Juergen Neubauer

Refined ettringite (Ca6Al2(SO4)3(OH)12∙26H2O) structure for quantitative X-ray diffraction analysis

A revised structure model of ettringite is presented, in order to provide quantitative X-ray diffraction (QXRD) of this mineral in cement pastes. The model is derived from two different existing structure models, both of which are suitable for restricted use but are inferior to the refined ettringite structure presented. In the first published ettringite structure proposed by Moore and Taylor [Acta Crystallogr. B 26, 386–393 (1970)], none of the 128 positions for H are given in the unit cell, which results in reduced scattering power for use of this model for quantification purposes. For the precise quantification of ettringite in samples together with anhydrous phases, the scattering factors of all atoms including the H positions are indispensable. The revised structure model is based on the data of Moore and Taylor, supplemented by the H positions determined by Berliner (Material Science of Concrete Special Volume, The Sydney Diamond Symposium, American Ceramic, Society, 1998, pp. 127–141) on the basis of a neutron diffraction structural investigation of deuterated ettringite at 20 K. Berliner’s (Material Science of Concrete Special Volume, The Sydney Diamond Symposium, American Ceramic Society, 1998, pp. 127–141) thermal parameter should not, however, be used, since a normal application is at room temperature. In order further to improve the structure model of ettringite, Rietveld refinement with the rigid body approach for OH and H 2 O molecules and SO 4 tetrahedra was employed. The refined and improved ettringite structure model was tested for quantitative phase analysis by the determination of actual ettringite contents in mixtures with an internal standard. Synthesized and orientation-free prepared ettringite powders were investigated by X-ray powder diffraction analysis and quantified in four different blends with zircon. The quantification results with the new structure model demonstrate the superior quality of the revised ettringite structure.

Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite

Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA.

Calorimetry investigations of milled α-tricalcium phosphate (α-TCP) powders to determine the formation enthalpies of α-TCP and X-ray amorphous tricalcium phosphate.

One α-tricalcium phosphate (α-TCP) powder was either calcined at 500°C to obtain fully crystalline α-TCP or milled for different durations to obtain α-TCP powders containing various amounts of X-ray amorphous tricalcium phosphate (ATCP). These powders containing between 0 and 71wt.% ATCP and up to 2.0±0.1wt.% β-TCP as minor phase were then hydrated in 0.1M Na2HPO4 aqueous solution and the resulting heat flows were measured by isothermal calorimetry. Additionally, the evolution of the phase composition during hydration was determined by in situ XRD combined with the G-factor method, an external standard method which facilitates the indirect quantification of amorphous phases. Maximum ATCP hydration was reached after about 1h, while that of crystalline α-TCP hydration occurred between 4 and 11h, depending on the ATCP content. An enthalpy of formation of -4065±6kJ/mol (T=23°C) was calculated for ATCP (Ca3(PO4)2), while for crystalline α-TCP (α-Ca3(PO4)2) a value of -4113±6kJ/mol (T=23°C) was determined.

Hydration enthalpy of amorphous tricalcium phosphate resulting from partially amorphization of β-tricalcium phosphate

Abstract As it was recently shown that β-tricalcium phosphate (β-TCP), similar to α-TCP, can be mechanically activated by prolonged ball milling, partially amorphized β-TCP is promising for the development of new bone cement formulations. Hence in the present study the hydration of partially amorphized β-TCP with different contents of an amorphous phase (amorphous tricalcium phosphate, ATCP) was investigated by isothermal calorimetry and quantitative X-ray diffraction (XRD) to obtain the hydration enthalpies of β-TCP and ATCP. Measurements were conducted at 23 °C, a 0.1 M Na2HPO4 aqueous solution was used as mixing liquid. For the hydration enthalpy of crystalline β-TCP, a value of ΔHR(β-TCP → CDHA) = −23.9 kJ/molTCP can be calculated from literature data. In this study ΔHR(ATCP → CDHA) = −83 ± 6 kJ/molTCP was determined from new measurement results for the hydration of amorphized β-TCP to calcium-deficient hydroxyapatite (CDHA). Hence the hydration enthalpy was shown to be increased by a factor of 3.5 due to amorphization. Additionally, the hydration enthalpy of ATCP resulting from amorphization of β-TCP was compared and demonstrated to be not significantly different to that of ATCP resulting from α-TCP amorphization, which was −78 ± 2 kJ/molTCP. This indicates that amorphization of α-TCP and β-TCP results in an amorphous phase with the same properties.