Rietveld refinements and spectroscopic structural studies of a Na-free carbonate apatite made by hydrolysis of monetite.

Seven nominally identical samples of Na-free carbonate apatite (CO(3)Ap) were prepared by reaction of CaHPO(4) with ammonium carbonate solution at 70 degrees C over 3 days. They were studied by chemical analysis, Rietveld analysis of powder X-ray diffraction (XRD) data, Ca/P ratio determinations (quantitative phase analysis of CaO, Ca(OH)(2) and hydroxyapatite formed after heating to 900 degrees C from Rietveld analysis of XRD data), He pycknometry, (1)H, (13)C and (31)P MAS NMR spectrometry and Fourier transform infrared and Raman spectroscopy. Spectroscopy showed the apatite products were B-type CO(3)Aps (CO(3)(2-) replacing PO(4)(3-)) and XRD that one sample contained 1.6 wt% calcite with a trace in another. Mean results of the six essentially calcite-free samples were: a=9.405(5)A, c=6.896(2)A; 11.2 wt% CO(3); unit cell contents, Ca(8.241)(PO(4))(4.344)(CO(3))(1.656)(OH)(0.139) x 2.29H(2)O; mole Ca/P ratio from chemical analyses, 1.897(22) and from powder XRD phase analysis of samples decarbonated at 900 degrees C, 1.892(25). Density determinations indicated that the 2.29mol of H(2)O were in the unit cell. Rietveld refinements were undertaken without and with explicit modelling of the CO(3)(2-) ion. The latter used constraints to maintain the CO(3)(2-) ion in its known geometry and the total of PO(4)(3-) and CO(3)(2-) ions per unit cell at six. Without the CO(3)(2-) ion in the model, PO(4) volume, P-O bond lengths and P occupancy were apparently reduced, consistent with CO(3)(2-) replacing PO(4)(3-) ions. With the CO(3)(2-) ion modelled, the reductions were less and the CO(3)(2-) ion occupied the "sloping" face of the replaced PO(4)(3-) ion in two-fold disorder about the mirror plane. The angle between the normal to the plane of the ion and the c-axis was 34 degrees , close to 35.3 degrees , the equivalent angle for the PO(4)(3-) ion. When modelled, the CO(3)(2-) ion occupancy was 1.81 ions per unit cell, in reasonable agreement with unit cell contents determined chemically (1.66). The OH(-) ion occupancy was elevated (2.33 ions per unit cell versus 0.14 inferred from the charge balance), which we ascribe to H(2)O molecules occupying sites in c-axis channels. The Ca/P ratio from occupancies (2.31) was also elevated over that determined chemically (1.90). We attribute this to loss of Ca from Ca sites increasing the apparent anisotropic displacement parameters of remaining Ca atoms, leading to an apparently increased occupancy.

Three-dimensional study of human dental fissure enamel by synchrotron X-ray microtomography.

The three-dimensional morphology of human tooth fissures and the quantification of mineral distribution in fissure enamel are pertinent to the development and diagnosis of caries. Synchrotron X-ray microtomography was used to measure linear attenuation coefficients (at 25 keV) at high spatial resolution with a volume-imaging element (cubic voxel) of 4.9x4.9x4.9 microm3 in a block from a human premolar that included part of a stained fissure. From the linear attenuation coefficient, the mineral concentration, expressed as gHAp cm-3 (where HAp is stoichiometric hydroxyapatite), was calculated. The mean mineral concentration in bulk enamel was 2.84 gHAp cm-3. Well-defined regions (1.5-2.6 gHAp cm-3), extending up to approximately 130 microm from the base of some narrower lengths of the fissure and up to approximately 50 microm deep from the fissure surface, were attributed to hypomineralization. Other regions of low mineral concentration, some (1.4-2.3 gHAp cm-3) lying within the expected course of the fissure base and some (2.2-2.7 gHAp cm-3) deep to the pit, were also considered to be of developmental origin. However, a diffuse distribution of low mineral concentrations (2.2-2.7 gHAp cm-3) in the pit walls was attributed primarily to demineralization from caries. The fissure contained heterogeneous material (

Scanning microradiographic study on the influence of diffusion in the external liquid on the rate of demineralization in hydroxyapatite aggregates.

Subsurface demineralization in enamel caries is known to entail diffusion of reagents and products both within the lesion and within the plaque biofilm external to the lesion. However, development of a predictive mathematical model for subsurface demineralization is hindered by limited quantitative understanding of the effects of these diffusion processes. The purpose of this quantitative study was to investigate and understand the effect of external diffusion length on the rate of demineralization in a simple model system. Ten, 500-microm thick sections cut from a porous hydroxyapatite (HAP) pellet were inserted in scanning microradiography (SMR) cells. The exposed thin edges of the sections were initially separated by columns of water (diffusion lengths) of 0-0.9 cm from a 1-l reservoir of demineralizing buffer (pH 4). Buffer was found to diffuse from the reservoir through the increasing diffusion lengths to the exposed HAP surface, whilst dissolved product diffused along the reverse path. Rates of HAP loss (from SMR measurements) decreased as the diffusion length increased. Experimental data were fitted to a general diffusion-reaction model. This showed that the solution near the HAP surface was almost completely saturated with HAP, and that the diffusion of dissolution products, rather than of buffer species, was rate limiting.

Rietveld refinements and spectroscopic studies of the structure of Ca-deficient apatite.

Nine samples of Ca-deficient apatite (Ca-def Ap) were prepared from suspensions of CaHPO4 (monetite) at 90 degrees C by raising the pH from approximately 4 through release of NH3 produced by the hydrolysis of urea. Products were dried at 100 degrees C for 24h and studied by chemical analyses, X-ray powder diffraction (XRPD) (and Rietveld analysis of this data), Ca/P ratio determination (quantitative phase analysis of samples after heating to 900 degrees C from Rietveld analysis of XRPD data), scanning electron microscopy, He pycknometry, 1H and 31P MAS NMR spectrometry and Fourier transform infrared and Raman spectroscopy. All samples contained apatite, but three also contained monetite. Infrared and Raman spectroscopy confirmed the presence of HPO4(2-) and absence of carbonate ions in the six monetite-free samples. Mean results for the six samples were: a = 9.4320(40), c = 6.8751(31) A; unit cell formula from chemical analysis neglecting protonation of phosphate ion, Ca(9.303(50))(PO4)6(OH)(0.606(99)).1.97(12)H2O; theoretical density 3.10 g cm(-3); experimental density (mean for three samples) 3.15 g cm(-3); and Ca/P mole ratio from chemical analysis and phase analysis after heating to 900 degrees C, 1.550(8) and 1.550(2), respectively. An earlier assignment of a line at 6 ppm in the 1H NMR spectrum of similar samples to HPO4(2-) ions could not be confirmed; hence no information about the HPO4(2-) ion content could be derived, in disagreement with the previous NMR study. A shoulder at approximately 0.9 ppm relative to 85 wt% H3PO4 in the 31P NMR spectrum was assigned to HPO4(2-) ions. Occupancies from the Rietveld structure refinements indicated preferential loss of Ca from Ca2 sites compared with Ca1, but the loss was substantially smaller than expected from chemical analyses. It is suggested that imperfect modelling of the structure in the refinement, particularly disorder associated with the Ca2 site, resulted in errors in Ca2 occupancies. The P-O bonds were slightly shorter than those in stoichiometric hydroxyapatite, rather than longer as might be expected from protonation of phosphate tetrahedra. However, consideration of known acid phosphate structures indicated that it was unlikely that the increase in P-O lengths would be sufficient to be detected. The observed decrease was tentatively assigned to the presence of Ca2+ ion vacancies.

Rietveld structure refinement of precipitated carbonate apatite using neutron diffraction data.

X-ray and time of flight neutron diffraction data, FTIR and MAS-NMR spectra, and ICP-AES and carbonate analyses have been collected from a sodium-containing carbonate apatite (CO(3) content 12.5(7)wt%). A structural model based on Holly Springs hydroxyapatite without CO(3)(2-) ions showed an apparent reduction in the PO(4) tetrahedral volume which is ascribed to CO(3)(2-) replacing PO(4)(3-) ions in the lattice. Four structural models from the literature with the CO(3)(2-) ion explicitly modelled were fitted to the neutron diffraction data by the Rietveld method. The best fit was obtained with the CO(3)(2-) ion in disorder between the mirror symmetry related faces of a vacant PO(4)(3-) site and with the normal to the plane of the CO(3)(2-) ion at approximately 30 degrees to the c-axis. This angle is consistent with results from previous polarised IR measurements on single crystals of francolite (a fluorocarbonate apatite) and human dental enamel. Further refinement of the model revealed a hitherto unknown atom site close to the unit cell origin, (possibly a water molecule). The refined hexagonal unit cell parameters from the neutron diffraction data were a=9.3446(3)A and c=6.9199(4)A.