2010B1840                          BL14B2PbO ⣔࠾ࡼࡧ Bi2O3 ⣔࣍࢘㓟ሷ࢞ࣛࢫࡢ XAFS ᵓ㐀ゎᯒ
XAFS Analysis of PbO and Bi2O3-based Borate Glasses⣚㔝 Ᏻᙪ, 㞴Ἴ ᚨ㑻, 㖝 Ⰻ἞
Yasuhiko Benino, Tokuro Nanba, Yoshiharu Hokoᒸᒣ኱Ꮫ኱Ꮫ㝔⎔ቃᏛ◊✲⛉ Okayama University, Graduate School of Environmental Science
Bi2O3-ZnO-B2O3 ⣔࢞ࣛࢫ࡟ᑐࡋ࡚ Zn-K ➃࠾ࡼࡧ Bi-LIII ➃࡟㛵ࡍࡿ XAFS ᐃࢆ⾜࠸ࠊᮏ⣔࢞ࣛࢫ࡟࠾ࡅࡿ Zn ࡢ㓄఩≧ែࡣࠊ࢞ࣛࢫ⤌ᡂ࡟౫Ꮡࡏࡎ Bi2ZnB2O7 ⤖ᬗ࡟㢮ఝࡍࡿࡇ࡜ࡀ EXAFSゎᯒ࠿ࡽ☜ㄆࡉࢀࡓࠋ໬ᏛⓗᏳᐃᛶࢆ᭷ࡍࡿప⼥Ⅼ࢞ࣛࢫࡢ㛤Ⓨ࡟࠾࠸࡚ࠊྛ✀ᵓ㐀ゎᯒ࡟ࡼࡿ㔜㔠ᒓ࣍࢘㓟ሷ࢞ࣛࢫࡢᵓ㐀⌮ゎࡀ୙ྍḞ࡛࠶ࡾࠊSPring-8 ᨺᑕග฼⏝ࡢ᭷ຠᛶࡀ♧ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 㔜㔠ᒓ࣍࢘㓟ሷ࢞ࣛࢫࠊప⼥Ⅼ࢞ࣛࢫࠊ࢞ࣛࢫᵓ㐀ࠊEXAFS ゎᯒ⫼ᬒ࡜◊✲┠ⓗ㸸ᨺᑕᛶᗫᲠ≀ࡢᆅᒙฎศࡢᏳ඲ᛶホ౯ࡢほⅬ࠿ࡽࠊ㏆ᖺࠊ⿕ࡤࡃ⥺㔞ࡢపῶ໬ࡀᮇᚅ࡛ࡁࡿࣚ࢘⣲ 129 ࡢᅛᐃ໬࡟㛵ࡍࡿᢏ⾡㛤Ⓨࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋࣚ࢘⣲ 129 ࡣࠊ༙ῶᮇࡀ 1570 ୓ᖺ࡜㠀ᖖ࡟㛗࠸ࡇ࡜࠿ࡽࠊᅛᐃ໬࡟ࡣࣚ࢘⣲ࢆ㛗ᮇ࡟ࢃࡓࡗ࡚Ᏻᐃ࡟ಖᣢࡍࡿᮦᩱࡀồࡵࡽࢀ࡚࠾ࡾࠊ௨ୗ࡟ㄝ᫂ࡍࡿ㖄࣍࢘㓟ሷ࢞ࣛࢫࢆ⏝࠸ࡓ࢞ࣛࢫᅛ໬ᢏ⾡ࡣࡑࡢ᭷ຊ࡞ೃ⿵࡛࠶ࡿࠋࡇࡢ᪉ἲ㸦BPI࢞ࣛࢫᅛ໬ᢏ⾡㸧࡛ࡣࠊࣚ࢘⣲ࢆྵࡴ BPI ⤖ᬗ㻔BiPbO2I㻕ࡀ PbO-ZnO-B2O3 ⣔࢞ࣛࢫ࡟ΰྜࡉࢀࠊప ࡟࡚⁐⼥ᚋࠊ෭༷ࡋ࡚ᚓࡽࢀࡿࣚ࢘⣲ྵ᭷ࣅࢫ࣐ࢫ㖄ள㖄࣍࢘㓟ሷ࢞ࣛࢫ࡜ࡋ࡚ࣚ࢘⣲ࢆᅛᐃ໬ࡍࡿࡶࡢ࡛࠶ࡿ[1]ࠋBPI ࢞ࣛࢫᅛ໬ᢏ⾡ࡢ☜❧࡜㧗ᗘ໬࡟ࡣࠊ࢞ࣛࢫ⤌ᡂ࠾ࡼࡧప ⁐⼥ᅛ໬ࣉࣟࢭࢫࡢᵓ⠏࡜ࡑࡢ᭱㐺໬ࡀᚲせ࡛࠶ࡾࠊຍ࠼࡚ࠊᚓࡽࢀࡓࣚ࢘⣲ྵ᭷࢞ࣛࢫࡢᵓ㐀ゎ᫂ࡀᛴົ࡜࡞ࡗ࡚࠸ࡿࠋBPI ࢞ࣛࢫᅛ໬య࡟࠾࠸࡚ࡣࠊ୺せᡂศ࡛࠶ࡿ Pbࠊྵ᭷㔞ࡀᑡ࡞࠸ Bi ࠾ࡼࡧ Znࠊಖᣢᡂศ࡛࠶ࡿ I ࡟㛵ࡍࡿᒁᡤᵓ㐀ࡀ࢞ࣛࢫᅛ໬యࡢ໬ᏛⓗᏳᐃᛶ࡜㛗ᮇಙ㢗ᛶࢆホ౯ࡍࡿ࡟࠶ࡓࡾ㔜せᛶࡀᣦ᦬ࡉࢀࠊ࢞ࣛࢫᵓ㐀ࡢ⌮ゎ࡟ᇶ࡙࠸࡚ᵓᡂ࢖࢜ࣥࡢ⁐ฟ㐣⛬ࡢゎ᫂ࢆ┠ⓗ࡜ࡋࡓ⁐ฟࣔࢹࣝᵓ⠏ࡀ୙ྍḞ࡛࠶ࡿࠋᮏ◊✲ㄢ㢟ࡣࠊBPI ࢞ࣛࢫ࠾ࡼࡧࡑࡢ㛵㐃࢞ࣛࢫ࡟㛵ࡍࡿࡇࢀࡲ࡛ࡢ◊✲㸦BL04B2 ࢆ฼⏝ࡋࡓ㧗࢚ࢿࣝࢠ࣮X ⥺ᅇᢡ ᐃࠊJ-PARC MLF ࢆ฼⏝ࡋࡓ୰ᛶᏊ⥺ᅇᢡ ᐃ࠾ࡼࡧ 11B MAS NMR ᐃ㸧࡟ࡼࡿᡂᯝ࡜㛵㐃௜ࡅࡿࡇ࡜࡟ࡼࡾࠊ࢞ࣛࢫᵓ㐀ࣔࢹࣝࡢᵓ⠏ࢆ┠ᣦࡍࡶࡢ࡛࠶ࡿࠋᐇ㦂㸸ᮏ◊✲ㄢ㢟࡛ࡣࠊࣅࢫ࣐ࢫள㖄࣍࢘㓟ሷ࢞ࣛࢫࢆᑐ㇟࡜ࡋ࡚ BL14B2 ࢆ฼⏝ࡋࡓ Zn-K ➃࠾ࡼࡧ Bi-LIII ➃࡟㛵ࡍࡿ XAFS ᐃࢆᐇ᪋ࡋࡓࠋ࢞ࣛࢫヨᩱࡣࠊBi2O3ࠊZnOࠊB2O3 ࢆฟⓎཎᩱ࡜ࡋ࡚
⾲ 1 ࡟♧ࡋࡓྛ࢞ࣛࢫ⤌ᡂ࡜࡞ࡿࡼ࠺࡟⛗㔞ࠊΰྜᚋࠊ㔠ᆣላ୰ 30 ศ㛫ࡢ⁐⼥ᚋࠊ෭༷ࡍࡿࡇ࡜
࡛ᚓࡓࠋᶆ‽ヨᩱ ZnO ࠾ࡼࡧ Bi2O3 ࡟ࡣཎᩱヨ⸆ࢆ౑⏝ࡋࠊBi3B5O12ࠊBi2ZnB2O7 ࡟ࡘ࠸࡚ࡣ໬Ꮫ
⾲ 1㸬Zn-K ➃࠾ࡼࡧ Bi-LIII ➃࡛ ᐃᑐ㇟࡜ࡋࡓᶆ‽ヨᩱ࠾ࡼࡧ࢞ࣛࢫヨᩱ
Zn-K ➃ ᶆ‽ヨᩱ࢞ࣛࢫヨᩱ

Bi-LIII ➃ ᶆ‽ヨᩱ
࢞ࣛࢫヨᩱZn foil, ZnO, Bi2ZnB2O7xBi2O3-yZnO-㻔100-x-y㻕B2O3㻔x, y㻕 = 㻔40, 10㻕, 㻔60,10㻕, 㻔10, 30㻕, 㻔20, 30㻕, 㻔40,30㻕, 㻔50, 30㻕, 㻔40,40㻕,
㻔0, 50㻕, 㻔10, 50㻕, 㻔20, 50㻕, 㻔33, 33㻕
Bi2O3, Bi3B5O12, Bi2ZnB2O7xBi2O3-yZnO-㻔100-x-y㻕B2O3
㻔x, y㻕 = 㻔50, 0), 㻔40, 10㻕, 㻔60,10㻕, 㻔10, 30㻕, 㻔20, 30㻕, 㻔40,30㻕, 㻔50, 40㻕,㻔40, 40㻕, 㻔10, 50㻕, 㻔20, 50㻕, 㻔33, 33㻕㔞ㄽ⤌ᡂࢆ᭷ࡍࡿ࢞ࣛࢫࡢ⇕ฎ⌮࡟ࡼࡾస〇ࡋࠊࡑࢀࡒࢀ༢┦⤖ᬗ໬ࢆ XRD ᐃ࡟࡚☜ㄆࡋࡓࠋXAFS ᐃ⏝࡜ࡋ࡚ྛヨᩱ⢊ᮎࢆ‽ഛࡋࠊ㐺ษ࡞྾཰ಀᩘ࠾ࡼࡧ྾཰➃ኚ໬㔞࡜࡞ࡿࡼ࠺࡟ BN⢊ᮎ࡛ᕼ㔘ࡋ࡚㘄๣ࢆᡂᙧࡋࡓࠋXAFS ᐃ࡟ࡣࠊSPring-8 BL14B2 ࡢᶆ‽ⓗ࡞㏱㐣ἲ⮬ື XAFSᐃࢩࢫࢸ࣒㻔Auto XAFS㻕ࢆ฼⏝ࡋࠊ ᐃࢹ࣮ࢱࣇ࢓࢖ࣝࡢኚ᥮࡜ゎᯒ࡟ࡣࠊࡑࢀࡒࢀ XAFS DataConverterࠊAthena ࢆ฼⏝ࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸ᶆ‽ヨᩱ࠾ࡼࡧ 4 ✀㢮ࡢ࢞ࣛࢫヨᩱ࡟ࡘ࠸࡚ࠊZn-K ྾཰➃ࡢ EXAFS ᣺ືࡢࣇ࣮࢚ࣜኚ᥮ࢆᅗ1 ࡟♧ࡋࡓࠋ࢞ࣛࢫヨᩱ࡛ࡣࠊR = 1.5 Å㸦఩┦ᅉᏊ࡟ࡼࡿ⿵ṇ࡞ࡋ㸧࡟ࡢࡳ᫂☜࡞ࣆ࣮ࢡࡀㄆࡵࡽࢀࠊືᚄศᕸゎᯒࡀ᭷ຠ࡛࠶ࡿࡢࡣ➨ 1 㓄఩ᅪࡢࡳ࡛࠶ࡗࡓࠋࡇࢀࡽࡢືᚄศᕸࡢẚ㍑࠿ࡽࠊ
Bi2O3-ZnO-B2O3 ⣔࢞ࣛࢫ࡟࠾ࡅࡿ Zn ࡢ㓄఩≧ែࡣࠊᶆ‽ヨᩱ࡛࠶ࡿ࣓ࣜࣛ࢖ࢺᆺ Bi2ZnB2O7 ⤖ᬗ[2]࡟㢮ఝࡋࠊZnO ྵ᭷㔞ࡸ Bi2O3/B2O3 ẚ࡞࡝ࡢ࢞ࣛࢫ⤌ᡂ࡟౫Ꮡࡏࡎ 4 㓄఩࡛࠶ࡿࡇ࡜ࡀ♧၀
ࡉࢀࡓࠋZnO ྵ᭷㔞ࡀ 10 mol%௨ୗࡢ࢞ࣛࢫヨᩱ࡟ࡘ࠸࡚ࡣ EXAFS ᣺ືࡢ ᐃ⢭ᗘࡀ୙༑ศ࡛
࠶ࡾࠊZn ࡢ㓄఩ᩘኚ໬➼ࡢᵓ㐀ࡢヲ⣽࡞ゎᯒࢆ⾜࠺࡟ࡣ ᐃ᮲௳ࡢ෌᳨ウࡀᚲせ࡛࠶ࡿࠋᅗ 1㸬Bi2O3-ZnO-B2O3 ⣔࢞ࣛࢫࡢ Zn-K ྾཰➃ࡢ EXAFS ᣺ືࡢࣇ࣮࢚ࣜኚ᥮.
୍᪉ࠊBi-LIII ྾཰➃ࡢ EXAFS ᣺ືࡢゎᯒ࡛ࡣࠊBi2O3 ྵ᭷㔞ࡀ 10 mol%࡟࠾࠸࡚ࡶ➨ 1 㓄఩ᅪࡢືᚄศᕸゎᯒࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋZnO ྵ᭷㔞ࡀ 10 mol%ࡢ⣔ิ࡛ࡣࠊ௚ࡢ࢞ࣛࢫヨᩱ࡜ẚ࡭࡚ Bi-O ㊥㞳ࡀ㛗ࡃ Bi ࡢ㓄఩≧ែࡀኚ໬ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࡀࠊBi2O3-ZnO- B2O3 ⣔࢞ࣛࢫ࡟࠾ࡅࡿ Bi ࡢ㓄఩≧ែ࡟ࡘ࠸࡚ࠊࡼࡾヲ⣽࡟ᐃ㔞ⓗ࡟ྲྀࡾᢅ࠺࡟ࡣ XAFS ᐃ᮲௳ࡢ᭱㐺໬ࢆྵࡵ࡚᭦࡞ࡿㄪᰝࡀᚲせ࡛࠶ࡿࠋ௒ᚋࡢㄢ㢟㸸
Bi2O3-ZnO-B2O3 ⣔࢞ࣛࢫ࡟ࡘ࠸࡚ࡣࠊBL04B2 ࢆ฼⏝ࡋࡓ㧗࢚ࢿࣝࢠ࣮X ⥺ᅇᢡ ᐃࠊJ-PARCMLF ࢆ฼⏝ࡋࡓ୰ᛶᏊ⥺ᅇᢡ ᐃ࠾ࡼࡧ 11B MAS NMR ᐃ࡟ࡼࡿ࢞ࣛࢫᵓ㐀ゎᯒࢆᐇ᪋ࡋ࡚࠸ࡿࠋࡇࢀࡽࡢ ᐃ࠿ࡽᚓࡽࢀࡿᵓᡂ࢖࢜ࣥࡢᒁᡤᵓ㐀࡟㛵ࡍࡿ᝟ሗࢆ⵳✚ࠊ⥲ྜⓗ࡟ゎ㔘ࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡾࠊBPI ࢞ࣛࢫᅛ໬ἲ࡛฼⏝ࡉࢀࡿከᡂศ࢞ࣛࢫࡢᵓ㐀ゎᯒ࠿ࡽࠊࡑࡢ࢞ࣛࢫᵓ㐀ࡢ⌮ゎ࡜໬ᏛⓗᏳᐃᛶࠊ⁐ฟ࣓࢝ࢽࢬ࣒ࡢゎ᫂࡟ᐤ୚ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋཧ⪃ᩥ⊩㸸
[1] A. Mukunoki, T. Chiba, Y. Suzuki, K. Yamaguchi, T. Sakuragi, T. Nanba, Proceedings of the 12th
International Conference on Environmental Remediation and Radioactive Waste Management
㻔ICEM2009, Liverpool, UK㻕, 16268㻌㻔2009㻕.
[2] J. Barbier, N. Penin, L.M. Cranswick, Chem. Mater. 17, 3130 㻔2005㻕.