http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1836.pdf 2010B1836 BL14B2 ࢜࢟ࢩሷࢪࣝࢥࢽ࣒࢘⁐ᾮࡢ EXAFS ᵓ㐀ゎᯒ㻔III㻕 EXAFS Analysis of Zirconium Oxychloride Solutions㻔III㻕 㧗ᓮ ྐ㐍 a, ᑠᕝ ಙ᫂ b, すᕝ ᣅ a, ᚋᒸ ᐅᏕ a Fumiyuki Takasakia, Nobuaki Ogawab, Taku Nishikawaa, Nobutaka Nochiokaa a ➨୍⛥ඖ⣲Ꮫᕤᴗ㻔ᰴ㻕, b ⛅⏣ᏛᕤᏛ㈨※Ꮫ㒊 aDaiichi Kigenso Kagaku Kogyo. Co. Ltd., b Faculty of Engineering and Resource Science, Akita University ࢜࢟ࢩሷࢪࣝࢥࢽ࣒࢘ࡢ⤖ᬗ ZrOCl2࣭8H2O ⁐ᾮࡢ EXAFS ᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋᐊ ࡛࢚࣮ࢪ ࣥࢢࡋࡓ[Zr]=0.1mol/L ࠾ࡼࡧ 0.01mol/L ⁐ᾮ࡛ࡣ⁐Ꮡᵓ㐀ᕪࡀ࡞ࡗࡓࠋࡲࡓࠊ㔜ྜయࢆᵓᡂ ࡍࡿ᭱ࡢ⛛ᗎ༢ࡣ 8㹼16 㔞య⛬ᗘ࡛࠶ࡿࡇࡀࢃࡗࡓࠋ୍᪉ࠊ⁐ᾮࢆ 50Υ࡛࢚࣮ࢪࣥࢢࡋ ࡓࡇࢁ 4 㔞యࡢᵓ㐀ࡀศゎࡋࡓ㓟ࢪࣝࢥࢽ࣒࢘ࡢ๓㥑య⪃࠼ࡽࢀࡿ᪂ࡋ࠸Ꮫ✀ࡀ᳨ฟࡉ ࢀࡓࠋ ࣮࣮࢟࣡ࢻ㸸 ࢜࢟ࢩሷࢪࣝࢥࢽ࣒࢘ࠊ㔜ྜࠊᯫᶫ ⫼ᬒ◊✲┠ⓗ㸸 ࢜࢟ࢩሷࢪࣝࢥࢽ࣒࢘ࡣ㧗ศᏊྜ≀ࡢᯫᶫࡋ࡚ࠊࡲࡓࠊከࡃࡢ Zr ྜ≀ࡢཎᩱ࡞ࡿ ᕤᴗⓗ㔜せ࡞ྜ≀࡛࠶ࡿࠋሷ Zr ⁐ᾮ୰࡛ࠊZr Ꮫ✀ࡀᡂศ⃰ᗘ౫Ꮡࡋ࡚ຍỈศゎࡋ㔜ྜ ᵓ㐀ࢆᙧᡂࡍࡿࡇࡣྂࡃࡽ▱ࡽࢀ࡚࠸ࡓࡀ[1]ࠊࡑࡢヲ⣽ࡘ࠸࡚ࡣศᯒᡭἲࡢ㝈⏺ࡢࡓࡵ ࢇࢃࡗ࡚࠸࡞ࡗࡓࠋࡋࡋࠊZr ⁐ᾮࡣࡌࡵ࡚ EXAFS ศᯒࢆ㐺⏝ࡋࡓᑠᕝࡽࡢ◊✲ ࡼࡗ࡚ Zr ⁐ᾮࡢ EXAFS ศᯒࡢ᭷ຠᛶࡀ♧ࡉࢀࡓ[2]ࠋ ሷ Zr ⁐ᾮࡢ⁐Ꮡᵓ㐀ࡣᯫᶫᶵ⬟ࡸࡑࢀࢆཎᩱࡍࡿୗὶ〇ရࡢ≀ᛶᙳ㡪ࡍࡿ⪃࠼ࡽࢀࠊ ⁐Ꮡᵓ㐀ࡢไᚚࡼࡗ࡚᪂ᶵ⬟ࢆᣢࡘሷ Zr ⁐ᾮࢆ㛤Ⓨ࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࠋࡑࡢไᚚࡢࡓࡵ ࡣࠊࡲࡎሷ Zr ⁐ᾮࡢᡂศ⃰ᗘࡸࡑࡢࡢ᮲௳౫Ꮡࡋࡓᵓ㐀ኚࡢヲ⣽ࢆ▱ࡿᚲせࡀ࠶ࡿࠋ 2007B1843ࠊ2008B2117 ࠾࠸࡚ࠊሷ Zr ⁐ᾮࡘ࠸࡚ EXAFS ᵓ㐀ゎᯒࢆᐇࡋࡓࠋࡑࡢ⤖ᯝࠊ [H+]ࠊ[Cl-]୧᪉౫Ꮡࡋࡓ Zr-Zr 㓄ᩘࡢቑῶࠊ༶ࡕ㔜ྜᗘࡢኚࡀほ ࡉࢀࡓࠋࡲࡓࠊ≉ᐃࡢẚ [Cl-]/[Zr]=0.7 ࡛ࡣᡂศ⃰ᗘࡼࡽࡎ㧗࠸ Zr-Zr 㓄ᩘࢆ⥔ᣢࡍࡿࡇࡀࢃࡗࡓࠋࡇࡢ⁐ᾮࡣ࣏ࣜ ࣅࢽࣝࣝࢥ࣮ࣝࣇ࣒ࣝࡢ⪏Ỉᛶࢆྥୖࡉࡏࡿᶵ⬟ඃࢀࡿࡇࡀࢃࡗࡓ[3]ࠋࡇࢀࡣ Zr ࡢ⁐ Ꮡᵓ㐀ᶵ⬟ࡢ㛵ಀࢆึࡵ࡚᫂ࡽࡋࡓⅬ࡛㠉᪂ⓗ࡞ᡂᯝ࡛࠶ࡗࡓࠋ ࢜࢟ࢩሷ Zr ⤖ᬗ㻔ZrOCl2࣭8H2O㻕୰ࡢ 4 㔞యࡢᵓ㐀ࢆ Fig.1 ♧ࡍࠋࡇࡢ⤖ᬗࡢ[Zr]=1M㻔mol/L㻕 ⁐ᾮ࡛ࡣࠊFig.1 ࡢ 4 㔞యᵓ㐀࡛⁐Ꮡࡋ࡚࠸ࡿࡇࡀ᫂ࡽ࡞ࡗ࡚࠸ࡿ[2]ࡓࡵࠊ࢜࢟ࢩሷ Zr ⤖ᬗ⁐ᾮ୰࡛⏕ᡂࡍࡿ㔜ྜయࡣ 4 㔞యࢆᵓᡂ༢ࡋࡓࡶࡢ࡛࠶ࡿ᥎ ࡋࡓࠋ㐣ཤࡢᐇ㦂ࡽ ▷㊥㞳㻔3.559ύ㻕ࡢ Zr-Zr 㓄ࡀ 4 ⛬ᗘ࡛㣬ࡍࡿࡇࡀண ࡉࢀࡓࡢ࡛ࠊࡑࢀᇶ࡙ࡃ 4 㔞యࡢ㔜 ྜࣔࢹࣝࡋ࡚ࠊᖹ㠃ᡂ㛗ࣔࢹࣝࢆணࡋࡓࠋ4 㔞యࡢᖹ㠃≧㔜ྜࣔࢹࣝࢆ Fig.2 ♧ࡍࠋFig.2 ࡢሙྜࠊ4 㔞యࡢ▷㊥㞳ࡢ Zr-Zr 㓄ᩘࡣ 3.3ࠊᑐゅࡢ㛗㊥㞳 Zr-Zr 㓄㻔5.032ύ㻕ᩘࡣ 2.8 ࡞ࡿࠋ ᑐゅࡢ㛗㊥㞳 Zr-Zr 㓄ᵓ㐀ࡣ 4 㔞యྠኈࡀ 2 㡬Ⅼ࡛⤖ྜࡋࡓሙྜࡋ⏕ᡂࡋ࡞࠸ࠋࡇࡢ㛗㊥㞳 ࡢ Zr-Zr 㓄ࢆᐃ㔞ⓗゎᯒࡍࡿࡇ࡛ࡼࡾලయⓗ࡞㔜ྜᵓ㐀ࣉ࣮ࣟࢳࡍࡿࡇࡀᮏᐇ㦂ࡢ 㔜せㄢ㢟࡛࠶ࡗࡓࠋᮏᐇ㦂࡛ࡣࠊᚤᙅ࡞ 4 㔞యࡢᑐゅ㓄ࡼࡿ EXAFS ືࢆ㧗⢭ᗘ࡛ほ ࡍࡿ ࡓࡵ㐣ཤࡢᐇ㦂ࡼࡾࡶ㛗㛫ࡢ ᐃࢆᐇࡋࠊ✚⟬ᅇᩘࢆቑࡸࡋࡓࠋ Zr Zr Zr Zr OH H OH 㸸4 㔞య 㸸2 㔜ࡢ OH-ᯫᶫ ▷㊥㞳ࡢ Zr-Zr 㓄 3.559ύ 㛗㊥㞳ࡢ Zr-Zr 㓄 5.032ύ Fig.1㸬࢜࢟ࢩሷ Zr ⤖ᬗ 㻔ZrOCl2࣭8H2O㻕୰ࡢ 4 㔞య Fig.2㸬4 㔞యࡢᖹ㠃≧㔜ྜࣔࢹࣝ ᐇ㦂㸸 ࢜࢟ࢩሷ Zr ⤖ᬗ㻔ZrOCl2࣭8H2Oࠊ≉⣭ヨ⸆ࠊ୕ὠᏛ㻕ࢆ࢜ࣥỈ⁐ゎࡋࠊ[Zr]=0.01M ࠾ࡼࡧ 0.1M ࡢ⁐ᾮࢆㄪ〇ࡋࡓࠋ⁐ᾮࡣᡤᐃࡢ᮲௳࡛࢚࣮ࢪࣥࢢࡋࡓࠋ[Zr]=1M ࡢ⁐ᾮࢆ 14 ᪥ ࡅ࡚ 5 ẁ㝵࡛ 0.01M ࡲ࡛ᕼ㔘ࡋࡓ⁐ᾮࢆㄪ〇ࡋࡓ㻔ヨᩱ No.11㻕ࠋ[Zr]=0.01M ࡢ⁐ᾮࢆᐊ ࡛ 14 ᪥ ࢚࣮ࢪࣥࢢࡋࡓᚋࠊ᪂ࡓㄪ〇ࡋࡓ[Zr]=0.01M ࡢ⁐ᾮ༙㔞ࡎࡘΰྜࡋࡓ⁐ᾮࢆ 12 ᪥ᐊ ࡛࢚࣮ ࢪࣥࢢࡋࡓ㻔ヨᩱ No.12㻕ࠋࡇࢀࡽࡣࠊ㔜ྜయࡢ᰾⏕ᡂᡂ㛗㏿ᗘኚࢆ࠼ࡿࡇ࡛ࠊࡼࡾࡁ ࡞⛛ᗎᵓ㐀ࡢ⏕ᡂࢆᮇᚅࡋࡓࡶࡢ࡛࠶ࡿࠋ࢜࢟ࢩሷ Zr ⤖ᬗࢆ⢊○ࡋࠊ❅࣍࢘⣲࡛ᕼ㔘ࡋࡓ 1mm ཌࠊ10mm ᚄࡢ࣌ࣞࢵࢺࢆసᡂࡋࡓ㻔ヨᩱ No.13㻕ࠋࡇࢀࡽࡢ⁐ᾮ࠾ࡼࡧ࣌ࣞࢵࢺࡢ Zr-K ྾ ➃ XAFS ࢆࢡࢵࢡࢫ࡛࢟ࣕࣥ ᐃࡋࡓࠋ ศග⤖ᬗࡣ Si㻔111㻕ࢆ⏝࠸ࡓࠋ⁐ᾮࡣ࣏ࣜ⿄ᐦᑒࡋࠊᑓ⏝ࡢ❆࣍ࣝࢲධࢀ࡚ᅛᐃࡋࡓࠋ ග㊰㛗ࡣࠊ࣌ࣞࢵࢺࡣ 1mmࠊ[Zr]=0.01M ࡣ 40mmࠊ0.1M ࡣ 15mm ࡋࡓࠋ[Zr]=0.01M ࡣ 5 ศࡢ ᐃࢆ 7 ᅇ⧞ࡾ㏉ࡋࠊࢫ࣌ࢡࢺࣝࢆ✚⟬ࡋࡓࠋ0.1M ࡣ 5 ᅇ⧞ࡾ㏉ࡋ࡚✚⟬ࡋࡓࠋEXAFS ᵓ㐀ゎᯒ ࡣ REX2000㻔RIGAKU㻕ࢆ⏝࠸ࡓࠋ ࣇ䤀࢚ࣜኚᙉᗘ ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 Table 1 ྛヨᩱࡢᏛ⤌ᡂ୪ࡧྛ Zr-Zr 㓄ࡢ㓄ᩘࠊ㓄㊥㞳࠾ࡼࡧ Debye-Waller ᅉᏊ㻔௨ ୗ DW㻕ࢆ♧ࡍࠋFig.3 ྛヨᩱࡢࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋFig.3 ࠾࠸࡚ࠊ3.0㹼3.5ύ㏆ ࡢ➨ࣆ࣮ࢡࢆ▷㊥㞳ࡢ Zr-Zr 㓄ࠊࡲࡓࠊ5ύ㏆ࡢ➨୕ࣆ࣮ࢡࢆ㛗㊥㞳ࡢ Zr-Zr 㓄ࡋ࡚ࣇ ࢵࢸࣥࢢࡋࡓࠋ㛗㊥㞳ࡢ Zr-Zr 㓄ࡢ DW ࡣ 0.09ύᅛᐃࡋࡓࠋ 㛗㊥㞳ࡢ Zr-Zr 㓄㊥㞳▷㊥㞳ࡢ Zr-Zr 㓄 Zr-O 㓄 ㊥㞳ࡢẚࡣ 2 ࡢᖹ᪉᰿㏆࠸್࡞ࡾࠊFig.3 ࡢ ᵏᵎᵌᵎᴾ ➨୕ࣆ࣮ࢡࡣ☜ 4 㔞యࡢᑐゅᡂศ࡛࠶ࡿࡇ ࡀ♧ࡉࢀࡓ㻔Table 1㻕ࠋ ▷㊥㞳ࡢ Table 2 4 㔞యࢆ༢ࡋࡓ㔜ྜᵓ㐀 Zr-Zr Zr-Zr 㓄 㓄ᩘࡢ⌮ㄽ್ࢆ♧ࡍࠋᐊ ࡛࢚࣮ࢪࣥࢢࡋࡓヨ ᩱ࡛ࡣࠊ▷㊥㞳ࡢ Zr-Zr 㓄ᩘࡀ 3.3㹼3.9ࠊ㛗㊥ 㛗㊥㞳ࡢ ᵓᵌᵎᴾ 㞳ࡢ Zr-Zr 㓄ᩘࡣ 1.7㹼2.0 ࡛࠶ࡗࡓࠋࡋࡓࡀࡗ Zr-Zr 㓄 ࡚ࠊᐊ ࡛࢚࣮ࢪࣥࢢࡋࡓ⁐ᾮ୰࡛ࡣࠊTable 2 ࡢ 8㹼16 㔞యྠኈࡀ 1 㡬Ⅼࡢࡳ࡛ OH ᯫᶫࢆᙧᡂ ᵎᵌᵎᴾ ࡋࠊ㔜ྜࡋࡓ⁐Ꮡᵓ㐀ࡀ᥎ ࡉࢀࡿࠋ ᰾⏕ᡂᡂ㛗㏿ᗘኚࢆ࠼ࡓヨᩱ No.11ࠊ 12 ࡛ࡶ Zr-Zr 㓄ᩘࠊ㊥㞳ࡶࡑࡢࡢヨᩱ ᕪࡀ࡞ࡃࠊ≉ู࡞ᵓ㐀࡛ࡣ࡞ࡗࡓࠋࡋࡋࠊຍ ヨ Ỉศゎ᮲௳ࡢ㑅ᢥࡼࡗ࡚㛗㊥㞳ࡢ Zr-Zr 㓄ᵓ ᩱ 㐀ࡢᙧᡂࠊ༶ࡕࠊ4 㔞యࡢ 2 㡬Ⅼྠኈࡢ⤖ྜࢆࡉ No. R/ύ ࡽቑࡸࡋࡓࡼࡾࡁ࡞⛛ᗎᵓ㐀ࢆ㐀ࡿࡇࡣ ྍ⬟࡛࠶ࡿ⪃࠼ࡽࢀࡿࠋ Fig.3㸬ྛヨᩱࡢࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝ Table 1㸬ྛヨᩱࡢᏛ⤌ᡂ୪ࡧྛ Zr-Zr 㓄ᩘࠊ㓄㊥㞳࠾ࡼࡧ Debye-Waller ᅉᏊ ࢚࣮ࢪࣥ ▷㊥㞳ࡢ 㛗㊥㞳ࡢ 㛗㊥㞳 R ヨ ࢢ Zr-Zr 㓄 Zr-Zr 㓄 [Zr] 㸭 ഛ⪃ pH ᩱ /M DW ᪥ ▷㊥㞳 R No. N R/ύ N R/ύ ᗘ /ύ ᩘ 1 0.01 2.12 ᐊ 3 3.4 3.595 0.079 1.9 5.146 1.43 2 0.01 2.10 ᐊ 12 3.8 3.602 0.084 1.8 5.137 1.43 3 0.01 2.06 ᐊ 26 3.5 3.606 0.081 1.9 5.140 1.43 4 0.01 1.94 50Υ 3 1.8 3.613 0.082 1.1 5.175 1.43 5 0.01 1.89 50Υ 12 1.3 3.480 0.084 6 0.01 1.87 50Υ 26 2.3 3.470 0.101 7 0.1 1.17 ᐊ 3 3.3 3.599 0.078 1.7 5.145 1.43 8 0.1 1.18 ᐊ 12 3.5 3.605 0.081 1.8 5.145 1.43 9 0.1 1.12 ᐊ 26 3.5 3.608 0.083 1.8 5.150 1.43 10 0.1 0.97 50Υ 26 1.5 3.640 0.095 0.9 5.163 1.42 11 0.01 2.08 ᐊ 12 3.9 3.606 0.084 1.9 5.161 1.43 ẁ㝵ⓗᕼ㔘 ࢚࣮ࢪࣥࢢ⁐ᾮ 12 0.01 2.07 ᐊ 12 3.5 3.603 0.080 2.0 5.154 1.43 ᪂⁐ᾮࡢΰྜ 13 ᐊ 2.0 3.559 0.063 1.0 5.032 1.41 ZrOCl2࣭8H2O ⤖ᬗ Table 2㸬4 㔞యࢆ༢ࡋࡓ㔜ྜయࡢᵓ㐀 Zr-Zr 㓄ᩘࡢ⌮ㄽ್ ᵓ㐀 ▷㊥㞳ࡢ Zr-Zr 㓄ᩘ 㛗㊥㞳ࡢ Zr-Zr 㓄ᩘ 2.5 1.5 2.67 1.67 2.75 1.75 3 2.25 㸸4 㔞య 㸸2 㔜ࡢ OH-ᯫᶫ ヨᩱ No.1㹼3ࠊ4㹼6 ࠾ࡼࡧ 7㹼9 ࡢྛ⤌࡛࢚࣮ࢪࣥࢢ㛫క࠺ pH ࡢపୗࡀぢࡽࢀࡓࠋᐊ ࡛ ࡢ࢚࣮ࢪࣥࢢ࡛ࡣ Zr-Zr 㓄ᩘࡸ㓄㊥㞳ࡣࡁࡃኚࡋ࡞࠸ࡀࠊ࢚࣮ࢪࣥࢢࡼࡗ࡚ഹ Ꮫኚࡍࡿࡇࡀ♧၀ࡉࢀࡓࠋ Fig.4 ࢚࣮ࢪࣥࢢ ᗘࡢ␗࡞ࡿ⁐ᾮࡢࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ࢚࣮ࢪࣥࢢ ᗘࡼࡗ ࡚ࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝࡁ࡞㐪࠸ࡀぢࡽࢀࡓࠋ[Zr]=0.1M ࡛ࡣࠊࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝࡢ ➨ࠊ➨୕ࣆ࣮ࢡࡀ 50Υࡢ࢚࣮ࢪࣥࢢࡼࡗ࡚㛗㊥㞳ഃࢩࣇࢺࡋࡓࠋ୍᪉ࠊZr-O 㓄㛵ࢃࡿ ➨୍ࣆ࣮ࢡࡣࢇࢩࣇࢺࡋ࡚࠸࡞ࡗࡓࠋࡇࡢࡇࡽࠊ4 㔞య࠾࠸࡚ Zr-Zr ྠኈࢆ⤖ࢇ࡛ ࠸ࡿ 2 㔜ࡢ OH-ᯫᶫࡢ୍㒊ࡀ⤖ྜࡽゎࢀࡓྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ 50Υ࡛࢚࣮ࢪࣥࢢࡋࡓ[Zr]=0.01M ⁐ᾮࡢࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝࡣ➨୕ࣆ࣮ࢡࡀㄆࡵࡽࢀࡎࠊ 4 㔞యࡢᵓ㐀ࡣࢇᾘኻࡋ࡚࠸ࡿࡇࡀࢃࡗࡓࠋࡲࡓࠊ➨୍ࠊ➨ࣆ࣮ࢡࡣ▷㊥㞳ഃࢩ ࣇࢺࡋ࡚࠾ࡾࠊZr-O 㓄࠾ࡼࡧ Zr-Zr 㓄ࡢ୧᪉ࡢ㊥㞳ࡀ⦰ࡲࡿࡇࡀࢃࡗࡓࠋࡉࡽࠊpH ࡣ ᐊ ẚ࡚ 50Υ࢚࣮ࢪࣥࢢࡢ࠺ࡀ 0.19 పࡗࡓࠋࡇࡢࡇࡽࠊZr-Zr 㛫ࢆࡍࡿ OH-ࡀ H+ ࢆᨺฟࡋ O2-ኚࡋࡓྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ ࢜࢟ࢩሷ Zr ⁐ᾮࢆຍ⇕ࡍࡿࡇ࡛㓟ࢪࣝࢥࢽ࣒࢘ࡀ⏕ᡂࡍࡿࡇࡣࡼࡃ▱ࡽࢀ࡚࠸ࡿ[4]ࠋ 50Υ࡛࢚࣮ࢪࣥࢢࡋࡓ⁐ᾮ࡛ࡣࡑࡢ୰㛫యࡀ⏕ᡂࡋࡓ⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡞ᵓ㐀ࡀ᳨ฟࡉࢀ ࡓඛࡣ࡞ࡃࠊࡑࡢᶵ⬟ࡶᮍ▱࡛࠶ࡿࠋࡇࢀࡽࡢ୰㛫యࡣ୍⯡ⓗ࡞ሷ Zr ⁐ᾮࡣ␗࡞ࡿ⪃࠼ ࡽࢀࡿࡓࡵࠊ᪂ᶵ⬟ࡢⓎ⌧ࡀᮇᚅࡉࢀࡿࠋ 䝣䞊䝸䜶ኚᙉᗘ 㻌㻌㻌㻌㻭㻶㻟 㼇㼆㼞㼉㻩㻜㻚㻝㻹㻘㻌ᐊ 㻘㻌㻞㻢᪥ 㻌㻌㻌㻌㻭㻶㻠 㼇㼆㼞㼉㻩㻜㻚㻝㻹㻘㻌㻡㻜䉝㻘㻌㻞㻢᪥ 㻌㻌㻌㻌㻭㻶㻣 㼇㼆㼞㼉㻩㻜㻚㻜㻝㻹㻘㻌ᐊ 㻘㻌㻞㻢᪥ 㻌㻌㻌㻌㻭㻶㻢 㼇㼆㼞㼉㻩㻜㻚㻜㻝㻹㻘㻌㻡㻜䉝㻘㻌㻞㻢᪥ 㻜 㻝 㻞 㻟 㻾㻛䊅 㻠 㻡 㻢 Fig.4㸬࢚࣮ࢪࣥࢢ ᗘࡢ␗࡞ࡿ⁐ᾮࡢࣇ࣮࢚ࣜኚࢫ࣌ࢡࢺࣝ ᚋࡢㄢ㢟㸸 ࡲ࡛࡞࠸᪂つ࡞⁐Ꮡᵓ㐀ࢆࡿྍ⬟ᛶࢆồࡵ࡚ࠊຍỈศゎ᮲௳ࢆ᳨ウࡍࡿࠋᮏᐇ㦂࡛ヨ ࡳࡓ㛗㊥㞳ࡢ Zr-Zr 㓄ࡢᐃ㔞ゎᯒࡼࢀࡤࠊFig.2 ࡢࡼ࠺࡞⛛ᗎⓗ࡞㔜ྜయࢆ᳨ฟ࡛ࡁࡿ⪃࠼ ࡽࢀࡿࠋࡇࡢࡼ࠺࡞⛛ᗎⓗ࡞㔜ྜయࡀ᪂ᶵ⬟Ⓨ⌧ࡢ㘽࡞ࡿࡶࡢ⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㓟 Zr ࡢ ๓㥑య᥎ᐃࡉࢀࡿᏛ✀ࡣ୍⯡ⓗ࡞ሷ Zr Ỉ⁐ᾮࡣ␗࡞ࡿᶵ⬟ࢆᣢࡘྍ⬟ᛶࡀ࠶ࡿࡓࡵࠊࡇ ࡢᏛ✀ࡢᛂ⏝ᶵ⬟ࢆ᥈⣴ࡍࡿࠋ ཧ⪃ᩥ⊩㸸 [1] A. 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