Chemistry of Rare Earth Containing Oxide-fluoride Compounds

Masayuki Takashima; Susumu Yonezawa; Jae-Ho Kim; Shiori Nishibu

Journal of Industrial and Engineering Chemistry, Vol.10, No.7, 1230-1241, December, 2004

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Chemistry of Rare Earth Containing Oxide-fluoride Compounds

Masayuki Takashima^†, Susumu Yonezawa¹, Jae-Ho Kim, and Shiori Nishibu¹

Cooperative Research Center, Department of mateials science and engineering, University of Fukui, Fukui 910-850, Japan
¹Department of materials Science and engineering, University of Fukui, Fukui 910-850, Japan

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The binary rare-earth oxide fluorides, Ln₂Ln'₂O₃F₆ in which Ln and Ln' are different rate earths, were synthesized by the solid state reaction between Ln₂O₃ and Ln'F₃ at a temperature around 1000℃. Among Ln₂Ln'₂O₃F₆ compounds, Nd₂Eu₂O₃F₆ gave the conductivity of 3.5 Sm^-1 at 600℃ under Po₂=0.4 Pa, and the transport numbers of oxide ion and electron were measured to be around 0.9 and less than 0.05, respectively, at a temperature ranging from 500 to 700℃. The crystal structure of Nd₂Eu₂O₃F₆ was determined to be the monoclinic lattice with the parameters of a₀ = 0.396 nm, b₀ = 1.13 nm, c₀ = 0.562 nm, β = 134.84^o, Z = 1. Nd₂Ln'₂O₃F₆ compounds were applicable properties as an oxide ion-conducting solid electrolyte. Besides, new oxide-fluoride glasses containing large amount of rare earth elements consist of LnF₃-BaF₂-AlF₃-GeO₂ were obtained reproducibly by quenching from the melts. The glasses were found to exhibit unique optical properties such as fluorescence.

Keywords:rare earth;oxide-fluoride;oxide ion conduction;rare earth glass;fluorescence

[References]

Powell JE, Handbook on the Physics and Chemistry of Rare Earths, edited by K. A. Gschneider, Jr. and L. Eyring, North-Holland Physics Publishing, Amsterdam, chapter 22 (1979)
Collins JF, Calkins VP, McGurty JA, The Rare Earths, edited by F. H. Spedding and A. H. Daane, Robert E. Krieger Publishing Co. Ltd., Huntington, N. Y., chapter 20, M. M. Woyski and W. J. Silvernail, ibid, chapter 21, W. K. Anderson, ibid, chapter 22 (1971)
Takahashi T, Physics of Solid Electrolytes, edited by J. Hladik, Academic Press, London, chapter 24 (1972)
Khattak CP, Wang FEY, Handbook on the Physics and Chemistry of Rare Earths, edited by K. A. Gschneider, Jr. and L. Eyring, North-Holland Physics Publishing, Amsterdam, chapter 29 (1979)
Fluoride Glasses, edited by A. E. Comyns, John Wiley & Sons, N. Y. (1989)
Takashima M, Kano G, Solid State Ion., 23, 99 (1987)
Takashima M, Yonezawa S, Tokuno T, Umehara H, Kato T, J. Fluor. Chem., 112, 241 (2001)
Takashima M, Kano G, Solid State Ion., 23, 99 (1987)
The Rare Earth, edited by F. H. Spedding and A. H. Daane, Robert E. Kriegert Publishing Co. Inc., Huntington, N. Y. (1970)
Povov AI, Kunudson GK, J. Am. Chem. Soc., 76, 3921 (1954)
Zachariasen WH, Acta Cryst., 4, 231 (1951)
Kutek F, J. Ruusi. Inorg. Chem., 9, 1500 (1964)
Shinn DB, Eick HA, Inorg. Chem., 8, 232 (1968)
Takashima M, Nosaka Y, Unishi T, Eur. J. Solid State Inorg. Chem., 29, 691 (1992)
Takashima M, Fukami S, Nosaka Y, Unishi T, J. Fluor. Chem., 57, 131 (1992)
Zachariasen WH, Acta Cryst., 4, 231 (1951)
Niihara K, Yajima S, Bull. Chem. Soc. Jpn., 44, 653 (1971)
Niihara K, Yajima S, Bull. Chem. Soc. Jpn., 45, 20 (1972)
Takashima M, Yonezawa S, Horita K, Takahashi H, J. Mater. Chem., 6, 795 (1996)
Klemm W, Klein HA, Z. Anorg. Allg. Chem., 248, 2367 (1941)
Chamberland BL, Inorganic Solid Fluorides, edited by P. Hagenmuller, Academic Press, Inc., Orland chapter 5 (1985)
Goto KS, Pluschkell W, Physics of Electrolytes, edited by J. Hladik, Academic Press, London, chapter 13 (1972)
Wagner C, Adv. Electrochem. Eng., 4, 1 (1966)
Kvist A, Physics of Electrolytes, edited by J. Hladik, Academic Press, London, chapter 8 (1972)
Takashima M, Kano G, Hirano K, Hibino Y, Nippon Kagaku Kaishi, 1987 (1779)
Jander W, Anorg Z, Allgem. Chem., 163, 1 (1927)
Kaminskii A, Laser Crystals, their Physical and Properties, Springer, New York (1990)
Wang Y, Ohwaki J, Appl. Phys. Lett., 63, 3268 (1993)
Auzel F, Pecile D, Morin D, J. Electrochem. Soc., 122, 101 (1975)
Dejneka MJ, J. Non-Cryst. Solids, 239, 149 (1998)
Taylor ER, Samson BN, Hewak DW, MedeirosNeto JA, Payne DN, Jordery S, Naftaly M, Jha A, J. Non-Cryst. Solids, 184, 61 (1995)
Iqbal T, Shahriari MR, Hajcak P, Sigel GH, Copeland LR, Reed WA, Appl. Optics, 33, 965 (1994)
Payne SA, Krupke WF, Chai BHT, J. Opt. Soc. Am., B11, 2054 (1994)
Syojiya M, Terumoto M, Kanno R, Kawamoto Y, J. Ceramic. Soc., 107, 419 (1999)
Poulain M, Poulain M, Mater. Sci. Forum, 67-68, 129 (1991)
Sun K, Lee WH, Risen WM, J. Non-Cryst. Solids, 92, 145 (1987)
Kato T, Takashima M, Yonezawa S, Sugiyama W, Abs. of The 18^th Fluorine Conference of Japan, pp.1-2 (1993)
Boutarfaia A, Poulain M, Solid State Ion., 144(1-2), 117 (2001)
Chen CC, Wu YJ, Hwa LG, Mater. Chem. Phys., 65, 306 (2000)
New Glass Forum INTERGLAND version 5 (2004)
Sosman RB, The Properties of Silica, Reinhold, New York (1927)
Rothermel JJ, Sun KH, Silverman A, J. Am. Ceram. Soc., 32, 153 (1949)
Kano T, Yanagida H, Rare Earth-Properties and Applications, pp. 159, Gihodo Shuppan, Tokyo (1990)
Rukmini E, Jayasankar CK, Opt. Mater., 4, 529 (1995)
Reddy MR, Raju SB, Veeraiah N, J. Phys. Chem., Solids, 61, 1567 (2000)
Rai SB, Singh AK, Singh SK, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 59, 3221 (2003)
Driesen K, Gorller-Walrand C, Binnemans K, Mater. Sci. Eng. C-Biomimetic Supramol. Syst., 18, 255 (2001)
Rai SB, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 58, 1559 (2002)
Judd BR, Phys. Rev. Lett., 127, 750 (1962)
Ofelt GS, J. Chem. Phys., 37, 511 (1962)

[1] Powell JE, Handbook on the Physics and Chemistry of Rare Earths, edited by K. A. Gschneider, Jr. and L. Eyring, North-Holland Physics Publishing, Amsterdam, chapter 22 (1979)

[2] Collins JF, Calkins VP, McGurty JA, The Rare Earths, edited by F. H. Spedding and A. H. Daane, Robert E. Krieger Publishing Co. Ltd., Huntington, N. Y., chapter 20, M. M. Woyski and W. J. Silvernail, ibid, chapter 21, W. K. Anderson, ibid, chapter 22 (1971)

[3] Takahashi T, Physics of Solid Electrolytes, edited by J. Hladik, Academic Press, London, chapter 24 (1972)

[4] Khattak CP, Wang FEY, Handbook on the Physics and Chemistry of Rare Earths, edited by K. A. Gschneider, Jr. and L. Eyring, North-Holland Physics Publishing, Amsterdam, chapter 29 (1979)

[5] Fluoride Glasses, edited by A. E. Comyns, John Wiley & Sons, N. Y. (1989)

[6] Takashima M, Kano G, Solid State Ion., 23, 99 (1987)

[7] Takashima M, Yonezawa S, Tokuno T, Umehara H, Kato T, J. Fluor. Chem., 112, 241 (2001)

[8] Takashima M, Kano G, Solid State Ion., 23, 99 (1987)

[9] The Rare Earth, edited by F. H. Spedding and A. H. Daane, Robert E. Kriegert Publishing Co. Inc., Huntington, N. Y. (1970)

[10] Povov AI, Kunudson GK, J. Am. Chem. Soc., 76, 3921 (1954)

[11] Zachariasen WH, Acta Cryst., 4, 231 (1951)

[12] Kutek F, J. Ruusi. Inorg. Chem., 9, 1500 (1964)

[13] Shinn DB, Eick HA, Inorg. Chem., 8, 232 (1968)

[14] Takashima M, Nosaka Y, Unishi T, Eur. J. Solid State Inorg. Chem., 29, 691 (1992)

[15] Takashima M, Fukami S, Nosaka Y, Unishi T, J. Fluor. Chem., 57, 131 (1992)

[16] Zachariasen WH, Acta Cryst., 4, 231 (1951)

[17] Niihara K, Yajima S, Bull. Chem. Soc. Jpn., 44, 653 (1971)

[18] Niihara K, Yajima S, Bull. Chem. Soc. Jpn., 45, 20 (1972)

[19] Takashima M, Yonezawa S, Horita K, Takahashi H, J. Mater. Chem., 6, 795 (1996)

[20] Klemm W, Klein HA, Z. Anorg. Allg. Chem., 248, 2367 (1941)

[21] Chamberland BL, Inorganic Solid Fluorides, edited by P. Hagenmuller, Academic Press, Inc., Orland chapter 5 (1985)

[22] Goto KS, Pluschkell W, Physics of Electrolytes, edited by J. Hladik, Academic Press, London, chapter 13 (1972)

[23] Wagner C, Adv. Electrochem. Eng., 4, 1 (1966)

[24] Kvist A, Physics of Electrolytes, edited by J. Hladik, Academic Press, London, chapter 8 (1972)

[25] Takashima M, Kano G, Hirano K, Hibino Y, Nippon Kagaku Kaishi, 1987 (1779)

[26] Jander W, Anorg Z, Allgem. Chem., 163, 1 (1927)

[27] Kaminskii A, Laser Crystals, their Physical and Properties, Springer, New York (1990)

[28] Wang Y, Ohwaki J, Appl. Phys. Lett., 63, 3268 (1993)

[29] Auzel F, Pecile D, Morin D, J. Electrochem. Soc., 122, 101 (1975)

[30] Dejneka MJ, J. Non-Cryst. Solids, 239, 149 (1998)

[31] Taylor ER, Samson BN, Hewak DW, MedeirosNeto JA, Payne DN, Jordery S, Naftaly M, Jha A, J. Non-Cryst. Solids, 184, 61 (1995)

[32] Iqbal T, Shahriari MR, Hajcak P, Sigel GH, Copeland LR, Reed WA, Appl. Optics, 33, 965 (1994)

[33] Payne SA, Krupke WF, Chai BHT, J. Opt. Soc. Am., B11, 2054 (1994)

[34] Syojiya M, Terumoto M, Kanno R, Kawamoto Y, J. Ceramic. Soc., 107, 419 (1999)

[35] Poulain M, Poulain M, Mater. Sci. Forum, 67-68, 129 (1991)

[36] Sun K, Lee WH, Risen WM, J. Non-Cryst. Solids, 92, 145 (1987)

[37] Kato T, Takashima M, Yonezawa S, Sugiyama W, Abs. of The 18^th Fluorine Conference of Japan, pp.1-2 (1993)

[38] Boutarfaia A, Poulain M, Solid State Ion., 144(1-2), 117 (2001)

[39] Chen CC, Wu YJ, Hwa LG, Mater. Chem. Phys., 65, 306 (2000)

[40] New Glass Forum INTERGLAND version 5 (2004)

[41] Sosman RB, The Properties of Silica, Reinhold, New York (1927)

[42] Rothermel JJ, Sun KH, Silverman A, J. Am. Ceram. Soc., 32, 153 (1949)

[43] Kano T, Yanagida H, Rare Earth-Properties and Applications, pp. 159, Gihodo Shuppan, Tokyo (1990)

[44] Rukmini E, Jayasankar CK, Opt. Mater., 4, 529 (1995)

[45] Reddy MR, Raju SB, Veeraiah N, J. Phys. Chem., Solids, 61, 1567 (2000)

[46] Rai SB, Singh AK, Singh SK, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 59, 3221 (2003)

[47] Driesen K, Gorller-Walrand C, Binnemans K, Mater. Sci. Eng. C-Biomimetic Supramol. Syst., 18, 255 (2001)

[48] Rai SB, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 58, 1559 (2002)

[49] Judd BR, Phys. Rev. Lett., 127, 750 (1962)

[50] Ofelt GS, J. Chem. Phys., 37, 511 (1962)