2009A1794      BL14B2XAFS ࡟ࡼࡿᑡ㔞ࡢ㓟໬㕲ࢆྵ᭷ࡍࡿࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫ୰ࡢFe ࢖࢜ࣥࡢᵓ㐀ゎᯒStructure Analysis of Fe Ion in Soda-Lime Silicate Glasses Containing
Small Amount of Iron Oxides by XAFS Method㛗ᔱ ᗮோ, ⓑᮌ ᗣ୍
Yukihito Nagashima, Koichi Shiraki᪥ᮏᯈ◪Ꮚ㻔ᰴ㻕ᢏ⾡◊✲ᡤ
TECHNICAL RESERCH LABORATORY, NIPPON SHEET GLASS CO. LTD.
0.005mol%ࡢᑡ㔞ࡢ㓟໬㕲ࢆྵ᭷ࡍࡿ Na2O/K2O-MgO/CaO-SiO2 ⣔࢞ࣛࢫࡢ Fe-K ➃ࡢ XAFS ࢆᐃࡋࠊ௨๓ ᐃࡢࡼࡾ㓟໬㕲ྵ᭷㔞ࡢከ࠸࢞ࣛࢫ୰࡛ࡢ Fe ࢖࢜ࣥࡢᵓ㐀࡜ࡢ㐪࠸ࢆㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊFe ࢖࢜ࣥࡢ X ⥺྾཰࡟ࡣ㓟໬㕲㔞࡛᫂░࡞㐪࠸ࡀㄆࡵࡽࢀࠊࡲࡓࡑࡢ FeO ๭ྜ࡟ࡼࡿኚ໬࡟ࡶ㐪࠸ࡀ࠶ࡿࡇ࡜ࡀศࡾࠊFe ࢖࢜ࣥࡢᵓ㐀ࡀ㓟໬㕲㔞࡟ࡼࡗ࡚␗࡞ࡿࡇ࡜ࡀࡼࡾ᫂☜࡟࡞ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸  XAFSࠊࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫࠊFe ࢖࢜ࣥࠊᵓ㐀⫼ᬒ࡜◊✲┠ⓗ㸸ࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫ࡜࿧ࡤࢀࡿ Na2O-MgO/CaO-SiO2 ⣔࢞ࣛࢫࡣᘓ⠏ࠊ⮬ື㌴⏝ࡢ❆࢞ࣛࢫ࠶ࡿ࠸ࡣ✀ࠎࡢࢹࣂ࢖ࢫࡢᇶᯈ࡜ࡋ࡚ᗈࡃ⏝࠸ࡽࢀ࡚࠸ࡿࡀࠊࡑࡢ୰࡟ࡣ㓟໬㕲ࡀ୙⣧≀࡜ࡋ࡚࠶ࡿ࠸ࡣពᅗⓗ࡟ຍ࠼ࡽࢀ࡚ᚲࡎᏑᅾࡍࡿࠋ㓟໬㕲ࡣ࢞ࣛࢫ୰࡛ࡣ㏻ᖖ FeO㸪Fe2O3 ࡢ୧᪉ࡀ࠶ࡿ
୍ᐃࡢ๭ྜ࡛Ꮡᅾࡋࠊ୍⯡ⓗ࡟ Fe2+ࡣ㓟⣲ 6 㓄఩ᵓ㐀ࢆྲྀࡾ⥙┠ಟ㣭࢖࢜ࣥ࡟ࠊFe3+ࡣ㓟⣲ 4 㓄఩ᵓ㐀ࢆྲྀࡾ⥙┠ᙧᡂ࢖࢜ࣥ࡟࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊFe2+ࡣ୺࡟ 1000nm ௜㏆࡟ࣆ࣮ࢡࢆᣢ
ࡘ྾཰ࢆ♧ࡋ࡚࢞ࣛࢫ࡟㟷ⰍࡢⰍㄪࢆ୚࠼ࠊFe3+ࡣ୺࡟⣸እᇦ࡟ᙉ࠸྾཰ࢆᣢࡕ㯤ⰍࡢⰍㄪࢆ୚
࠼ࡿࠋࡋࡓࡀࡗ࡚ࠊ࢞ࣛࢫࡢⰍㄪ࠶ࡿ࠸ࡣ㏆㉥እࠊ⣸እ㏱㐣⋡࡞࡝ࡢගᏛ≉ᛶࢆタィࡍࡿୖ࡛ࡑ
ࢀࡽࡀ࢞ࣛࢫ୰࡛࡝ࡢࡼ࠺࡞ᵓ㐀ࢆྲྀࡗ࡚࠸ࡿ࠿ࡣ㠀ᖖ࡟㔜せ࡞᝟ሗ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊୖグᵓ㐀௨እ࡟ Fe2+ࡣ୍㒊㓟⣲ 4 㓄఩ᵓ㐀ࢆྲྀࡾ[1]ࠊFe3+ࡣࡑࡢ㔞࠶ࡿ࠸ࡣ㓟໬㕲୰ࡢ FeO ࡢ๭ྜ㻔௨ᚋ FeO ๭ྜ㻕࡟ࡼࡗ࡚ࡣ㓟⣲ 6 㓄఩ᵓ㐀ࢆྲྀࡾ࠺ࡿ[2]࡜⪃࠼ࡽࢀ࡚࠸ࡿ࡞࡝ࠊ࢞ࣛࢫ୰࡛ࡢࡑࡢᵓ㐀ࡣ᏶඲࡟ゎ᫂ࡉࢀ࡚࠸ࡿ࡜ࡣゝ࠼࡞࠸ࠋࡲࡓࠊ➹⪅ࡽࡣ᫖ᖺ SPring-8 ࡛ࡢㄢ㢟 2008A1917
࡟࠾࠸࡚ 0.005 ࣔࣝ%ࢆ᭱ప࡟ࡑࢀࡼࡾከ࠸㔞ࡢ㓟໬㕲ࢆ୺࡟ῧຍࡋࡓࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫࡢ
Fe-K ➃ࡢ XAFS ᐃࢆึࡵ࡚⾜࠸ࠊFe ࡢ X ⥺྾཰ ᐃࡀ࢞ࣛࢫ୰ࡢ Fe ࢖࢜ࣥࡢᵓ㐀ゎᯒ࡟᭷ຠ࡜ࡢឤゐࢆᚓࡓࠋࡑࡇ࡛ࠊᮏㄢ㢟࡛ࡣ 0.005 ࣔࣝ%ࡢ㓟໬㕲ࢆῧຍࡋࠊࡑࡢ FeO ๭ྜ࠶ࡿ࠸ࡣẕ⤌ᡂࢆኚ໬ࡉࡏࡓ࢞ࣛࢫࡢ Fe-K ➃ࡢ XAFS ᐃࢆ⾜࠸ࠊ㓟໬㕲㔞ࠊࡑࡢ FeO ๭ྜ࠶ࡿ࠸ࡣẕ⤌ᡂ࡟ࡼࡿ Fe ࡢ X ⥺྾཰ࡢኚ໬ࢆࡼࡾ᫂☜࡟ࡍࡿࡇ࡜ࢆヨࡳࡓࠋᐇ㦂㸸ࣔࣝ%࡛ 72SiO2㺃1Al2O3㺃6MgO㺃8CaO㺃13Na2O 㻔SML ⤌ᡂ㻕ࢆẕ⤌ᡂ࡜ࡍࡿࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫ
ࢆࠊ5cm ゅ×5mm ཌ࡟ษ᩿◊☻ࡋ XAFS ᐃ⏝ࡢヨᩱ࡜ࡋࡓࠋ㓟໬㕲ࢆῧຍࡋ࡞࠸࢞ࣛࢫࡣࠊཎᩱࡢ୙⣧≀➼࠿ࡽΰධࡍࡿ㓟໬㕲ࢆ 3ppm ྵ᭷ࡍࡿࡇ࡜ࡀ໬Ꮫศᯒ࠿ࡽศࡗ࡚࠸ࡿࠋ௒ᅇࡢ ᐃ࡛ࡣ㓟໬㕲ࡢῧຍ㔞ࡣ 0.005 ࣔࣝ%࡜ࡋࠊࡇࡢሙྜ㏻ᖖࡢཎᩱ㓄ྜ࠾ࡼࡧ⁐⼥᮲௳࡛ࡣ࢞ࣛࢫ୰ࡢ
FeO ๭ྜࡣ⣙ 20%࡛࠶ࡗࡓࠋFeO ๭ྜࡢᙳ㡪ࢆぢࡿヨᩱ࡜ࡋ࡚ࡣࠊ࢞ࣛࢫࡢ⁐⼥ࢆ㏻ᖖࡼࡾ㑏ඖᛶ࡛⾜࠺ࡇ࡜࡟ࡼࡗ࡚ FeO ๭ྜࢆ⣙ 80%࡟㧗ࡵࡓࡶࡢࠊ࠶ࡿ࠸ࡣཎᩱ୰࡟㓟໬๣࡜ࡋ࡚ 0.2 㔜㔞%ࡢ CeO2 ࢆῧຍࡍࡿࡇ࡜࡟ࡼࡗ࡚ FeO ๭ྜࢆ࡯ࡰ 0 ࡜ࡋࡓࡶࡢࢆྜࢃࡏ࡚స〇ࡋࡓࠋẕ⤌ᡂࡢᙳ㡪ࢆぢࡿࡓࡵ࡟ࡣࠊࣔࣝ%࡛
72SiO2㺃1Al2O3㺃14MgO㺃13Na2O㻔SM ⤌ᡂ㻕
72SiO2㺃1Al2O3㺃14CaO㺃13K2O 㻔PL ⤌ᡂ㻕࡜ࡋࡓẕ⤌ᡂࡢ࢞ࣛࢫࢆྜࢃࡏ࡚స〇ࡋࡓࠋࡇࡢሙྜࡢ FeO ๭ྜࡣࠊSM ⤌ᡂ࡛ࡣ⣙ 15%ࠊPL ⤌ᡂ࡛ࡣ⣙ 45%࡛࠶ࡗࡓࠋ
ࡇࡢࡼ࠺࡟స〇ࡋࡓ࢞ࣛࢫヨᩱ࡟ࡘ࠸࡚ࠊBL14B2 ࡟࠾࠸࡚ 19 ⣲Ꮚ SSD ࢆ⏝࠸ࡓ⺯ගἲ࡛ Feࡢ K ➃ࡢ X ⥺྾཰ࡢ ᐃࢆ⾜ࡗࡓࠋࡲࡓࠊཧ↷ヨᩱ࡜ࡋ࡚ヨ⸆ࡢ Fe2O3 ⢊ᮎ࡟ࡘ࠸࡚ XAFS ࢆ❅໬࣍࢘⣲⢊ᮎ࡜ΰྜࡋຍᅽᡂᆺ࡟ࡼࡾ࣌ࣞࢵࢺ≧࡟ᡂᙧࡋࡓᚋ㏱㐣ἲ࡟ࡼࡾ ᐃࡋ๓ᅇ ᐃࡢ⤖ᯝ࡜ẚ㍑ࡋࡓࡀࠊ࢚ࢿࣝࢠ࣮ࡢࢬࣞࡣ࡯࡜ࢇ࡝࡞࠿ࡗࡓࠋ
⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
1. 㓟໬㕲ࢆῧຍࡋ࡞࠸ሙྜ 㓟໬㕲ࢆῧຍࡏࡎࡑࡢ㓟໬㕲ྵ᭷㔞ࡀ 3ppm ࡢ࢞ࣛࢫࡢሙྜ࡟ࡣࠊ7105eV ௜㏆௨ୖ࡟ㄆࡵࡽࢀ
ࡿ Fe ࡢ྾཰ࡣࢃࡎ࠿࡟ㄆࡵࡽࢀࡓࡶࡢࡢࠊῧຍ㔞 0.005%ࡢ࢞ࣛࢫࡢሙྜ࡟ẚ࡭࡚ࡶ㠀ᖖ࡟ᙅ࠿ࡗࡓࠋ ࡇࡢ ᐃࡣࡇࡢࡼ࠺࡞ᚤ㔞ࡢ㓟໬㕲ࢆྵ᭷ࡍࡿヨᩱࡢ XAFSᐃࡣ㐣ཤ࡟⤒㦂ࡀ↓ࡃࠊ≉࡟
0.005%ࡢࡼ࠺࡞ᴟᚤ㔞ࡢሙྜ࡟ࡣほᐹࡉࢀࡿ X ⥺྾཰ࡀヨᩱ୰ࡢ Fe ࡟ࡼࡿࡶࡢ࡛ࡣ࡞ࡃࠊX ⥺ࡢ⤒㊰୰࡟Ꮡᅾࡍࡿ Fe ࡟ࡼࡿࡶࡢ࡛࠶ࡿྍ⬟ᛶࡶ࠶ࡿ࡜ࡢ SPring-8 ࡢᢸᙜ⪅࠿ࡽࡢᣦ᦬࡟ࡼࡾ⾜࡞ࡗࡓࡶࡢ࡛࠶ࡿࡀࠊࡇࡢ ᐃ࡟ࡼࡾῧຍ㔞ࡀ 0.005%࡜ᴟᚤ㔞࡛࠶ࡗ࡚ࡶほᐹࡉࢀࡓ 7105eV ௜㏆௨ୖࡢ X ⥺྾཰ࡣ࢞ࣛࢫ୰ࡢ Fe ࢖࢜ࣥ࡟ࡼࡿࡶࡢ࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊ㓟໬㕲ྵ᭷㔞ࡀ 0.005%ࡢሙྜࡢ X ⥺྾཰࡛ࡶ 3ppm ࡢሙྜ࡟ẚ࡭࠿࡞ࡾᙉࡃࠊ㓟໬㕲㔞ࡣࡉࡽ࡟ᑡ㔞࡛ࡶ࢞ࣛࢫ୰ࡢ Fe ࡢ X ⥺྾཰ࡢ ᐃࡣྍ⬟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ㻲㼑㻜㻚㻜㻜㻡㼋㻲㼑㻻㼪㻜㻲㼑㻜㻚㻜㻜㻡㼋㻲㼑㻻㻌㻞㻜㻑㻵㼚㼠㼑㼚㼟㼕㼠㼥㻌㻔㼍㼞㼎㼕㼠㻚㼡㼚㼕㼠㻕㻵㼚㼠㼑㼚㼟㼕㼠㼥㻌㻔㼍㼞㼎㼕㼠㻚㼡㼚㼕㼠㻕

2㸬FeO ๭ྜࡢᙳ㡪
FeO ๭ྜࢆ࡯ࡰ 0 ࠿ࡽ⣙ 80%ࡢ㛫࡛ኚ໬ࡉࡏࡓ࢞ࣛࢫࡢࠊ
Fe-K ➃ࡢ XANES ࢫ࣌ࢡࢺࣝࢆ Fig.1㻔1㻕࡟♧ࡍࠋẚ㍑ࡢࡓࡵࠊࡇࢀࡲ࡛ ᐃࡋࡓ㓟໬㕲㔞 0.5%ࡢሙྜ࡟ࡘ࠸࡚ࠊFeO ๭ྜࢆ࡯ࡰ 0 ࠿ࡽ⣙
60%ࡢ㛫࡛ኚ໬ࡉࡏࡓ࢞ࣛࢫࡢࡑࢀࡽࢆ Fig.1㻔2㻕࡟♧ࡋࡓࠋ㻲㼑㻜㻚㻡㼋㻲㼑㻻㼪㻜㻲㼑㻜㻚㻡㼋㻲㼑㻻㻞㻜㻑㻲㼑㻜㻚㻜㻜㻡㼋㻲㼑㻻㻌㻤㻜㻑
㻣㻝㻜㻜

㻣㻝㻝㻜

㻣㻝㻞㻜

㻣㻝㻟㻜

㻣㻝㻠㻜

㼑㼚㼑㼞㼓㼥㻌㻔㼑㼂㻕

㻣㻝㻡㻜

㻣㻝㻢㻜

㻣㻝㻣㻜

㻣㻝㻤㻜㻲㼑㻜㻚㻡㼋㻲㼑㻻㻢㻜㻑
㻣㻝㻜㻜

㻣㻝㻝㻜

㻣㻝㻞㻜

㻣㻝㻟㻜

㻣㻝㻠㻜

㻣㻝㻡㻜㻣㻝㻢㻜

㻣㻝㻣㻜

㻣㻝㻤㻜

㼑㼚㼑㼞㼓㼥㻌㻔㼑㼂㻕

㻔1㻕 㓟໬㕲㔞 0.005㸣             㻔2㻕 㓟໬㕲㔞 0.5㸣Fig.1. 㓟໬㕲ῧຍ㔞 0.005%࠾ࡼࡧ 0.5%࡛ FeO ๭ྜࢆኚ໬ࡉࡏࡓ
࢞ࣛࢫࡢ Fe ࡢ XANES ࢫ࣌ࢡࢺࣝ㓟໬㕲ῧຍ㔞 0.5%ࡢሙྜ࡟ࡣࠊFe ࡢ྾཰ࡣ FeO ๭ྜࡢቑຍ࡜ඹ࡟ప࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋࠊࡑࡢ఩⨨ࢆ྾཰ᙉᗘࡀ᭱኱ࡢ᫬ࡢ 1/2 ࡟࡞ࡿ࢚ࢿࣝࢠ࣮࡛⾲ࡋࡓሙྜࠊFeO ๭ྜࡀ࡯ࡰ 0 ࡢሙྜ
࡛ 7222eVࠊ⣙ 20%ࡢሙྜ࡛ 7121eVࠊ⣙ 60%ࡢሙྜ࡛ 7119eV ࡛࠶ࡗࡓࠋࡇࢀࡣࠊFe ࡢ X ⥺྾཰ࡣࡑࡢཎᏊ౯ࡀᑠࡉࡃ࡞ࡿ࡯࡝ప࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡍࡿࡢ࡟┦ᙜࡍࡿ࡜ゎ㔘ࡉࢀࡓࠋࡇࢀ࡟ᑐࡋ௒ᅇ ᐃࡋࡓ 0.005%ࡢሙྜ࡟ࡣࠊFe ࡢ X ⥺྾཰ࡢ఩⨨ࡣ FeO ๭ྜࡀኚ໬ࡋ࡚ࡶ࡯࡜ࢇ࡝ኚ໬ࡏࡎࠊࡑࡢ఩⨨ࢆ྾཰ࡀ᭱኱ࡢ᫬ࡢ 1/2 ࡟࡞ࡿ࢚ࢿࣝࢠ࣮࡛⾲ࡋࡓሙྜࠊFeO ๭ྜࡀ࡯ࡰ 0 ࡢሙྜ࡛ࡶ 7119eV ࡛ 0.5%ࡢሙྜ࡜ẚ㍑ࡋ྾཰ࡣ᫂ࡽ࠿࡟ప࢚ࢿࣝࢠ࣮ഃ࡟఩⨨ࡋࠊ⣙ 20%ࡢሙྜ
࡜⣙ 80%ࡢሙྜ࡜࡛࡯࡜ࢇ࡝ᕪࡀ↓ࡃ 7118eV ࡛ࠊࡑࢀࡽࡢ XANES ࢫ࣌ࢡࢺࣝࡢᙧ≧ࡣ 0.5%ࡢ
ሙྜࡢ FeO ๭ྜࡀ⣙ 60%ࡢሙྜࡢࡑࢀ࡟Ⰻࡃఝ࡚࠸ࡓࠋ
ୖグ⤖ᯝࡣࠊ㓟໬㕲㔞ࡀ 0.005%⛬ᗘ࡜㠀ᖖ࡟ᑡ࡞࠸ሙྜ Fe ࡢ X ⥺྾཰ࡣࡑࡢ FeO ๭ྜ࡟࡯࡜ࢇ࡝ᙳ㡪ࡉࢀࡎࠊFe3+ࡀ Fe2+࡟㏆࠸࢚ࢿࣝࢠ࣮ࡢ X ⥺ࢆ྾཰ࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࡞ࡐࡑࡢࡼ࠺࡞ᣲືࢆ♧ࡍࡢ࠿ࡣ௒ࡢ࡜ࡇࢁศ࠿ࡗ࡚࠸࡞࠸ࠋ㻵㼚㼠㼑㼚㼟㼕㼠㼥㻌㻔㼍㼞㼎㼕㼠㻚㼡㼚㼕㼠㻕

3. ẕ⤌ᡂࡢᙳ㡪ẕ⤌ᡂࡀ SM ⤌ᡂ࠾ࡼࡧ PM ⤌ᡂࡢ࢞ࣛࢫࡢ Fe-K ➃ࡢ XANES ࢫ࣌ࢡࢺࣝࢆࠊFig.1 ࡟♧ࡋࡓẕ⤌ᡂࡀ SML ⤌ᡂࡢሙྜ࡜ඹ࡟ Fig.2 ࡟♧ࡍࠋ㻲㼑㻜㻚㻜㻜㻡㼋㻿㻹㻸㻲㼑㻜㻚㻜㻜㻡㼋㻿㻹㻲㼑㻜㻚㻜㻜㻡㼋㻼㻯㻣㻝㻜㻜㻣㻝㻝㻜㻣㻝㻞㻜㻣㻝㻟㻜㻣㻝㻠㻜㻣㻝㻡㻜㻣㻝㻢㻜㻣㻝㻣㻜㻣㻝㻤㻜㼑㼚㼑㼞㼓㼥㻌㻔㼑㼂㻕Fig.2. ẕ⤌ᡂࢆኚ໬ࡉࡏࡓ࢞ࣛࢫࡢ Fe ࡢ XANES ࢫ࣌ࢡࢺࣝ2㸬࡛ SML ⤌ᡂࡢሙྜ࡟ㄆࡵࡽࢀࡓࠊX ⥺྾཰ࡢ࢚ࢿࣝࢠ࣮ࡀ㓟໬㕲㔞 0.5%ࡢሙྜ࡜ẚ㍑ࡋప
࢚ࢿࣝࢠ࣮ഃ࡟ほᐹࡉࢀࡿ⌧㇟ࡣࠊSM ⤌ᡂࠊPL ⤌ᡂࡢሙྜ࡟ࡶྠᵝ࡟ㄆࡵࡽࢀࡓࠋ๓ᅇ ᐃࡢ0.17%ࡢሙྜ࡜ྠᵝࠊ௒ᅇࡢ ᐃ࡛ࡣ࢞ࣛࢫࡢẕ⤌ᡂࡢኚ໬࡟కࡗ࡚㓟໬㕲ࡢ FeO ๭ྜࡶኚ໬ࡋ࡚࠾ࡾࠊ࢞ࣛࢫࡢẕ⤌ᡂࡢ┦㐪ࡢࡳ࡟ࡼࡿ XANES ࢫ࣌ࢡࢺࣝࡢᙧ≧ኚ໬ࢆぢࡿࡇ࡜ࡀฟ᮶࡞࠿ࡗࡓࠋࡋ࠿ࡋࠊ๓ᅇ ᐃ⤖ᯝ࡜ྜࢃࡏࠊࡑࡢኚ໬ࡣ FeO ๭ྜࡢኚ໬ࡢࡳ࡟ࡼࡿࡶࡢ࡛ࡣ࡞ࡃ࢞ࣛࢫࡢẕ⤌ᡂࡢ㐪࠸ࡶ཯ᫎࡋࡓࡶࡢ࡜⪃࠼࡚࠸ࡿࠋ๓ᅇ ᐃࡢ 0.17%ࡢሙྜ࡟ࡣ࢞ࣛࢫࡢẕ⤌ᡂࡢ㐪࠸࡟ࡼࡗ࡚ XANES ࢫ࣌ࢡࢺࣝࡢᙧ≧ࡣ㠀ᖖ࡟ࢃࡎ࠿ࡋ࠿ኚ໬ࡋ࡞࠿ࡗࡓࡀࠊ௒ᅇࡢ ᐃ࡛ࡣࡑࡢኚ໬ࡣࡑࢀࡼࡾࡶ኱ࡁ࠿ࡗࡓࠋࡇࡢࡇ࡜ࡣ㓟໬㕲㔞ࡀ 0.005%⛬ᗘ࡜㠀ᖖ࡟ᑡ࡞࠸ሙྜ࡟ࡣࠊ࢞ࣛࢫ୰ࡢ Fe ࢖࢜ࣥࡢᵓ㐀ࡀ࢞ࣛࢫࡢẕ⤌ᡂ࡟ࡼࡗ࡚ኚ໬ࡋࡸࡍ࠸ࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ2㸬࡛㏙࡭ࡓࡼ࠺࡟㓟໬㕲㔞ࡀᑡ࡞࠸ሙྜࡢ Fe ࡢ X ⥺྾཰≉ᛶ࡟ࡘ࠸࡚ࡣࡲࡔ༑ศゎ᫂ࡉࢀ࡚࠾ࡽࡎࠊࡇࡢ࢞ࣛࢫࡢẕ⤌ᡂࡢ㐪࠸࡟ࡼࡿ XANES ࢫ࣌ࢡࢺࣝࡢᙧ≧ࡢኚ໬ࡀࠊ࡝ࡢࡼ࠺࡞ᵓ㐀ⓗኚ໬࡟ࡼࡿࡶࡢ࠿ࡢゎᯒࡣ௒ᚋࡢㄢ㢟࡛࠶ࡿࠋ௒ᚋࡢㄢ㢟㸸 ௨ୖ௒ᅇࡢ ᐃ⤖ᯝ࡟๓ᅇࡢ ᐃ⤖ᯝࢆྜࢃࡏࠊࢯ࣮ࢲࣛ࢖࣒࢞ࣛࢫ࡟ 0.005㸫0.5 ࣔࣝ%⛬ᗘྵࡲࢀ࡚࠸ࡿ㓟໬㕲ࡢ♧ࡍ Fe ࡢ X ⥺྾཰ࡣࠊࡑࡢ㓟໬㕲㔞࡟౫Ꮡࡋࡑࡢ㔞ࡀᑡ࡞࠸ሙྜ࡟ࡣ Fe3+
ࡀ Fe2+ࡢࡼ࠺࡞྾཰ࢆ㉳ࡇࡍ࡜࠸࠺᪂つ࡞▱ぢࡀᚓࡽࢀࡓࠋࡋ࠿ࡋࠊࡑࢀࡀ࡝ࡢࡼ࠺࡞ Fe ࢖࢜ࣥࡢᵓ㐀࡟ࡼࡿࡶࡢ࠿ࡣ X ⥺྾཰ ᐃࡢࡳ࡛ࡣᅔ㞴࡛࠶ࡿࡇ࡜ࡶศࡗ࡚ࡁࡓࠋ௒ᚋࡣᚓࡽࢀࡓ
XANES ࢫ࣌ࢡࢺࣝࡢᙧ≧ࢆࠊ➨୍ཎ⌮ィ⟬࡟ࡼࡿ X ⥺྾཰ࡢィ⟬➼࠿ࡽゎᯒࡍࡿࡇ࡜ࢆྜࢃࡏ࡚⾜࠸ࠊ࢞ࣛࢫ୰ࡢ Fe ࢖࢜ࣥࡢᵓ㐀ࢆࡼࡾ᫂ࡽ࠿࡟ࡋ࡚࠸ࡃணᐃ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸
[1]D. Goldman, J. Berg, J. Non-Cryst. Solids, 38&39, 1980, 183-188[2]B. Hannoyer, M. Lenglet, J. Duerr, R. Cortes, J. Non-Cryst. Solids,151, 1992, 209-216