Cristallogenèse exploratoire, structure cristalline et propriétés physiques des deux nouveaux composés dans le système PbO-Fe2O3-P2O5

摘要

A new oxyphosphate compound PbFe3O(PO4)3 has been discovered. Its crystal structure was characterized by single crystal X-ray diffraction (XRD) between 293 and 973 K (monoclinic symmetry P 21/m, a = 7.5826 Å, b = 6.3759 Å, c = 10.4245 Å and  = 99.956 °, Z = 2, at room temperature). DC magnetic susceptibility and specific heat measurements performed on single crystals unveiled an unusual sequence of second order ferromagnetic-like phase transitions at Tc1 = 31.8 K, T2 = 23.4 K and Tc3 ~ 10 K. AC magnetic susceptibility suggests a glassy-like dynamics between ~ 20 K and Tc3. A first extraction of the critical exponents (β,γ,δ) was performed by ac magnetic susceptibility in both PbFe3O(PO4)3 powders and single crystals and the values were found to be consistent with mean-field theory.AFe3O(PO4)3 (A= Ca, Sr and Pb) powder compounds were studied by means of X-Ray diffraction (XRD), from 300 to 6 K in the case of A=Pb, electron-probe microanalysis (EPMA) coupled with wavelength dispersion spectroscopy (WDS), Raman and diffuse reflectance spectroscopies, specific heat and magnetic properties measurements. Magnetization, magnetic susceptibility and specific heat measurements carried out on AFe3O(PO4)3 (A= Ca, Sr and Pb) powders firmly establish a series of three ferromagnetic (FM)-like second order phase transitions spanned over the 32 – 8 K temperature range. Diffuse reflectance measurements reveal two broad absorption bands at 1047 and 837 nm, in both PbFe3O(PO4)3 and SrFe3O(PO4)3 powders, with peak cross sections ~10-20 cm2 typical of spin-forbidden and forced electric dipole transitions.Further exploration of the PbO-Fe2O3-P2O5 system led to the discovery of a new langbeinite phase, Pb3Fe4(PO4)6, the crystal structure of which was solved by room temperature single crystal XRD (P 21 3, Z=4, a=9,7831(2) Å). This phase does not undergo any structural phase transition down to 6 K nor any kind of long range ordering down to 2 K.