Comparison of Different Classical and Instrumental Analysis Methods for Precise Quantification of Calcium and Phosphorous Ratio in Hydroxyapatite
The largest comparison of analytical techniques, useful for calcium phosphates, has been conducted, presenting recommendations for quality control and research of calcium phosphates. Results from three classical quantification methods (gravimetry, titramety, photometry) and three instrumental measurement methods (XRF, FAAS ICP-OES) are reported to determine the most accurate, fastest and cheapest analysis method. Remarks are given for increasing the accuracy for each method and corrections made for adsorbed water. For routine analysis, a recommendation is given to ICP-OES for a fast analysis, together with a less frequent use of gravimetry to validate the results and provide a periodic cros…
Thermokinetic Investigation of the Drying Conditions on Amorphous Calcium Phosphate
The present work investigated dried calcium phosphate powders which still retain an amorphous or poorly crystalline structure under a variety of conditions. In previous studies, freeze-drying was found to be the optimum drying condition. However, several publications, as well as our previous studies, have shown that calcium phosphate amorphous, or a poorly crystalline structure, can retain their structure even if the samples are dried immediately after synthesis up to 200°C. In our study, we used the thermokinetic studies FTIR and XRD and showed that the samples are amorphous, or poorly crystalline, but were unable to answer the questions: Is there a difference between the differently dried…
The Antimicrobial Action of Silver Halides in Calcium Phosphate
Silver halides represent a yet unexplored avenue for imparting antimicrobial activity to calcium phosphates. Negtively charged silver halide colloids (AgI, AgBr and AgCl) were added to synthesized amorphous calcium phosphate. Concurrent melting of silver halides and crystallization to carbonated apatite at 700 oC increased the silver halide surface area available to bacteria and formed a lower solubility apatite. The effect of the matrix solubility on antimicrobial response could then be investigated. Pseudomonas aeruginosa was more sensitive to silver iodide and silver bromide than Staphylococcus aureus. Silver iodide demonstrated greater activity than silver bromide. Silver chloride did n…
Hydrothermal Processing for Increasing the Hydroxyl Ion Concentration in Hydroxyl Depleted Hydroxyapatite
Thermal spraying is commercially used to produce hydroxyapatite coatings, but the high temperature depletes hydroxyl ions in the structure. To return hydroxyapatite to its original state, it is necessary to restore the hydroxyl ion content in the structure. In this work, the effect of hydrothermal treatment on the hydroxyl ions was investigated in hydroxyapatite powder and thermally sprayed hydroxyapatite coatings. Samples were hydrothermally treated at 200 °C for 24 h and 48 h. Chemical phases were determined by X-ray diffraction, functional groups and hydroxyl ion concentration was examined by Fourier transform infra-red spectroscopy. Results showed that hydrothermal processing of hydroxy…
Crystallized nano-sized alpha-tricalcium phosphate from amorphous calcium phosphate: microstructure, cementation and cell response
New insight on the conversion of amorphous calcium phosphate (ACP) to nano-sized alpha tricalcium phosphate (α-TCP) provides a faster pathway to calcium phosphate bone cements. In this work, synthesized ACP powders were treated with either water or ethanol, dried, crystallized between 700 and 800 °C, and then cooled at different cooling rates. Particle size was measured in a scanning electron microscope, but crystallite size calculated by Rietveld analysis. Phase composition and bonding in the crystallized powder was assessed by x-ray diffraction and Fourier-transform infrared spectroscopy. Results showed that 50 nm sized α-TCP formed after crystallization of lyophilized powders. Water trea…
Formation of Calcium-Deficient Hydroxyapatite via Hydrolysis of Nano-Sized Pure Α-Tricalcium Phosphate
Nano-sized pure α-tricalcium phosphate (α-TCP) fabricated by a novel synthesis approach shows great potential for a faster transformation into calcium-deficient hydroxyapatite (CDHA) than conventionally prepared α-TCP. In this work, amorphous tricalcium phosphate precursors were precipitated and treated with a solvent (water or ethanol), and dried (freeze-dried and oven-dried) before heating at 775 °C. Nanosized α-TCP powders were investigated for their phase composition and crystallinity, particle shape and size, reactivity and cellular biocompatibility. Reaction with water showed faster CDHA formation for freeze-dried powder, at 6 hours, compared to ethanol treated powders, whereas a high…
Hydrothermally Synthesized Strontium Peroxyapatite
The current research focuses on peroxide ion incorporation in the structure of strontium hydroxyapatite (SrHAp) by exposure to H2O2 ina closed hydrothermal vessel under mild conditions at 130 to 170 °C. Peroxide enriched strontium apatite (SrPerAp) was characterized for structure by X-Ray diffraction, for peroxide content- by permanganometric titration and then viewed by SEM. This study continued from previous work that used 30%H2O2 and showed a higher included peroxide content after processing with 50% H2O2 at 130 °C 70% of the theoretical peroxide content in apatitic channels of strontium apatite. This is the highest peroxide content incorporated to date and employs a lower temperature th…
Charge State of Silver Halide Colloids Determines the Antibacterial Activity in Amorphous Calcium Phosphate
Removal of bacteria is important not only at implantation, but after long-term implant/prosthesis use. This requires strategies that employ different approaches for combating bacteria. Halides have the potential of an additional mechanism, and together with silver may provide a more powerful antibacterial strategy. Silver iodide was synthesized as colloids with a positive and negative charge and incorporated into an amorphous calcium phosphate (ACP) to provide a possible greater antibacterial action. Colloids were characterized by FTIR spectroscopy and the charge measured by zeta potential. Phase analysis by X-ray diffraction patterns confirmed the formation of b-AgI nanoparticles. Minimum …
Exploring Zinc Apatites through Different Synthesis Routes
nclusion of zinc in apatites is not completely understood due to complexes in solution preventing the incorporation or the inclusion of defects. Some work has shown zinc addition by alternative synthesis routes, but the level of incorporation has not been reassessed. This work uses a newly developed approach whereby zinc is included in an amorphous phase and subsequently crystallized. Different phosphate reactants (ammonium, sodium or potassium phosphates) were mixed together with calcium salts (calcium nitrate or calcium acetate) and the pH level adjusted (with ammonia or KOH) to investigate the ease of forming an amorphous phase and the inclusion of zinc. X-ray diffraction revealed that a…
Production and Characterization of Oxyhydroxyapatites
The amount and alignment of hydroxyl ions influence the bioactivity of hydroxyapatite. Hydroxyl ions in hydroxyapatite are the most mobile and upon heating are the first to leave the lattice to form oxyhydroxyapatite. This work describes a method for producing hydroxyapatite with different amounts of hydroxyl ions, and reports on the changes in Fourier transform infrared absorption at increasing level of dehydroxylation. Detailed analysis of spectra in the 500 – 700 cm-1 range showed a peak shift for the hydroxyl ion absorption line at 632 cm-1 to 637 cm-1 and an increase in the wavenumber for the phosphate line at 575 cm-1.
Synthesis of Peroxyapatite by Hydrothermal Processing
Peroxide ions in apatite provides an additional resource for imparting an antibacterial capability in apatite. A hydrothermal process has been developed for including peroxide ions into the apatite lattice. Three oxygen generation compounds, hydrogen peroxide, ammonium persulphate and paracetic acid were investigated for peroxyapatite generation. Hydrogen peroxide provides the highest peroxide containing apatite. Both the oxygen generation and the apatite lattice formation represented the two critical factors for producing peroxyapatite. Unlike with high temperature processing, the cooling rate did not influence the retained peroxide content. This new process provides a building block for i…