Hostname: page-component-586b7cd67f-dsjbd Total loading time: 0 Render date: 2024-11-28T09:23:12.234Z Has data issue: false hasContentIssue false
  • English
  • Français

Ferroelectric and proton conducting behavior of a new elpasolite-related vanadium oxyfluoride (NH4,K)3VO2F4

Published online by Cambridge University Press:  31 January 2011

Sadequa J. Patwe ,
S. Nagabhusan Achary ,
Kalpathy Ganapathy Girija ,
C.G. Sivan Pillai  and
Avesh K. Tyagi
Avesh K. Tyagi
Affiliation:
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
Get access

Abstract

A new elpasolite-type (NH4,K)3VO2F4 compound was prepared and characterized by x-ray diffraction, differential scanning calorimeter (DSC), impedance analysis, and electrical polarization measurements. It crystallizes in an orthorhombic lattice with unit-cell parameters: a = 8.9584(4), b = 18.6910(14), c = 6.2174(4) Å, V = 1041.04(11) Å3, Z = 6. NH4+, and K+ ions are distributed statistically over crystallographically four equivalent sites. There are two distinguishable vanadium atoms forming cis- and trans-VO2F4 octahedra present in the unit cell. High-temperature studies by DSC and in situ x-ray diffraction revealed a first-order structural transformation from orthorhombic to cubic lattice around 343 K. Impedance measurements show two different kinds of conductivity behaviors for the two phases. In orthorhombic phase a significant conductivity resulting from involvement of protonic species is observed. In the orthorhombic phase, a clear ferroelectric hysteresis loop is observed.

Keywords

Phase transformationFerroelectricElectrical properties
Type
Articles
Information
Journal of Materials Research , Volume 25 , Issue 7 , July 2010 , pp. 1251 - 1263
Copyright
Copyright © Materials Research Society 2010

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Flerov, I.N., Gorev, M.V., Aleksandrov, K.S., Tressaud, A., Grannec, J., Couzi, M.Phase transitions in elpasolites (ordered perovskites). Mater. Sci. Eng., R 24, 81 (1998)CrossRefGoogle Scholar
2.Galasso, F.S.Structure, Properties and Preparation of Perovskite-Type Compounds (Pergamon Press, Oxford 1969)Google Scholar
3.Udovenko, A.A., Laptash, N.M., Masiennikova, I.G.Orientation disorder in ammonium elpasolites. Crystal structures of (NH4)3AlF6, (NH4)3TiOF5 and (NH4)3FeF6. J. Fluorine Chem. 124, 5 (2003)CrossRefGoogle Scholar
4.Woodward, P.M.Octahedral tilting in perovskites. Acta Crystallogr., Sect. B 53, 44 (1997)CrossRefGoogle Scholar
5.Flerov, I.N., Gorev, M.V., Tressaud, A., Grannec, J.Ferroelastic phase transitions in Rb2KM3+F6 elpasolites. Ferroelectrics 217, 21 (1998)CrossRefGoogle Scholar
6.Flerov, I.N., Gorev, M.V., Fokina, V.D., Molokeev, M.S.Phase transitions in oxides, fluorides and oxyfluorides with the ordered perovskite structure. Ferroelectrics 346, 77 (2007)CrossRefGoogle Scholar
7.Ravez, J., Peraudeau, G., Arend, H., Abrahams, S.C., Hagenmuller, P.A new family of ferroelectric materials with composition A2BMO3F3 (A, B = K, Rb, Cs, for rA ≥ rB and M = Mo, W). Ferroelectrics 26, 767 (1980)CrossRefGoogle Scholar
8.Flerov, I.N., Fokina, V.D., Bovina, A.F., Bogdanov, E.V., Molokeev, M.S., Kocharova, M.S., Pogorel'tsev, E.I., Laptash, N.M.Mechanism and nature of phase transitions in the (NH4)3MoO3F3 oxyfluoride. Phys. Solid State 50, 515 (2008)CrossRefGoogle Scholar
9.Brink, F.J., Withers, R.L., Friese, K., Madariaga, G., Norén, L.An electron diffraction and XRPD study of superlattice ordering in the elpasolite-related oxyfluoride K3MoO3F3. J. Solid State Chem. 163, 267 (2002)CrossRefGoogle Scholar
10.Withers, R.L., Brink, F.J., Liu, Y., Norén, L.Cluster chemistry in the solid state: Structured diffuse scattering, oxide/fluoride ordering and polar behavior in transition metal oxyfluorides. Polyhedron 26, 290 (2007)CrossRefGoogle Scholar
11.Brink, F.J., Norén, L., Goossens, D.J., Withers, R.L., Liu, Y., Xu, C-N.Synthesis, electron diffraction, XRD and DSC study of the new elpasolite-related oxyfluoride, Tl3MoO3F3. J. Solid State Chem. 174, 44 (2003)CrossRefGoogle Scholar
12.Flerov, I.N., Fokina, V.D., Bovina, A.F., Laptash, N.M.Phase transitions in perovskite-like oxyfluorides (NH4)3WO3F3 and (NH4)3TiOF5. Solid State Sci. 6, 367 (2004)CrossRefGoogle Scholar
13.Fokina, V.D., Flerov, I.N., Gorev, M.V., Bogdanov, E.V., Bovina, A.F., Laptash, N.M.Thermophysical studies of the phase transitions in (NH4)3NbOF6 crystals. Phys. Solid State 49, 1548 (2007)CrossRefGoogle Scholar
14.Fokina, V.D., Flerov, I.N., Gorev, M.V., Molokeev, M.S., Vasiliev, A.D., Laptash, N.M.Effect of cationic substitution on ferroelectric and ferroelastic phase transitions in oxyfluorides A2A′WO3F3 (A, A′: K, NH4, Cs). Ferroelectrics 347, 60 (2007)CrossRefGoogle Scholar
15.Flerov, I.N., Gorev, M.V., Fokina, V.D., Bovina, A.F., Molokeev, M.S., Boiko, Yu.V., Voronov, V.N., Kochraova, A.G.Structural phase transition in elpasolite-like (NH4)2KWO3F3. Phys. Solid State 48, 106 (2006)CrossRefGoogle Scholar
16.Molokeev, M.S., Vasiliev, A.D., Kocharova, A.G.Crystal structures of room- and low-temperature phases in oxyfluoride (NH4)KWO3F3. Powd. Diff. 22, 227 (2007)CrossRefGoogle Scholar
17.Fokina, V.D., Gorev, M.V., Kocharova, A.G., Pogoreltsev, E.I., Flerov, I.N.Phase transitions and thermodynamic properties of (NH4)3VO2F4 cryolite. Solid State Sci. 11, 836 (2009)CrossRefGoogle Scholar
18.Von Pausewang, G., Rudorff, W.On alkali oxofluorometalate of transition metal: A3MeOxF6−x structures, with x = 1, 2, 3. Z. Anorg. Allg. Chem. 364, 69 (1969)CrossRefGoogle Scholar
19.Leimkuhler, M., Mattes, R.The structure of the VO2F43− ion: Crystal structure of (NH4)3VO2F4. J. Solid State Chem. 65, 260 (1986)CrossRefGoogle Scholar
20.Gillespie, R.J., Rao, U.R.K.51V and 19F N.M.R. study of [VO2F4]3− in solution. N.M.R. evidence is presented for the existence of VO2F43− in aqueous solutions. J. Chem. Soc. Chem. Comm. 422 (1983)CrossRefGoogle Scholar
21.Adhyapak, S.V., Kadam, R.M., Page, A.G., Rao, U.R.K.EPR studies of some vanadium oxyfluoro anionic complexes. Phase Transit. 51, 199 (1994)CrossRefGoogle Scholar
22.Rao, U.R.K., Venkateswarlu, K.S., Wani, B.R., Sastry, M.D., Dalvi, A.G.I., Joshi, B.D.E.P.R. study of molecular dynamics and phase transition in γ-irradiated (NH4)3VO2F4. Mol. Phys. 47, 637 (1982)CrossRefGoogle Scholar
23.Mel'nikova, S.V., Kocharova, A.G.Optical studies of phase transitions in the (NH4)3VO2F4 crystal. Phys. Solid State 51, 597 (2009)CrossRefGoogle Scholar
24.Wani, B.R., Rao, U.R.K., Venkateswarlu, K.S., Gokhale, A.S.Thermal behavior of (NH4)3VO2F4 and Na(NH4)2VO2F4. Thermochim. Acta 58, 87 (1982)CrossRefGoogle Scholar
25.Von Pausewang, G.On alkali oxofluorometalate of transition metals (III). Investigation on oxyfluoride of tetravalent vanadium. Z. Anorg. Allg. Chem. 381, 189 (1971)Google Scholar
26.Von Pausewang, G., Dehnicke, K.On alkali oxofluorometalate of transition metals (II). Crystal structure of some oxyfluorides with pentavalent vanadium. Z. Anorg. Allg. Chem. 369, 265 (1969)Google Scholar
27.Sengupta, A.K., Bhaumik, B.B.Vanadium (V) oxufluorides. IV. Dioxotetrafluorovanadates. Z. Anorg. Allg. Chem. 390, 311 (1972)CrossRefGoogle Scholar
28.Patwe, S.J., Rao, U.R.K.Characterization and thermal behavior of reaction product in the three solid component system MVO3–MHF2–M′HF2 (M = Li, M = M = M′ = Na, K, Rb and NH4). J. Mater. Sci. Lett. 14, 1702 (1995)CrossRefGoogle Scholar
29.Patwe, S.J., Rao, U.R.K.Mode of thermal decomposition of diammonium lithium oxyfluoro vanadate (DALOFV) and diammonium rubidium oxyfluoro vanadate (DAROFV). Thermochim. Acta 264, 205 (1995)CrossRefGoogle Scholar
30.Rodriguez-Carvajal, J.Multi-Pattern Rietveld Refinement Program FullProf .2k Version 3.30 (Laboratoire Léon Brillouin (CEA-CNRS) CEA/Saclay, France 2005)Google Scholar
31.Stomberg, R.Crystal structure of sodium pentafluorooxovanadate(V), Na2(VF5O), and potassium catena-fluorodifluorodioxovanadate(V), K2n(VF3O2)n, two decomposition products in the system V2O5/(MF, HF)/H2O2/H2O. Acta Chem. Scand. Ser. A 28, 325 (1986)CrossRefGoogle Scholar
32.Zavalij, P.Y., Whittingham, M.S.Structural chemistry of vanadium oxides with open frameworks. Acta Crystallogr., Sect. B 55, 627 (1999)CrossRefGoogle ScholarPubMed
33.Flerov, I.N., Gorev, M.V., Grannec, J., Tressaud, A.Role of metal fluoride octahedra in the mechanism of phase transitions in A2BMF6 elpasolites. J. Fluorine Chem. 116, 9 (2002)CrossRefGoogle Scholar
34.Hamadkne, M., Grannec, J., Ravez, J., Ldidoudi-Guehria, A.Phase transition in the composition Na3MF6, (M = Ti, Co, In; X = O, F). J. Fluorine Chem. 78, 141 (1996)CrossRefGoogle Scholar
35.Hazen, R.M., Prewitt, C.T.Effect of temperature and pressure on interatomic distances in oxygen based minerals. Am. Mineral. 62, 309 (1977)Google Scholar
36.Eyert, V., Höck, K-H.Electronic structure of V2O5: Role of octahedral deformations. Phys. Rev. B: Condens. Matter 57, 12727 (1998)CrossRefGoogle Scholar
37.Galy, J., Ratuszna, A., Iglesias, J.E., Castro, A.Complex thermal evolution of V2O5 and MoO3 cell parameters in the range 15 < T (K) < 900. Solid State Sci. 8, 1438 (2006)CrossRefGoogle Scholar
38.Enhalbert, R., Galy, J.A refinement of the structure of V2O5. Acta Crystallogr., Sect. C 42, 1467 (1986)CrossRefGoogle Scholar
39.Balog, P., Orosel, D., Cancarevic, Z., Schön, C., Jansen, M.V2O5 phase diagram revisited at high pressures and high temperatures. J. Alloys Compd. 429, 87 (2007)CrossRefGoogle Scholar
40.Patwe, S.J., Achary, S.N., Tyagi, A.K.Crystal structure, electrical, and thermal properties of Ca0.5Th0.5VO4. J. Mater. Res. 24, 3551 (2009)CrossRefGoogle Scholar
41.Patwe, S.J., Achary, S.N., Tyagi, A.K.Lattice thermal expansion of zircon-type LuPO4 and LuVO4: A comparative study. Am. Mineral. 94, 98 (2009)CrossRefGoogle Scholar
42.Errandonea, D., Lacomba-Perales, R., Ruiz-Fuertes, J., Segura, A., Achary, S.N., Tyagi, A.K.High-pressure structural investigation of several zircon-type orthovanadates. Phys. Rev. B: Condens. Matter 79, 184104 (2009)CrossRefGoogle Scholar
43.Mittal, R., Garg, A.B., Vijayakumar, V., Chaplot, S.L., Achary, S.N., Tyagi, A.K., Godwal, B.K., Busetto, E., Lausi, A.Investigation of the phase stability of LuVO4 at high pressure by powder x-ray diffraction measurements and lattice dynamical calculations. J. Phys. Condens. Matter 20, 075223 (2008)CrossRefGoogle Scholar
44.Achary, S.N., Patwe, S.J., Tyagi, A.K.Crystal structure and thermal expansion studies of α-VO(PO3)2. J. Alloys Compd. 461, 474 (2008)CrossRefGoogle Scholar
45.Kim, C., Lee, G., Lio, K., Ryu, K.S., Kang, S.G., Chang, S.H.Polymer electrolytes prepared by polymerizing mixtures of polymerizable PEO-oligomers, copolymer of PVDC and poly(acrylonitrile), and lithium triflate. Solid State Ionics 123, 251 (1999)CrossRefGoogle Scholar
46.Baskaran, R., Selvasekarapandian, S., Kuwata, N., Kawamura, J., Hattori, T.Ac impedence, DSG and FT-IR investigations on (x)PVAc-(1-x)PVdF blends with LiClO4. Mater. Chem. Phys. 98, 55 (2006)CrossRefGoogle Scholar
47.Scott, J.F.Ferroelectrics go bananas. J. Phys. Condens. Matter 20, 021001 (2008)CrossRefGoogle Scholar
48.Mani, R., Achary, S.N., Chakraborty, K.R., Deshpande, S.K., Joy, J.E., Nag, A., Gopalakrishnan, J., Tyagi, A.K.FeTiTaO6: A lead-free relaxor ferroelectric based on the rutile structure. Adv. Mater. 20, 1348 (2008)CrossRefGoogle Scholar
49.Ramesha, K., Llobet, A., Proffen, Th., Serrao, C.R., Rao, C.N.R.Observation of local non-centrosymmetry in weakly biferroic YCrO3. J. Phys. Condens. Matter 19, 102202 (2007)CrossRefGoogle Scholar