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Methods of ( 19 F, 1 H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF 2 -ZrF 4 and polycrystals KSnZrF 7 , Li ( Na )( NH 4 ) 6 Zr 4 F 23 , and M 2 ZrF 6 (M = K, NH 4 ). Factors responsible for the form of ionic motions and their energetics at 170-550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.

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