RESUMO
The interaction of TiN with Na2O-K2O-P2O5 melts was investigated at (Na+K)/P molar ratios of 0.9, 1.0, and 1.2 and at Na/K molar ratios of 1.0 and 2.0. Interactions in the system led to the loss of nitrogen and the partial loss of phosphorus and resulted in the formation of KTiP2O7 and langbeinite-type K2-x Na x Ti2(PO4)3 (x=0.22-0.26) solid solutions over the temperature range of 1173 to 1053â K. The phase compositions of the obtained samples were determined by using X-ray diffraction (including Rietveld refinement), scanning electron microscopy (using energy-dispersive X-ray spectroscopy and element mapping), FTIR spectroscopy, and thermogravimetric analysis/differential thermal analysis. K1.75Na0.25Ti2(PO4)3 was characterized by single-crystal X-ray diffraction [P213 space group, a=9.851(5)â Å]. The 3D framework is built up by TiO6 octahedra and PO4 tetrahedra sharing all the oxygen vertices with the formation of cavities occupied by K(Na) cations. Only one of the two crystallographically inequivalent potassium sites is partially substituted by sodium, and this was confirmed by calculating the bond-valence sum. The thermodynamic stability of K1.75Na0.25Ti2(PO4)3 crystals and the preferable occupation sites of NaK cationic substitutions were investigated by DFT-based electronic structure calculations performed by the plane-wave pseudopotential method.
RESUMO
A series of complexes Ln(Pip)3(Phen) (Ln(iii) = La, Ce-Nd, Sm-Lu, Y; HPip (CAPh type ligand) = 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, Phen = 1,10-phenanthroline) has been synthesized. The lanthanum(iii) doped europium(iii) complexes ([LaxEu1-x(Pip)3(Phen)], x = 0.99, 0.95, 0.50) have been obtained by the co-crystallization method. The complexes have been characterized by means of X-ray diffraction, IR, (1)H and (31)P-NMR and absorption spectroscopy. Emission and excitation luminescence spectra were recorded at 295 and 77 K. The lifetime values (τ) for the emission of all europium complexes were determined. The (5)D0 luminescence quantum efficiency is 73-89%. The symmetries of the nearest europium surrounding in pure and doped complexes were evaluated from the Stark splitting of (5)D0-(7)FJ transitions. Crystal structures of [Ln(Pip)3(Phen)] (Ln = Nd (1), Eu (2) and Tb (3)) have been determined. Lattice parameters of the [Ln(Pip)3(Phen)] (Ln = Tb, Yb) and the doped [LaxEu1-x(Pip)3(Phen)] (x = 0.99, 0.95, 0.50) complexes have been measured. The presence of four polymorphs within a number of rare earth elements has been estimated: two in triclinic (Ln1 = La, Nd; Ln2 = Eu), one in the monoclinic (Ln3 = Tb) and one in the rhombic (Ln4 = Tb, Yb) symmetry. Complex 3 can be obtained in two crystal modifications: monoclinic and orthorhombic ones.
RESUMO
The work deals with the problem of determination of automobile petrol of various octane numbers and petroleum contamination of some objects on the basis of analysis of photoluminescence spectra of automobile petrol samples. For this purpose steady state luminescence properties of samples of automobile petrol of different types being in sale were measured. Samples of automobile petrol diluted in hexane were prepared and their luminescence spectra were measured at room and liquid nitrogen temperatures of samples. We constructed concentration dependences of luminescence intensity of both wide band luminescence of liquid solutions obtained at room temperature and peak intensities of luminescence lines of quasi linear spectra of solutions frozen at 77 K. Possibility to use luminescence method for analysis of petrol pollutions on some objects is illustrated by results of investigation of pine-wood pieces contaminated by automobile petrol.
