SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

Section B%                             %/%

࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࣮࢜ࢫࢸࢼ࢖ࢺࢫࢸࣥࣞࢫ㗰ࡢ㧗 㓟໬࡟࠾ࡼࡰࡍ Cu ࡢᙳ㡪Effect of Cu on Formation of Al2O3 Scale on Austenitic Stainless Steelᯘ 㔜ᡂ a, ⡿⏣ 㕥ᯞ b, బ఑ ຌ c, ୖ⏣ ගᩄ d, Ἑෆ ♩ᩥ e
Shigenari Hayashia, Suzue Yonedab, Isao Saekic, Mitsutoshi Uedad, Norifumi Kochiea໭ᾏ㐨኱Ꮫ, b ໭ᾏ㐨⥲ྜ◊✲ᶵᵓ, c ᐊ⹒ᕤᴗ኱Ꮫ㻘㻌㼐 ᮾிᕤᴗ኱Ꮫ㻘㻌㼑䠄ᰴ䠅᪂᪥㚩ఫ㔠
Hokkaido University, bHokkaido Research Organization, cMuroran Institute of Technology,dTokyo Institute of Technology, eNippon Steel & Sumitomo Metal Corporationa࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࣮࢜ࢫࢸࢼ࢖ࢺ⣔⪏⇕ࢫࢸࣥࣞࢫ㗰ࡢ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ⬟࡟࠾ࡼࡰࡍ Cu ⃰ᗘࡢᙳ㡪ࢆㄪᰝࡍࡿࡓࡵࠊCu ⃰ᗘࡢ␗࡞ࡿ Fe-Ni-Cr-AlࠊNi-Cr-AlࠊNi-Al ྜ㔠ࢆ⏝࠸࡚ࠊึᮇ㓟໬ࢫࢣ࣮ࣝࡢᙧᡂ࡜ࡑࡢᚋࡢ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡢᙧᡂ࣭㑄⛣࡟ཬࡰࡍ Cu ࡢᙳ㡪ࢆ in-situ 㧗X ⥺ᅇᢡࢆ⏝࠸ࡓᵓ㐀ゎᯒ࡟ࡼࡾ᳨ウࡋࡓࠋCu ῧຍྜ㔠࡛ࡣࠊ㓟໬ึᮇ࡟ෆ㒊࢔࣑ࣝࢼ࠿ࡽ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࡬ࡢ㑄⛣ᣲືࡀほᐹࡉࢀࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ௒ᅇࡢᐇ㦂࡛ࡣ Fe ࡸ NiࠊCr ࢆ୺య࡜ࡍࡿ㑄⛣㓟໬≀ࡀ㛗᫬㛫ṧᏑࡋࠊ㐃⥆ⓗ࡞ಖㆤᛶ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡢᙧᡂ࡟⮳ࡽ࡞࠿ࡗࡓ
ࡓࡵࠊCu ࡢ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂಁ㐍ຠᯝ࡟ࡘ࠸࡚᫂☜࡞▱ぢࢆᚓࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 In-situࢼ࢖ࢺࢫࢸࣥࣞࢫ㗰ᐃࠊ㧗X ⥺ᅇᢡࠊ㧗 ึᮇ㓟໬ࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝࠊCu ῧຍ࣮࢜ࢫࢸ

⫼ᬒ࡜◊✲┠ⓗ㸸 ⏘ᴗ⏺࡛⌧ᅾᗈࡃ౑⏝ࡉࢀ࡚࠸ࡿ⪏⇕ࢫࢸࣥࣞࢫ㗰ࡣࠊ⾲㠃࡟ಖㆤᛶࢡ࣑ࣟ࢔ࢫࢣ࣮ࣝࢆᙧᡂࡋࠊࡇࢀࡀ⪏⇕㗰ࢆ㧗 ⎔ቃ࠿ࡽ㐽᩿ࡍࡿࡇ࡜࡟ࡼࡾ⪏㓟໬࣭⭉㣗ᛶࢆ☜ಖࡍࡿࠋࡋ࠿ࡋࠊࢡ࣑ࣟ࢔ࢫࢣ࣮ࣝࡢ㧗 ⪏㓟໬࣭⭉㣗ᛶࡣࠊ900°௚ ௨ୖࡢ㧗 ࡲࡓࡣ㑏ඖᛶࡢ㧗⭉㣗ᛶ⎔ቃୗ➼࡛ࡣᮇᚅ࡛ࡁ࡞࠸ࡓࡵࠊࡼࡾ㧗 ࡛Ᏻᐃ࠿ࡘಖㆤᛶ࡟ඃࢀࡿ࢔࣑ࣝࢼࢫࢣ࣮ࣝࢆᙧᡂࡍࡿᏳ౯࡞⪏⇕㗰ࡢ㛤Ⓨࡀᮃࡲࢀ࡚࠸ࡿࠋ ࢔࣑ࣝࢼࢫࢣ࣮ࣝࢆᙧᡂࡍࡿ⪏⇕ࢫࢸࣥࣞࢫ㗰࡜ࡋ࡚ࡣࠊࣇ࢙ࣛ࢖ࢺ⣔ࡢ Fe-20Cr-10Al(at%)㗰
㸦࣮࣋ࢫ⤌ᡂ㸧ࡀᐇ⏝໬ࡉࢀ࡚࠾ࡾࠊ㟁Ẽ⅔ࡢ㟁⇕⥺ࡸ᤼Ẽ࢞ࢫί໬⏝ࡢゐ፹ᢸᣢࡢࡓࡵࡢ㔠ᒓᢸయ࡜ࡋ࡚౑⏝ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࣇ࢙ࣛ࢖ࢺ⣔⪏⇕㗰࡛ࡣࠊ800°௚ ࢆ㉸࠼ࡿ㧗 ࡛ࡣᶵᲔⓗ≉ᛶ࡟ຎࡿࡓࡵࠊᵓ㐀⏝⪏⇕ྜ㔠࡜ࡋ࡚࣮࢜ࢫࢸࢼ࢖ࢺ(Ȗ-Fe)⣔⪏⇕ࢫࢸࣥࣞࢫ㗰(Fe-Ni-Cr-Al㗰)ࡀᚲせ࡛࠶ࡿࠋࡋ࠿ࡋࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝࢆᙧᡂࡍࡿᏳ౯࡞࣮࢜ࢫࢸࢼ࢖ࢺ⣔⪏⇕ࢫࢸࣥࣞࢫ㗰ࡢᐇ⏝໬ࡣ㐍ࢇ࡛࠸࡞࠸ࠋᣑᩓಀᩘࡢᑠࡉ࠸࣮࢜ࢫࢸࢼ࢖ࢺ⣔⪏⇕ࢫࢸࣥࣞࢫ㗰ୖ࡟ࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝࢆᙧᡂࡍࡿࡓࡵ࡟ࡣࣇ࢙ࣛ࢖ࢺ⣔ࡼࡾࡶ㧗⃰ᗘࡢ Al ῧຍࡀᚲせ࡛࠶ࡿࠋࡋ࠿ࡋ Al ࢆ㧗⃰ᗘ࡛ྵ᭷ࡍࡿࢫࢸࣥࣞࢫ㗰࡛ࡣࠊ◳ࡃ࡚⬤࠸ ȕ-NiAl ➼ࡢ㧗⼥Ⅼࡢ㧗 Al 㔠ᒓ㛫໬ྜ≀┦ࡀᙧᡂࡋࠊࡇࢀࡀ㗰ࡢ〇㐀ᛶࡸຍᕤᛶࢆⴭࡋࡃపୗࡍࡿࡓࡵࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝࢆᙧᡂࡍࡿ࣮࢜ࢫࢸࢼ࢖ࢺ⣔⪏⇕㗰ࡢᐇ⏝໬ࡣࠊᅔ㞴࡜࡞ࡗ࡚࠸ࡿࠋⴭ⪅ࡽࡣ㗰୰࡬ࡢ⣙ 5at%Cu ࡢῧຍࡀ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂࡢࡓࡵ࡟ᚲせ࡞⮫⏺ Al ⃰ᗘࢆⴭࡋࡃపῶࡍࡿࡇ࡜ࢆⓎぢࡋࡓ[1]ࠋࡇࡢ Cu ࡟ࡼࡿ⮫⏺ Al ⃰ᗘపୗᶵᵓࡣ⌧≧࡛ࡣ඲ࡃ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡽࡎࠊ᪩ᛴ࡟ࡑࡢ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡀᚲせ࡜࡞ࡗ࡚࠸ࡿࠋ࣓࢝ࢽࢬ࣒ࡢゎ᫂࡟ࡣࠊඛ
ࡎࡣ Fe-Ni-Cr-Al-Cu ྜ㔠ୖ࡟࢔࣑ࣝࢼࢫࢣ࣮ࣝࡀᙧᡂࡍࡿࡲ࡛ࡢ㑄⛣ⓗ㓟໬ẁ㝵࡟࠾ࡅࡿึᮇ㓟໬ᣲືࢆㄪᰝࡋࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡀᙧᡂ࡟⮳ࡿࡲ࡛ࡢึᮇ㓟໬ẁ㝵࡛⏕ࡌࡿ⌧㇟ࢆᐇ㦂ⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡿࠋ ᮏ◊✲ࡢ┠ⓗࡣࠊࡇࢀࡲ࡛ࡢ᳨ウ࠿ࡽ࣮࢜ࢫࢸࢼ࢖ࢺ⣔ Fe-Ni-Cr-Al ྜ㔠ୖ࡬࢔࣑ࣝࢼࢫࢣ࣮ࣝࡢᙧᡂࢆಁ㐍ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓྜ㔠୰ࡢ Cu ῧຍ࡟ࡘ࠸࡚ࠊಖㆤᛶ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡀᙧᡂࡍࡿࡲ࡛ࡢึᮇ㓟໬ẁ㝵࡟࠾ࡅࡿ㑄⛣㓟໬≀ࡢᙧᡂᣲືࢆヲ⣽࡟᳨ウࡋ࡚ࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝ
ࡢᙧᡂ࡟࠾ࡼࡰࡍ Cu ࡢᙳ㡪࡟ࡘ࠸࡚ᐇ㦂ⓗ࡟ㄪᰝࡍࡿࡇ࡜࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊCu ⃰ᗘࡢ␗࡞ࡿ Fe-Ni-Cr-Al-Cu ྜ㔠࡜ࠊࡼࡾ༢⣧࡞⣔࡜ࡋ࡚ Ni-Cr-Al-Cu ྜ㔠ࠊࡉࡽ࡟ Cr ࡢຠᯝࢆ᳨ウࡍࡿ┠䠉㻞㻟㻡䠉SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

Section Bⓗ࡛ Cr ࢆྵࡲ࡞࠸ Fe-Ni-Al-Cu ࠾ࡼࡧ Ni-Al-Cu ྜ㔠ࢆ⏝࠸࡚ࠊࡇࢀࡽࡢྜ㔠⾲㠃࡟㓟໬ࡢึᮇ࡟ᙧᡂࡍࡿ㓟໬⓶⭷࡜ࡑࡢ᫬㛫ኚ໬ࠊ࢔࣑ࣝࢼࢫࢣ࣮ࣝ࡬ࡢ㑄⛣ᣲືࢆ SPring-8 ࡢᨺᑕගࢆ⏝࠸ࡓ᫬ศ๭ in-situ X ⥺ᅇᢡࢆ⏝࠸ࡓᵓ㐀ゎᯒ࡟ࡼࡾ᳨ウࡋࡓࠋᐇ㦂㸸 ᮏ ᐃࡣࠊࣅ࣮࣒ࣛ࢖ࣥ BL19B2 ࡛ᐇ᪋ࡋࠊX ⥺ࡢ࢚ࢿࣝࢠ࣮ࡣ 12.4 keV(1.000 A)ࢆ⏝࠸ࡓࠋᅗ1 ࡟♧ࡍᵝ࡟ࠊከ㍈ࢦࢽ࣓࣮࢜ࢱ࣮࡟㧗 ࢫࢸ࣮ࢪ(ANTON PARR ♫〇 DHS110)ࢆ⤌ࡳྜࢃࡏࠊヨᩱ࡬ࡢධᑕゅ(ヨᩱ⾲㠃࡜ධᑕ X ⥺ࡢ࡞ࡍゅ)Į = 12°࡜ࡋࡓࠋ஧ḟඖ᳨ฟჾ PLATUS300K ࢆ୰ᚰゅ
ᗘ 2ș = 24°࡛タ⨨ࡋࠊ࣓࢝ࣛ㛗ࢆ 450.14 mm ࡜ࡋ࡚ᅇᢡ X ⥺ࢆ஧ḟඖ᳨ฟࡋࡓࠋ࣓࢝ࣛ㛗ࡣࠊࢦࢽ࣓࣮࢜ࢱ࣮ୖ࡟タ⨨ࡋࡓ஧ḟඖ᳨ฟჾࢆ␗࡞ࡿゅᗘ࡛㓄⨨ࡋࡓ㝿ࡢࢲ࢖ࣞࢡࢺࢫ࣏ࢵࢺࡢ఩⨨ࢆ᳨ฟࡋࠊࡑࢀࡽࢲ࢖ࣞࢡࢺࢫ࣏ࢵࢺࡢ఩⨨࠿ࡽᗄఱᏛⓗ࡟ồࡵࡓࠋ ᐃヨᩱ࡜ࡋ࡚ Cu ⃰ᗘࢆኚ࠼ࡓ FCC ẕ┦ࡢ Fe-17Ni-17Cr-7.7Al-(0, 3.5,5, 6)at%Cu ྜ㔠ࠊࡼࡾ༢⣧࡞⣔࡜ࡋ࡚ Fe ࢆྵࡲ࡞࠸ Ni-17Cr-10Al-(0, 15, 30)Cu ྜ㔠ࢆ⏝࠸ࡓࠋࡲࡓࠊẚ㍑ࡢࡓࡵ࡟ Cr ࢆྵࡲ࡞࠸Fe-17Ni-7.7Al-(0, 3.5, 5, 6)Cu, Ni-12Al-(0, 15,30)Cu ྜ㔠ࢆ⏝ពࡋࡓࠋヨᩱࡣࠊ኱Ẽ୰ࠊᐊ
࠿ࡽ 20°௚/min ࡛ 1000°௚ ࡲ࡛᪼ ࡋࠊࡑࡢᚋ᭱኱࡛ 10 min ࡢ➼ 㓟໬ࢆ⾜ࡗࡓࠋ᪼ࢆྵࡴ㓟໬୰࡟ᙧᡂࡍࡿ⾲㠃㓟໬⓶⭷࠿ᅗ 1㸬ᮏᐇ㦂࡛⏝࠸ࡓ㧗 ࢫࢸ࣮ࢪࡢ ᐃ᮲௳ࡽࡢᅇᢡಙྕࢆ 10 ⛊ẖ࡟ 5 ⛊㛫 ᐃࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 ᅗ 2 ࡟ Fe-17Ni-17Cr-7.7Al ࠾ࡼࡧ Fe-17Ni-17Cr-7.7Al-6Cu ྜ㔠ࢆ 1000°௚ ࡲ࡛᪼ ᚋࠊ10 ศ㛫ࡢ➼ 㓟໬ࢆ⾜ࡗࡓ㝿ࡢ X⥺ᅇᢡࣃࢱ࣮ࣥࢆ♧ࡍࠋ࡝ࡕࡽࡢྜ㔠ୖ࡟ࡶ 650°௚ ௜㏆࠿ࡽFe2O3 ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡀㄆࡵ
ࡽࢀࠊࡑࡢᚋࠊCr ࢆᅛ⁐ࡋࡓ್༙ᖜࡢᗈ࠸(Fe, Cr)2O3 ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡀ☜ㄆࡉࢀࡓࠋࡇࡢ Crࢆᅛ⁐ࡋࡓ Į-Fe2O3 ࡢ⏕ᡂࡣࠊ(a)᪼ ୰࡟ Cr ࡢ㓟໬ࡀ⏕ࡌ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࡀࠊCu ῧຍྜ㔠࡛ࡣᅛ⁐యࢫࢣ࣮ࣝࡀᙧ
ᡂࡍࡿ๓࡟ Cr2O3 ࠿ࡽࡢᅇᢡࣆ
࣮ࢡࡀㄆࡵࡽࢀࡿࡢ࡟ᑐࡋ࡚ࠊ
Cu ↓ῧຍྜ㔠࡛ࡣ Cr2O3 ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡣㄆࡵࡽࢀ࡞࠸ࠋࡲ
ࡓࠊ࡝ࡕࡽࡢヨᩱࡶ㓟໬ ᗘࡀ700°௚ ࢆ㉺࠼ࡿ࡜(Fe, Al)2O3 ࡜ᛮࢃࢀࡿ Fe2O3-Al2O3 ᅛ⁐యࢫ(b)ࢣ࣮ࣝࡀᙧᡂࡍࡿࡇ࡜ࡀࢃ࠿ࡿࠋCu ῧຍྜ㔠࡛ࡣࠊࡑࡢᚋ ĮAl2O3 ࠿ࡽࡢᚤᙅ࡞ᅇᢡࣆ࣮ࢡࡀほᐹࡉࢀࠊࡑࢀࡣᐇ㦂⤊஢ࡲᅗ 2㸬Fe-17Ni-17Cr-7.7Al (a)-6Cu, (b)-0Cu ྜ㔠ࡢ㧗 X ⥺ᅇᢡ࡛ṧᏑࡍࡿࡢ࡟ᑐࡋ࡚ࠊCu ↓ῧࣉࣟࣇ࢓࢖ࣝ
ຍྜ㔠࡛ࡣ Al2O3 ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡣㄆࡵࡽࢀ࡞࠿ࡗࡓࠋ᪼ ୰࡟ㄆࡵࡽࢀࡿึᮇ Fe2O3(2ș = 22.6° ͳʹതͲ) ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡣࠊCu ῧຍྜ㔠࡛ࡣᙧᡂึ
ᮇ࡟ᙉᗘࡀᛴ⃭࡟ቑຍࡍࡿࡀࠊࡑࡢᚋ 1000°௚ ࢆ㉺࠼ࡿ࡜పୗࡋࠊ➼ 㓟໬୰࡟ࡉࡽ࡟పୗࡍࡿࡢ

䠉㻞㻟㻢䠉SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

Section B࡟ᑐࡋ࡚ࠊCu ↓ῧຍྜ㔠࡛ࡣࠊᙉᗘࡣᚎࠎ࡟ቑຍࡋ࡚ 1000°௚ ࡟฿㐩ᚋ࡟ᛴ⃭࡟ቑຍᚋࠊᐇ㦂⤊஢ࡲ࡛ᙉ࠸ᙉᗘࡀ⥅⥆ࡍࡿࡇ࡜ࡀࢃ࠿ࡿࠋCu ῧຍྜ㔠࡛ㄆࡵࡽࢀࡓ Fe2O3 ࡢᙧᡂᣲືࡣࠊෆ㒊
Al2O3 ࡢᙧᡂ࡟కࡗ࡚ྜ㔠⾲㠃㏆ഐ࡟ᑟධࡉࢀࡿᅽ⦰ᛂຊ࡟ࡼࡾࠊẕᮦ୰ࡢ Fe ᇶᮦࡀ⾲㠃࡟ᢲࡋฟࡉࢀࠊࡑࢀࡀ㓟໬ࡉࢀ࡚ Fe2O3 ࡀᙧᡂࡋࡓࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊࡑࡢᚋࠊෆ㒊 Al2O3 ࡀ㐃⥆ⓗ࡟࡞ࡾࠊಖㆤᛶࢆⓎ᥹ࡍࡿࡇ࡜࡟ࡼࡾ Fe ࡢ౪⤥ࡀ⤯ࡓࢀ࡚ࠊࣆ࣮ࢡᙉᗘࡀపୗࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊCu ↓ῧຍྜ㔠࡛ࡣࠊྠᵝࡢᣲືࡣほᐹࡉࢀࡎࠊ➼ 㓟໬୰࡟ Fe2O3 ࡢᙉᗘࡀቑຍࡋࡓࡇ࡜
࠿ࡽࠊCu ῧຍࡣ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡢᙧᡂࢆಁ㐍ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ ࡼࡾ༢⣧࡞ Ni-Cr-Al-Cu ྜ㔠⣔ࢆ⏝࠸ࡓ Ni-17Cr-10Al ࠾ࡼࡧ Ni-17Cr-10Al-30Cu ྜ㔠ࢆ 1000°௚ࡲ࡛᪼ ᚋࠊ10 ศࡢ➼ 㓟໬ࢆ⾜ࡗࡓ㝿ࡢ X ⥺ᅇᢡࣃࢱ࣮ࣥࢆᅗ 3 ࡟♧ࡍࠋ⏝࠸ࡓ Ni ᇶྜ㔠࡛ࡣࠊCu ῧຍࡢ᭷↓࡟㛵ࢃࡽࡎࠊ࡝ࡕࡽࡢྜ㔠ୖ࡟ࡶ Al2O3 ࡢᙧᡂࡣㄆࡵࡽࢀࡿࡀࠊCu ↓ῧຍྜ㔠
࡛ࡣ 800°௚ ௜㏆ࡼࡾ NiO ࡢ⏕ᡂࡀㄆࡵࡽࢀࠊNiO ࠿ࡽࡢᅇᢡᙉᗘࡣ㓟໬᫬㛫ࡢ⤒㐣࡟కࡗ࡚ᙉࡃ
࡞ࡿࡢ࡟ᑐࡋ࡚ࠊCu ῧຍྜ㔠࡛ࡣ 650°௚ ௜㏆࡛ᚤᙅ࡞ NiO࠿ࡽࡢᅇᢡಙྕࡣㄆࡵࡽࢀࡿ
ࡀࠊࡑࢀࡣ 1000°௚ ࡲ࡛᪼ ᚋ࡟ࡣᾘኻࠊࡲࡓࡣࢫࣆࢿࣝᆺ㓟໬≀࡬࡜㑄⛣ࡋࠊ
1000°௚ ࡢ➼㓟໬୰࡟ࡣㄆࡵࡽࢀ࡞ࡃ࡞ࡿࠋࡲࡓࠊ
࡝ࡕࡽࡢヨᩱୖࡶ 1000°௚࡟᪼ ᚋ࡟ࡣࠊࢫࣆࢿࣝᆺࡢ㓟໬≀ࡀᙧᡂࡍࡿࡀࠊCu ↓ῧຍྜ㔠ୖ࡛ࡣࠊᙧᡂࡋࡓ㓟໬≀ࡣ(a)NiCr2O4 ࡛࠶ࡿࡢ࡟ᑐࡋ࡚ࠊCuῧຍྜ㔠࡛ࡣ NiAl2O4 ࡀᙧᡂࡋ࡚࠾ࡾࠊCu ῧຍ࡟ࡼࡾᙧᡂࡍࡿ㓟໬ࢫࢣ࣮ࣝࡣࠊࡼࡾ Al ࣜࢵࢳ࡜࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࡞
࠾ࠊCu ῧຍྜ㔠࡛ࡣࠊ500°௚ ௜㏆࠿ࡽ CuO ࠿ࡽࡢᅇᢡಙྕࡀㄆࡵࡽࢀࠊࡑࢀࡣࢫࣆࢿࣝᆺ㓟໬≀ࡢᙧᡂ࡜࡯ࡰྠ᫬࡟ᾘኻࡍࡿࡇ࡜࠿ࡽࠊCuO ࡣࢫࣆࢿࣝ(b)ᆺ㓟໬≀୰࡟ᅛ⁐ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ࡞࠾ࠊCr2O3 ࠿ࡽࡢᅇᢡࣆ࣮ࢡࡣࠊCu ↓ῧຍྜ㔠࡛ࡼࡾ▷᫬㛫࠿ࡽㄆࡵࡽ
ᅗ 3㸬Ni-17Cr-10Al (a)-30Cu, (b)-0Cu ྜ㔠ࡢ㧗 X ⥺ᅇᢡࢀࡿࠋࡇࢀࡣࠊFe ᇶྜ㔠ࡢሙྜࣉࣟࣇ࢓࢖ࣝ
࡜ࡣ㏫ࡢ⤖ᯝ࡛࠶ࡿࡀࠊCu ↓ῧຍྜ㔠࡛ࡣ Al2O3 ࡣෆ㒊㓟໬≀࡜ࡋ࡚ᙧᡂࡋࠊ⾲㠃࡟ Cr2O3୺యࡢ㓟໬≀ࡀᙧᡂࡋࡓ࡜⪃࠼ࢀࡤࠊCu ῧຍྜ㔠࡛ࡣ㐃⥆ⓗ࡞ Al2O3 ࡀᙧᡂࡋࡓࡇ࡜ࡀ♧၀ࡉࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊᡤⅭ࡟ᙧᡂࡋࡓ NiO ࡜ Al2O3 ࡢ཯ᛂ࡟ࡼࡾẚ㍑ⓗཌ࠸ NiAl2O4 ࡀᙧᡂࡋࡓࡓࡵࠊAl2O3 ࠿ࡽࡢᅇᢡಙྕࡀ᳨ฟࡉࢀ࡞࠿ࡗࡓ࡜
ᛮࢃࢀࡿࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ
Ni-Cr-Al ⣔ྜ㔠࡟࠾࠸࡚ࡶࠊCu࡟ࡼࡾ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡢᙧ
ᅗ 4㸬Ni-12Al-30Cu ྜ㔠ࡢ㧗 X ⥺ᅇᢡࣉࣟࣇ࢓࢖ࣝ
ᡂࡀಁ㐍ࡉࢀ࡚࠸ࡿ࡜⪃࠼ࡽ䠉㻞㻟㻣䠉SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

Section Bࢀࡿࠋ ᅗ 4 ࡟ Cr ࢆྵࡲ࡞࠸ Ni-12Al-30Cu ྜ㔠ࡢ ᐃ⤖ᯝࢆ♧ࡍࠋᅗ 3 ࡟♧ࡋࡓ Ni-Cr-Al-Cu ῧຍྜ㔠࡜ྠᵝ࡟ࠊึᮇ࡟ CuO ࡜ NiO ࡀᙧᡂࡍࡿࡀ CuO ࡣ⣙ 1000Υ࡛ᾘኻࡋࠊࡑࡢᚋࡣ NiO ࡢᅇᢡಙྕࡢࡳࡀほᐹࡉࢀࡿࠋ୍᪉ࠊAl2O3 ࠾ࡼࡧ NiAl2O4 ┦࠿ࡽࡢᅇᢡಙྕࡣ඲ࡃほᐹࡉࢀ࡞࠿ࡗࡓࠋAl ⃰ᗘࡢ㧗࠸ྜ㔠࡛ࡶ Cr ↓ῧຍ࡛ࡣ Al2O3 ࡣ᳨ฟࡉࢀ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊCr ῧຍࡣ࢔࣑ࣝࢼࢫࢣ࣮ࣝ
ᙧᡂࢆಁ㐍ࡋ࡚࠸ࡿ࡜ゝ࠼ࡿࡀࠊCu ࡢຠᯝࢆ☜ㄆࡍࡿࡇ࡜ࡣฟ᮶࡞࠿ࡗࡓࠋ ᮏᐇ㦂࡛ᚓࡽࢀࡓ⤖ᯝ࠿ࡽࡣࠊCu ῧຍࡣ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂࡢಁ㐍ຠᯝࢆ♧ࡍࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ୍᪉ࠊ࠸ࡎࢀࡢྜ㔠࡛ࡶࠊ᏶඲࡞እᒙ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࡟ࡣ⮳ࡽࡎࠊFe2O3 ࡸ NiOࠊNiAl2O4ࠊNiCr2O4 ➼ࡢ㑄⛣㓟໬≀ࡀ㛗᫬㛫ṧᏑࡍࡿ⤖ᯝ࡜࡞ࡗࡓࡓࡵ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂᶵᵓ
࡟ཬࡰࡍ Cu ῧຍࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿ࡟ࡣ⮳ࡽ࡞࠿ࡗࡓࠋ௒ᚋࡢㄢ㢟㸸ᮏ ᐃ࡛ࡣࠊCu ῧຍࡢ᭷↓࡟ࡼࡿึᮇ㓟໬ᣲືࢆゎᯒࡋࠊ␗࡞ࡿ㑄⛣㓟໬≀ࡢᙧᡂᣲືࢆほᐹࡍࡿࡇ࡜ࡀฟ᮶ࡓࠋCu ࡣ Al2O3 ࡢᙧᡂࢆಁ㐍ࡋ࡚࠸ࡿࡇ࡜ࡀᮏᐇ㦂࠿ࡽ☜ㄆࡉࢀࡓࡀࠊ୍᪉ࠊ௒ᅇࡢ ᐃ࡛ࡣࠊ㧗 Cu ῧຍྜ㔠࡛ࡶ᏶඲࡞እᒙ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࡟ࡣ⮳ࡽ࡞࠿ࡗࡓࠋᐇ㦂ᚋࡢ⤌ᡂศᯒ࠿ࡽࠊ௒ᅇࡢ ᐃ࡛⏝࠸ࡓྜ㔠ヨᩱࡣ┠ᶆ⤌ᡂࡼࡾࡶప Al ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚
࠾ࡾࠊእᒙ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂࡣࠊྜ㔠୰ࡢ Al ⃰ᗘ࡟ᴟࡵ࡚ᩄឤ࡛࠶ࡾࠊ0.5%ࡢ㐪࠸ࡀ⤖ᯝࢆ኱ࡁࡃᕥྑࡍࡿࡇ࡜࠿ࡽࠊ௒ᅇ⏝࠸ࡓྜ㔠⤌ᡂࡀప Al ⤌ᡂ࡛࠶ࡗࡓࡇ࡜ࡀࠊ᏶඲࡞࢔࣑ࣝࢼࢫࢣ࣮ࣝࡀᙧᡂࡋ࡞࠿ࡗࡓ᭱኱ࡢ⌮⏤࡜⪃࠼ࡽࢀࡿࠋ௒ᚋࡣࠊCu ῧຍ࡟ࡼࡿ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂᶵᵓࢆ᫂☜࡟⌮ゎࡍࡿࡓࡵ࡟ࡣࠊCu ⃰ᗘࡢቑຍ࡟కࡗ࡚ࠊ㓟໬࣮ࣔࢻࡀእᒙ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂ࡬࡜᫂☜࡟㑄⛣ࡍࡿྜ㔠⤌ᡂࢆ⏝࠸ࡿ࡜࡜ࡶ࡟ࠊ஦๓ࡢணഛᐇ㦂ࢆᐇ᪋ࡋ࡚㓟໬ᣲືࢆᢕᥱࡋ࡚࠾ࡃᚲせࡀ࠶ࡿࠋࡲࡓࠊ௒ᅇࡢᐇ㦂࡛ࡣࠊAl ⤌ᡂࡢᑡ࡞࠸ 6%Al ྜ㔠ࡶ ᐃணᐃ࡜ࡋ࡚⏦ㄳࢆ⾜ࡗࡓࡀࠊ஦๓ࡢணഛᐇ㦂⤖ᯝ࠿ࡽࠊ⣙ 8%Al ⤌ᡂࡀࠊᮏྜ㔠⣔ࡢ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂࡢࡓࡵࡢ⮫⏺ Al ⃰ᗘ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࡓࡵࠊ6%Al ྜ㔠ࢩ࣮ࣜࢬࡢ ᐃࡣᐇ᪋ࡋ࡞࠿ࡗࡓࠋࡲࡓࠊCr ↓ῧຍྜ㔠࡟ࡘ࠸࡚ࡣࠊNi ᇶྜ㔠ࡢ ᐃ࠿ࡽ Cr ↓ῧຍᮦୖ࡟ࡣ࢔࣑ࣝࢼࢫࢣ࣮ࣝࡀᙧᡂࡋ࡞࠸ࡇ࡜ࡀ☜ㄆࡉࢀࡓࡇ࡜࡟ຍ࠼ࠊ ᐃ᫬㛫ࡀ༑ศ࡛ࡣ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊCr ↓ῧຍࡢ Fe ᇶྜ㔠ࡢ ᐃࡣᐇ᪋ࡋ࡞࠿ࡗࡓࠋ
Cr ࡣ࢔࣑ࣝࢼࢫࢣ࣮ࣝᙧᡂࡢ⮫⏺ Al ⃰ᗘࢆୗࡆࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊCu ࡜ Cr ࡜ࡢ┦஫ⓗ࡞ຠᯝ࡟ࡘ࠸࡚ࡣࠊ⌧≧࡛ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡽࡎࠊ௒ᚋࠊ㐺ษ࡞ྜ㔠⣔࠾ࡼࡧ⤌ᡂࢆ⏝࠸ࡓ᳨ウ
ࡀᚲせ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸
[1] S. Hayashi, et al., Proc. Adv. High-Temp. Mater. Tech. for Sustainable and Reliable Power Engineering,(2015) 371.

(Received: March 7, 2019; Early edition: May 9, 2019,
Accepted: July 16, 2019; Published: August 29, 2019䠉㻞㻟㻤䠉