Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to study the porous and non-porous alpha-tricalcium phosphate (alpha-Ca-3(PO4)(2), alpha-TCP) prepared through a sintering procedure at 1200-1400 degrees C of beta-tricalcium phosphate (beta-Ca-3(PO4)(2), beta-TCP). The interpretation of experimental and calculated X-ray and electron diffraction patterns showed that the final product at 1400 degrees C was primarily alpha-TCP but roughly 3.0-8.0 wt.% of the starting beta-TCP phase and up to 8.0 wt.% of CaO were in the final product. TEM images and electron diffraction patterns showed that the CaO phase - formed by decomposition of TCP - exists as micron-sized areas of various oriented nanocrystals embedded into the bulk alpha-TCP material and also as self-standing spherulite particles of a few microns in size. Surprisingly, formation of CaO from TCP decomposition occurred at temperatures below those predicted from the phase diagram of the CaO-P2O5 system. (C) 2009 Elsevier Ltd. All rights reserved.