In this work we investigated the isomorphic substitution and thermal decomposition of sedimentary fluor apatite (FAp) (with Ca/P ratio [ 1.67) from Tunisia after high-energy-milling (HEM) activation at different times from 10 to 600 min. The chemical composition of the material includes: 29.6 % P 2 O 5 total and 46.5 % CaO (main components) and 3.5 % F; 0.55 % R 2 O 3 (R = Al, Fe); 1.1 % SO 3 ; 1.9 % SiO 2 (a low content in a comparison with other natural apatites from North Africa or Asia); 0.35 % MgO; 0.05 % Cl; 6.6 % CO 2 are impurities. HEM is a well-known approach for preparing various solid materials and for increasing their reactivity. The solid-state transformation of the initial and HEM-activated apatite samples was examined by chemical analysis, BET, powder XRD, FTIR spectroscopy, and thermal analysis. The structure of natural apatite allows isomorphic substitutions of carbonate, hydroxyl, and metal ions by PO 4 3-, Ca 2? , and F -. The obtained powder XRD data indicate an increased defectiveness of the apatite structure in the course of the HEM. The solid-state transformations of the initial and HEM-activated apatite are examined by TG-DTA analyses. It is found that the thermal stability of the activated samples decreases as compared to the initial sample. This is related to the increased defectivity of the apatite structure during the high-energy milling shown by the XRD data. The thermal analysis allows the differentiation of the structurally bonded A, B, and A-B types carbonate ions from these originating from the calcite and dolomite admixtures. The results obtained demonstrate that the mechanical distortion and the structural changes related to the migration of the carbonate ions from B type to A-type channel positions are the main factors responsible for the enhanced solubility of the high-energy activated FAp.

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This paper investigated thermal properties of natural thaumasite, such as phase composition and reaction mechanism of thermal decomposition using simultaneous TG/DTG-DSC in Ar and Air medium up to 1673 K, coupled with masspectrometer for analysis of evolving gases, and in-situ powder X-ray diffraction measurements. The transitional solid phases, grown with increasing of temperature at thaumasite thermal decomposition, are calcium hydrogen carbonate (Ca(HCO 3) 2) and hydrogen sulphate (Ca(HSO 4) 2), calcite, anhydrite, calcium silicates (wolastonite and larnite), calcium silico-carbonate (spurrite), and calcium silico-sulphate (ternesite). The thermal decomposition in both gaseous media includes the stages of dehydration, dehydroxylation, dacarbonation and desulphuration with obtaining a solid residue of varying degrees of crystallinity. The main solid phase, grown at the highest temperatures, is larnite. Based on the obtained results it was proposed the scheme of chemical reactions, which presents the reaction mechanism of thaumasite thermal decomposition. The defined scheme has both fundamental importance by adding new details of reference data, and practical application for thaumasite identification in chemical archaeology, and in the chemistry of cement and cement-based materials.

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