http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1836.pdf

2010B1836                            BL14B2࢜࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘⁐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 Nochiokaaa➨୍⛥ඖ⣲໬Ꮫᕤᴗ㻔ᰴ㻕, b ⛅⏣኱ᏛᕤᏛ㈨※Ꮫ㒊 aDaiichi Kigenso Kagaku Kogyo. Co. Ltd.,b
Faculty of Engineering and Resource Science, Akita University࢜࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘ࡢ⤖ᬗ ZrOCl2࣭8H2O ⁐ᾮࡢ EXAFS ᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋᐊ ࡛࢚࣮ࢪࣥࢢࡋࡓ[Zr]=0.1mol/L ࠾ࡼࡧ 0.01mol/L ⁐ᾮ࡛ࡣ⁐Ꮡᵓ㐀࡟ᕪࡀ࡞࠿ࡗࡓࠋࡲࡓࠊ㔜ྜయࢆᵓᡂࡍࡿ᭱኱ࡢ⛛ᗎ༢఩ࡣ 8㹼16 㔞య⛬ᗘ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ୍᪉ࠊ⁐ᾮࢆ 50Υ࡛࢚࣮ࢪࣥࢢࡋ
ࡓ࡜ࡇࢁ 4 㔞యࡢᵓ㐀ࡀศゎࡋࡓ㓟໬ࢪࣝࢥࢽ࣒࢘ࡢ๓㥑య࡜⪃࠼ࡽࢀࡿ᪂ࡋ࠸໬Ꮫ✀ࡀ᳨ฟࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࢜࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘ࠊ㔜ྜࠊᯫᶫ⫼ᬒ࡜◊✲┠ⓗ㸸࢜࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘ࡣ㧗ศᏊ໬ྜ≀ࡢᯫᶫ๣࡜ࡋ࡚ࠊࡲࡓࠊከࡃࡢ Zr ໬ྜ≀ࡢཎᩱ࡜࡞ࡿ
ᕤᴗⓗ࡟㔜せ࡞໬ྜ≀࡛࠶ࡿࠋሷ໬ Zr ⁐ᾮ୰࡛ࠊZr ໬Ꮫ✀ࡀᡂศ⃰ᗘ࡟౫Ꮡࡋ࡚ຍỈศゎࡋ㔜ྜᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜ࡣྂࡃ࠿ࡽ▱ࡽࢀ࡚࠸ࡓࡀ[1]ࠊࡑࡢヲ⣽࡟ࡘ࠸࡚ࡣศᯒᡭἲࡢ㝈⏺ࡢࡓࡵ࡯࡜ࢇ࡝ࢃ࠿ࡗ࡚࠸࡞࠿ࡗࡓࠋࡋ࠿ࡋࠊZr ⁐ᾮ࡟ࡣࡌࡵ࡚ EXAFS ศᯒࢆ㐺⏝ࡋࡓᑠᕝࡽࡢ◊✲࡟
ࡼࡗ࡚ Zr ⁐ᾮࡢ EXAFS ศᯒࡢ᭷ຠᛶࡀ♧ࡉࢀࡓ[2]ࠋ
ሷ໬ Zr ⁐ᾮࡢ⁐Ꮡᵓ㐀ࡣᯫᶫᶵ⬟ࡸࡑࢀࢆཎᩱ࡜ࡍࡿୗὶ〇ရࡢ≀ᛶ࡟ᙳ㡪ࡍࡿ࡜⪃࠼ࡽࢀࠊ⁐Ꮡᵓ㐀ࡢไᚚ࡟ࡼࡗ࡚᪂ᶵ⬟ࢆᣢࡘሷ໬ Zr ⁐ᾮࢆ㛤Ⓨ࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࠋࡑࡢไᚚࡢࡓࡵ࡟
ࡣࠊࡲࡎሷ໬ Zr ⁐ᾮࡢᡂศ⃰ᗘࡸࡑࡢ௚ࡢ᮲௳࡟౫Ꮡࡋࡓᵓ㐀ኚ໬ࡢヲ⣽ࢆ▱ࡿᚲせࡀ࠶ࡿࠋ
2007B1843ࠊ2008B2117 ࡟࠾࠸࡚ࠊሷ໬ Zr ⁐ᾮ࡟ࡘ࠸࡚ EXAFS ᵓ㐀ゎᯒࢆᐇ᪋ࡋࡓࠋࡑࡢ⤖ᯝࠊ[H+]ࠊ[Cl-]୧᪉࡟౫Ꮡࡋࡓ Zr-Zr 㓄఩ᩘࡢቑῶࠊ༶ࡕ㔜ྜᗘࡢኚ໬ࡀほ ࡉࢀࡓࠋࡲࡓࠊ≉ᐃࡢẚ[Cl-]/[Zr]=0.7 ࡛ࡣᡂศ⃰ᗘ࡟ࡼࡽࡎ㧗࠸ Zr-Zr 㓄఩ᩘࢆ⥔ᣢࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ⁐ᾮࡣ࣏ࣜࣅࢽࣝ࢔ࣝࢥ࣮ࣝࣇ࢕࣒ࣝࡢ⪏Ỉᛶࢆྥୖࡉࡏࡿᶵ⬟࡟ඃࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓ[3]ࠋࡇࢀࡣ Zr ࡢ⁐Ꮡᵓ㐀࡜ᶵ⬟ࡢ㛵ಀࢆึࡵ࡚᫂ࡽ࠿࡟ࡋࡓⅬ࡛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࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿ[2]ࡓࡵࠊ࢜࢟ࢩሷ໬ Zr⤖ᬗ⁐ᾮ୰࡛⏕ᡂࡍࡿ㔜ྜయࡣ 4 㔞యࢆᵓᡂ༢఩࡜ࡋࡓࡶࡢ࡛࠶ࡿ࡜᥎ ࡋࡓࠋ㐣ཤࡢᐇ㦂࠿ࡽ▷㊥㞳㻔3.559ύ㻕ࡢ Zr-Zr 㓄఩ࡀ 4 ⛬ᗘ࡛㣬࿴ࡍࡿࡇ࡜ࡀண ࡉࢀࡓࡢ࡛ࠊࡑࢀ࡟ᇶ࡙ࡃ 4 㔞యࡢ㔜ྜࣔࢹࣝ࡜ࡋ࡚ࠊᖹ㠃ᡂ㛗ࣔࢹࣝࢆண᝿ࡋࡓࠋ4 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 ࡜࡞ࡿࠋᑐ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ᯒࡍࡿࡇ࡜࡛ࡼࡾලయⓗ࡞㔜ྜᵓ㐀࡟࢔ࣉ࣮ࣟࢳࡍࡿࡇ࡜ࡀᮏᐇ㦂ࡢ㔜せㄢ㢟࡛࠶ࡗࡓࠋᮏᐇ㦂࡛ࡣࠊᚤᙅ࡞ 4 㔞యࡢᑐゅ㓄఩࡟ࡼࡿ EXAFS ᣺ືࢆ㧗⢭ᗘ࡛ほ ࡍࡿࡓࡵ࡟㐣ཤࡢᐇ㦂ࡼࡾࡶ㛗᫬㛫ࡢ ᐃࢆᐇ᪋ࡋࠊ✚⟬ᅇᩘࢆቑࡸࡋࡓࠋ

ZrZr

ZrZr
OHHOH

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యFig.2㸬4 㔞యࡢᖹ㠃≧㔜ྜࣔࢹࣝᐇ㦂㸸࢜࢟ࢩሷ໬ Zr ⤖ᬗ㻔ZrOCl2࣭8H2Oࠊ≉⣭ヨ⸆ࠊ୕ὠ࿴໬Ꮫ㻕ࢆ࢖࢜ࣥ஺᥮Ỉ࡟⁐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 ᪥࢚࣮ࢪࣥࢢࡋࡓᚋࠊ᪂ࡓ࡟ㄪ〇ࡋࡓ[Zr]=0.01M ࡢ⁐ᾮ࡜༙㔞ࡎࡘΰྜࡋࡓ⁐ᾮࢆ 12 ᪥ᐊ ࡛࢚࣮ࢪࣥࢢࡋࡓ㻔ヨᩱ No.12㻕ࠋࡇࢀࡽࡣࠊ㔜ྜయࡢ᰾⏕ᡂ࡜ᡂ㛗㏿ᗘ࡟ኚ໬ࢆ୚࠼ࡿࡇ࡜࡛ࠊࡼࡾ኱ࡁ࡞⛛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 ࢆࢡ࢖ࢵࢡࢫ࡛࢟ࣕࣥ ᐃࡋࡓࠋ஧ศග⤖ᬗ࡟ࡣ Si㻔111㻕ࢆ⏝࠸ࡓࠋ⁐ᾮࡣ࣏ࣜ⿄࡟ᐦᑒࡋࠊᑓ⏝ࡢ❆௜࣍ࣝࢲ࡟ධࢀ࡚ᅛᐃࡋࡓࠋග㊰㛗ࡣࠊ࣌ࣞࢵࢺࡣ 1mmࠊ[Zr]=0.01M ࡣ 40mmࠊ0.1M ࡣ 15mm ࡜ࡋࡓࠋ[Zr]=0.01M ࡣ 5 ศࡢᐃࢆ 7 ᅇ⧞ࡾ㏉ࡋࠊࢫ࣌ࢡࢺࣝࢆ✚⟬ࡋࡓࠋ0.1M ࡣ 5 ᅇ⧞ࡾ㏉ࡋ࡚✚⟬ࡋࡓࠋEXAFS ᵓ㐀ゎᯒ࡟ࡣ REX2000㻔RIGAKU㻕ࢆ⏝࠸ࡓࠋࣇ䤀࢚ࣜኚ᥮ᙉᗘ

⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
Table 1 ࡟ྛヨᩱࡢ໬Ꮫ⤌ᡂ୪ࡧ࡟ྛ Zr-Zr 㓄఩ࡢ㓄఩ᩘࠊ㓄఩㊥㞳࠾ࡼࡧ Debye-Waller ᅉᏊ㻔௨
ୗ DW㻕ࢆ♧ࡍࠋFig.3 ࡟ྛヨᩱࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋFig.3 ࡟࠾࠸࡚ࠊ3.0㹼3.5ύ௜㏆ࡢ➨஧ࣆ࣮ࢡࢆ▷㊥㞳ࡢ Zr-Zr 㓄఩ࠊࡲࡓࠊ5ύ௜㏆ࡢ➨୕ࣆ࣮ࢡࢆ㛗㊥㞳ࡢ Zr-Zr 㓄఩࡜ࡋ࡚ࣇ
࢕ࢵࢸ࢕ࣥࢢࡋࡓࠋ㛗㊥㞳ࡢ Zr-Zr 㓄఩ࡢ DW ࡣ 0.09ύ࡟ᅛᐃࡋࡓࠋ
㛗㊥㞳ࡢ Zr-Zr 㓄఩㊥㞳࡜▷㊥㞳ࡢ Zr-Zr 㓄఩Zr-O 㓄఩㊥㞳ࡢẚࡣ 2 ࡢᖹ᪉᰿࡟㏆࠸್࡜࡞ࡾࠊFig.3 ࡢᵏᵎᵌᵎᴾ➨୕ࣆ࣮ࢡࡣ☜࠿࡟ 4 㔞యࡢᑐゅᡂศ࡛࠶ࡿࡇ࡜
ࡀ♧ࡉࢀࡓ㻔Table 1㻕ࠋ▷㊥㞳ࡢTable 2 ࡟ 4 㔞యࢆ༢఩࡜ࡋࡓ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 ࡛࠶ࡗࡓࠋࡋࡓࡀࡗZr-Zr 㓄఩࡚ࠊᐊ ࡛࢚࣮ࢪࣥࢢࡋࡓ⁐ᾮ୰࡛ࡣࠊTable 2
ࡢ 8㹼16 㔞యྠኈࡀ 1 㡬Ⅼࡢࡳ࡛ OH ᯫᶫࢆᙧᡂᵎᵌᵎᴾࡋࠊ㔜ྜࡋࡓ⁐Ꮡᵓ㐀ࡀ᥎ ࡉࢀࡿࠋ᰾⏕ᡂ࡜ᡂ㛗㏿ᗘ࡟ኚ໬ࢆ୚࠼ࡓヨᩱ No.11ࠊ
12 ࡛ࡶ Zr-Zr 㓄఩ᩘࠊ㊥㞳࡜ࡶ࡟ࡑࡢ௚ࡢヨᩱ࡜ᕪࡀ࡞ࡃࠊ≉ู࡞ᵓ㐀࡛ࡣ࡞࠿ࡗࡓࠋࡋ࠿ࡋࠊຍヨỈศゎ᮲௳ࡢ㑅ᢥ࡟ࡼࡗ࡚㛗㊥㞳ࡢ Zr-Zr 㓄఩ᵓᩱ㐀ࡢᙧᡂࠊ༶ࡕࠊ4 㔞యࡢ 2 㡬Ⅼྠኈࡢ⤖ྜࢆࡉ
No.
R/ύࡽ࡟ቑࡸࡋࡓࡼࡾ኱ࡁ࡞⛛ᗎᵓ㐀ࢆ㐀ࡿࡇ࡜ࡣྍ⬟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
Fig.3㸬ྛヨᩱࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝ

Table 1㸬ྛヨᩱࡢ໬Ꮫ⤌ᡂ୪ࡧ࡟ྛ Zr-Zr 㓄఩ᩘࠊ㓄఩㊥㞳࠾ࡼࡧ Debye-Waller ᅉᏊ࢚࣮ࢪࣥ
▷㊥㞳ࡢ
㛗㊥㞳ࡢ
㛗㊥㞳 Rヨࢢ
Zr-Zr 㓄఩
Zr-Zr 㓄఩
[Zr]
㸭ഛ⪃
pH
ᩱ
/MDW
᪥
▷㊥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 ᐊ3
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
123.5 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 ⤖ᬗTable 2㸬4 㔞యࢆ༢఩࡜ࡋࡓ㔜ྜయࡢᵓ㐀࡜ Zr-Zr 㓄఩ᩘࡢ⌮ㄽ್ᵓ㐀▷㊥㞳ࡢ Zr-Zr 㓄఩ᩘ㛗㊥㞳ࡢ Zr-Zr 㓄఩ᩘ
2.5

1.5

2.67

1.67

2.75

1.75

32.25

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ࡣ኱ࡁࡃኚ໬ࡋ࡞࠸ࡀࠊ࢚࣮ࢪࣥࢢ࡟ࡼࡗ࡚ഹ࠿࡟໬Ꮫኚ໬ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
Fig.4 ࡟࢚࣮ࢪࣥࢢ ᗘࡢ␗࡞ࡿ⁐ᾮࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ࢚࣮ࢪࣥࢢ ᗘ࡟ࡼࡗ࡚ࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝ࡟኱ࡁ࡞㐪࠸ࡀぢࡽࢀࡓࠋ[Zr]=0.1M ࡛ࡣࠊࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝࡢ➨஧ࠊ➨୕ࣆ࣮ࢡࡀ 50Υࡢ࢚࣮ࢪࣥࢢ࡟ࡼࡗ࡚㛗㊥㞳ഃ࡟ࢩࣇࢺࡋࡓࠋ୍᪉ࠊZr-O 㓄఩࡟㛵ࢃࡿ➨୍ࣆ࣮ࢡࡣ࡯࡜ࢇ࡝ࢩࣇࢺࡋ࡚࠸࡞࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ4 㔞య࡟࠾࠸࡚ Zr-Zr ྠኈࢆ⤖ࢇ࡛࠸ࡿ 2 㔜ࡢ OH-ᯫᶫࡢ୍㒊ࡀ⤖ྜ࠿ࡽゎ࠿ࢀࡓྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ
50Υ࡛࢚࣮ࢪࣥࢢࡋࡓ[Zr]=0.01M ⁐ᾮࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝ࡟ࡣ➨୕ࣆ࣮ࢡࡀㄆࡵࡽࢀࡎࠊ4 㔞యࡢᵓ㐀ࡣ࡯࡜ࢇ࡝ᾘኻࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ➨୍ࠊ➨஧ࣆ࣮ࢡࡣ▷㊥㞳ഃ࡟ࢩࣇࢺࡋ࡚࠾ࡾࠊZr-O 㓄఩࠾ࡼࡧ Zr-Zr 㓄఩ࡢ୧᪉ࡢ㊥㞳ࡀ⦰ࡲࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊpH ࡣᐊ ࡟ẚ࡭࡚ 50Υ࢚࣮ࢪࣥࢢࡢ࡯࠺ࡀ 0.19 ప࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊZr-Zr 㛫ࢆ௓ࡍࡿ OH-ࡀ H+ࢆᨺฟࡋ O2-࡟ኚ໬ࡋࡓྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ࢜࢟ࢩሷ໬ Zr ⁐ᾮࢆຍ⇕ࡍࡿࡇ࡜࡛㓟໬ࢪࣝࢥࢽ࣒࢘ࡀ⏕ᡂࡍࡿࡇ࡜ࡣࡼࡃ▱ࡽࢀ࡚࠸ࡿ[4]ࠋ
50Υ࡛࢚࣮ࢪࣥࢢࡋࡓ⁐ᾮ࡛ࡣࡑࡢ୰㛫యࡀ⏕ᡂࡋࡓ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡞ᵓ㐀ࡀ᳨ฟࡉࢀࡓඛ౛ࡣ࡞ࡃࠊࡑࡢᶵ⬟ࡶᮍ▱࡛࠶ࡿࠋࡇࢀࡽࡢ୰㛫యࡣ୍⯡ⓗ࡞ሷ໬ Zr ⁐ᾮ࡜ࡣ␗࡞ࡿ࡜⪃࠼ࡽࢀࡿࡓࡵࠊ᪂ᶵ⬟ࡢⓎ⌧ࡀᮇᚅࡉࢀࡿࠋ

䝣䞊䝸䜶ኚ᥮ᙉᗘ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⁐ᾮࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝ௒ᚋࡢㄢ㢟㸸 ௒ࡲ࡛࡟࡞࠸᪂つ࡞⁐Ꮡᵓ㐀ࢆ࡜ࡿྍ⬟ᛶࢆồࡵ࡚ࠊຍỈศゎ᮲௳ࢆ෌᳨ウࡍࡿࠋᮏᐇ㦂࡛ヨࡳࡓ㛗㊥㞳ࡢ Zr-Zr 㓄఩ࡢᐃ㔞ゎᯒ࡟ࡼࢀࡤࠊFig.2 ࡢࡼ࠺࡞⛛ᗎⓗ࡞㔜ྜయࢆ᳨ฟ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡞⛛ᗎⓗ࡞㔜ྜయࡀ᪂ᶵ⬟Ⓨ⌧ࡢ㘽࡟࡞ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㓟໬ Zr ࡢ๓㥑య࡜᥎ᐃࡉࢀࡿ໬Ꮫ✀ࡣ୍⯡ⓗ࡞ሷ໬ Zr Ỉ⁐ᾮ࡜ࡣ␗࡞ࡿᶵ⬟ࢆᣢࡘྍ⬟ᛶࡀ࠶ࡿࡓࡵࠊࡇࡢ໬Ꮫ✀ࡢᛂ⏝ᶵ⬟ࢆ᥈⣴ࡍࡿࠋཧ⪃ᩥ⊩㸸
[1] A. Clearfield, Rev. Pure Appl. Chem., 14, 91, 㻔1964㻕.
[2] ᑠᕝಙ᫂, 㜰᰿ⱥே, ᐑỌᓫྐ, ᯇᯘಙ⾜, ụ⏣㔜Ⰻ, ศᯒ໬Ꮫ, 35, 785, 㻔1986㻕.
[3] 㧗ᓮྐ㐍, ᑠᕝಙ᫂, 㕥ᮌᩄஂ, ୰ᓥ㟹, ⬥⏣ᓫᘯ, 㕥ᮌ⌮⣪, ศᯒ໬Ꮫ, 59㻔6㻕, 447, 㻔2010㻕.
[4] ᮧ℩჆ኵ, ຍ⸨ᝋᮁ, ❔ᴗ༠఍㞧ㄅ, 84, 478, 㻔1976㻕.