ABSTRACT Ion mobility in solid solutions of the fluorite structure 50Pb2–30BiF3–20KF (I) and 50Pb2–30BiF3–20NaF (II) was studied by NMR method. Analysis of 19F, 23Na NMR spectra made it possible to reveal the character of ion motions in the fluoride and sodium sublattices with temperature variation, to determine the types and temperature ranges in which they took place. It was found that the dominant form of ionic mobility in the samples I and II above 380 K was the diffusion of fluoride and sodium ions. According to preliminary results of electro-physical studies, the conductivity reached values of ~ 2×10–2 – 10–3 S/cm above 500 K. The solid solutions I and II can be recommended as a basis for use in the development of new functional materials.
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V. Kavun, A. Slobodyuk, I. Telin, R. Yaroshenko, I. Maslennikova, V. Goncharuk and V. Kharchenko, "Ion Mobility in the Fluorite Solid Solutions 50PbF2–30BiF3–20K(Na)F According to 19F, 23Na NMR Data," Advances in Materials Physics and Chemistry, Vol. 2 No. 4, 2012, pp. 71-73. doi: 10.4236/ampc.2012.24B020.
 R. Hagenmuller, J.M. Reau, C. Lucat., S. Matar, G. Villeneuve, “Ionic-conductivity of fluorite-type fluorides,” Solid State Ionics, vol. 3–4, pp. 341–345, August 1981.
 J.M. Reau, P. Hagenmuller, “Fast ionic conductivity of fluorine anions with fluorite- or tysonite-type structures,” Rev. Inorg. Chem., vol. 19, No. 1-2, pp. 45–77, January-June 1999.
 P. Berastegui, S. Hull, “Structure and conductivity of some fluoride ion conductors,” Solid State Ionics, vol. 154–155, pp. 605–608, December 2002.
 V. Trnovcova, P.P. Fedorov, I. Furar, “Fluoride solid electrolytes,” Rus. J. Electrochem., vol. 45, No. 6, pp. 630-639, June 2009.
 N.I. Sorokin, P.P. Fedorov, B.P. Sobolev, “Superionic materials based on lead fluoride,” Inorg. Mater., vol. 33, No. 1, pp. 1-11, January 1997.
 C. Lucat, A. Rhandour, J.M. Reau, J. Portier, P. Hagenmuller, “Fast ionic conduction of fluorides with the fluorite-type structure,” J. Solid State Chem., vol. 29, pp. 373 – 377, September 1979.
 S. Matar, J.M. Reau, C. Lucat, J. Grannec, P. Hagenmuller, “Synthese et etude des proprietes de conductivite ionique des phases appartenant aux systemes KBiF4 - BiF3 et RbBiF4 - BiF3,” Mater. Res. Bull., vol. 15, pp. 1295–1301, September 1980.
 C. Lucat, J. Portier, J.M. Reau, P. Hagenmuller, J.L. Soubeyroux, “Etude par diffraction de neutrons de la solution solide Pb1-xBixF2+x: Correlations entre structure et conductivity ionique,” J. Solid State Chem., vol. 32., No. 3, pp. 279 – 287, May 1980.
 P. Darbon, J.M. Reau, P. Hagenmuller, “Evolution des proprietes de transport des solutions solides M1-xM'xF2+x (M = Sr, Pb; M' = Sb, Bi) et M1-xM''xF2+2x (M'' = Zr, Th) pour les faibles taux de substitution,” Solid State Ionics, vol. 2, No. 2, pp. 131 – 138, April 1981.
 Y. Ito, K. Koto, S. Yoshikado, T. Ohachi, “Anion disorder and its resulting ionic conductivity of [beta]-Pb1-xBixF2+x (x ≤ 0.30) and [beta]-Pb1-xYxF2+x,” Solid State Ionics, vol. 18–19, pp. 1202 – 1207, January 1986.
 M.W. Shafer, G.V. Chandrashekhar, “Fluoride ion conductivity - composition relationships in the fluorite phase region of the KF–BiF3 system,” Solid State Ionics, vol. 5, pp. 629–632, October 1981.
 S. Matar, J.M. Reau, J. Grannec, L. Rabardel, “On a low-temperature form of KBiF4,“ J. Solid State Chem., vol. 50, pp. 1–6, November 1983.
 G.V. Zimina, P.P. Fedorov, A.Yu. Zamanskaya, B.P. Sobolev, “Solid-phase reaction in the BiF3-KF system,” J. Inorg. Chem., vol. 29, No. 5, pp. 1300 – 1304, May 1984.
 E.N. Novikova, P.P. Fedorov, G.V. Zimina, et al., “Structural diagram and conductivity of phases in the NaF-BiF3 system,” J. Inorg. Chem., vol. 26, No. 3, pp. 774–777, March 1981.
 J. Senegas, C. Chartier, J. Grannec, “NMR-Study of diffuse phenomena in the phases of the NaF–BiF3 system,” J. Solid State Chem., vol. 49, No. 1, pp. 99–106, August 1983.
 M. El Omari, E. Hafidi, M. El Omari, A. Abaouz, A. Yacoubi, J.M. Reau, J. Senegas, “Short-range order and diffusion processes in the Na1?xBixF1+2x anion-excess solid solution,” Mater. Let., vol. 53, pp. 138–144, March 2002.
 V.Ya. Kavun, N.F. Uvarov, A.S. Ulihin, A.B. Slobodyuk, E.B. Merkulov, R.M. Yaroshenko, V.K. Goncharuk, “Transport properties of fluoride-type solid solution in the KF-BiF3 and PbF2 – MF- BiF3 systems (M=K, Cs) studied by 19F NMR and conductivity measurements,” Solid State Ionics, in press.
 S.P. Gabuda, Yu.V. Gagarinskiy, S.A. Polishchuk, NMR in the Inorganic Fluorides. Moscow, Russia: Atomizdat, 1978.
 V.Ya. Kavun, A.B. Slobodyuk, E.A. Tararako, E.Yu. Mikhteeva, V.K. Goncharuk, N.F. Uvarov, V.I. Sergienko, “Synthesis, ion mobility, and superionic conductivity of (1-x)PbF2 – xMFn (M = Li, Na, K, Rb, Cs, Zr) solid solutions,” Inorg. Mater., vol. 41, No. 11, pp. 1388–1396, November 2005.
 V.Ya. Kavun, V.I. Sergienko, Diffusion Mobility and Ionic Transport in the Crystalline and Amorphous Fluorides of IV Group Elements and Antimonium (III). Vladivostok, Russia: Dalnauka, 2004.