Molecular interactions in hydroxyapatite (HAP) polymer composites have been studied using photoacoustic spectroscopy. HAP is mineralized by wet precipitation under two conditions: first is in the absence of polyacrylic acid (PAAc) (ex-situ HAP) and second in the presence of PAAc (in-situ HAP). Porous and solid composites of ex-situ and in-situ HAP with polycaprolactone (PCL) have also been made to evaluate their applicability as bone scaffolds. Photoacoustic Fourier transform infrared (PA-FTIR) spectroscopy studies indicate that both in-situ and ex-situ HAP have HPO4 (2-) in their structure, which leads to Ca2+ deficiency. During crystallization of in-situ HAP, PAAc dissociates to form carboxylate ions, which binds to calcium ions and act as suitable site for nucleation for HAP crystallization. PA-FTIR spectra of porous and solid composites indicate that porous composites adsorb more water, which is hydrogen bonded with carbonyl of PCL. Mechanical tests on solid samples indicate that ex-situ HAP/PCL composites have higher elastic modulus than in-situ HAP/PCL composites. However, in case of porous composites, in-situ HAP/PCL composites are found to have higher elastic modulus. In-situ HAP is chemically and structurally different from ex-situ HAP. This modified HAP causes variation in microstructure of porous composite and hence alteration of its load transfer mechanisms and hence mechanical properties.
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