Mechanism of calcium phosphates precipitation in liquid crystals

The possibility of using as a precursor an easily wet meso-porous powder would be a breakthrough in the preparation of nuclear waste storage ceramics. A concentrated solution containing ions to be stored would wet a dry powder and then, subjected to mild compression, lead to a micro-crystalline matrix of calcium phosphate at acceptable temperatures. Since no porous calcium phosphate different from calcined bone (patented) is described as porous precursor, we have compared the different synthesis routes towards meso-porous ceramics. First, we considered homogeneous precipitation of slats in water: using initially off-stoichiometry in reaction, micron-sized hydroxyapatite particles are produced with a specific surface up to 100 m2/g. Then, we consider the classical route of precipitation of an hybrid material in the miscibility gap of a phase diagram, when an hexagonal liquid crystal is used a matrix for precipitation. The surfactant family consists in single chain surfactants containing phosphates as head-group to poison the growing surface of calcium phosphate nano-domains. Since the reaction is still too brutal, we considered using a cat-anionic precursor material of controllable surface charge. For certain concentrations and molar ratios, a new structure not yet described in surfactant precipitation literature is observed: since the periodicity is lower than twice the chain length, a disordered constant curvature monolayer (instead of the classical cylinder of twice chain length diameter) of surfactant is implied. Finally, we have investigated synthesis routes implying slow dissolution of pre-formed calcium phosphate in an already existing hexagonal matrix. For all these routes of synthesis, micro-structural determinations using SAXS, WARS and BET are performed, with a special attention to comparison of the precipitation material, the matrix obtained with all elements present, and also the material obtained after calcinations. (authors)