisation of the HA and α-TCP ceramics. A high depolarisation current was observed for both the porous HA and α-TCP ceramics. Sintering in water vapour also increased the depolarisation current due to reduced dehydration reactions, which result in a greater concentration of hydroxyl ions.

Polarization of porous hydroxyapatite scaffolds: Influence on osteoblast cell proliferation and extracellular matrix production

Improvements to clinically used biomaterials such as hydroxyapatite (HA) are of potential benefit to the patient. One modification, the addition of surface charges, has been shown to have an important role influencing cell response. In this study, porous HA scaffolds with both positive and negative surface charges were manufactured. The samples were sintered in air to produce porous HA ceramic scaffolds in the form of cylinders 12 mm in height × 7 mm in diameter. These were polarized with a dc voltage of 3 kV/cm. MC3T3E1 cells were placed on either negative or positive ends of the charged (or unpoled control) HA scaffolds. At 7 days, picogreen analysis was performed to analyze the cell number at the negative (4 mm), central (4 mm), and positive (4 mm) portions of the 12 mm cylindrical scaffold. At 4 weeks, micro-CT analysis was performed to quantify the regional volume of mineralized matrix deposition on the 3D scaffold. At 7 days, there were significantly more cells present at the negative end of the scaffold when seeded from the negative end in comparison to the other samples tested. Micro-CT data at 4 weeks correlated with this finding, demonstrating an increase in mineralized matrix at the negatively charged end of the scaffold seeded from the negative end in comparison to the positively charged and unpoled control scaffolds. The results indicate that the charge on HA influences cell activity and that this phenomenon can be translated to a clinically relevant porous scaffold structure.

Calcium Phosphate Open Porous Scaffold Bioceramics

Calcium phosphate (CaP) ceramics possessing an interconnecting porosity network in the appropriate size range for vascularisation offer the possibility of providing a structural matrix for replacement of diseased or damaged bone. Such bioceramics must possess sufficient mechanical strength to avoid failure whilst offering a bioactive surface for bone regeneration. The objective of the current study was to produce a hydroxyapatite/tricalcium phosphate (HA/TCP) bioceramic that imitated the orientated trabecular structure found in cancellous bone. The structure-property relationship of these bioceramics was then analysed. It was hypothesised that the mechanical properties would be linked to the shape of the pore structure due to the orientation of the open porous scaffolds (OPS) produced. OPS bioceramics possessed an interconnected macroporosity network of 40-70% by volume with bending strengths of 0.30MPa ± 0.01MPa and apparent densities of 0.35g/cm3 ± 0.05g/cm3. Typically, pore sizes in the range of 150-300µm were produced. The fabrication of CaP OPS resulted in a wide range of macroporosity in the correct size range for osseointegration to occur. Elongating the pore structure did not affect the total porosity of the bioceramics. Strengths were low due to microcrack formation on sintering and not due to the shape of the pores present in the scaffold as initially hypothesised.

Influence of Porosity on Polarisation and Electrical Properties of Hydroxyapatite Based Ceramics

This paper studies the effect of porosity on the electrical properties and polarisation behaviour of hydroxyapatite based ceramics prepared in both dense and porous form. Porosity was introduced into the hydroxyapatite using either burnt-out polymer spheres to produce isolated pores or using polymer foams to create interconnected porosity. The samples were sintered in water vapour at 1300°C and polarised at 400°C with a dc voltage of 3kV/cm applied for 1 hour. Thermally stimulated depolarisation current measurements were used to investigate the degree of polarisation of the hydroxyapatite ceramics and dielectric spectroscopy used to measure the ac conductivity of the materials at the polarisation temperature. The porous materials were successfully polarised and the presence of a high surface area to volume ratio in the porous samples was thought to increase the level of polarisation.

The structure and properties of electroceramics for bone graft substitution

Hydroxyapatite (HA) and barium titanate (BT) powders were mixed and sintered to form hydroxyapatite – barium titanate (HABT) ceramics. These materials were then poled and their piezoelectric properties were measured. The microstructure of unpoled samples was examined using scanning electron microscopy (SEM).The piezoelectric constants (d33 and d31) of the ceramics were found to be dependent on the proportion of BT in the ceramic In materials containing less than 70% BT, no piezoelectric effect was found. Above this value, the piezoelectric constant increased with the addition of BT up to a value of 108pCN-1 for pure BT. Values of d33 for ceramics containing more than 80% BT are above values previously shown to have a positive influence on bone growth in vivo. SEM analysis indicated that the grain size within the materials decreased as the proportion of BT in the material was reduced. Examination of the microstructure of the ceramics indicated the presence of electrical domains in the 100% BT and 95% BT ceramics. Domains were not visible below 95% BT. The reduction in grain size may influence the reduction in piezoelectric activity within the materials but cannot be considered to be the only cause.