http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1811.pdf

2019A1811

BL19B2㕲ୖ࡟ᙧᡂࡍࡿ࢘ࢫࢱ࢖ࢺ⓶⭷ࡢ┦ኚែ࡟క࠺⓶⭷୰ࡢᛂຊኚ໬ᣲື
Stress Development Accompaned with the Phase Transformation ofThermally Grown Oxide Scale of FeO formed on Fe at High Temperatureᯘ 㔜ᡂ a, ᒣࣀෆ ཭㔛㤶 a, ෆᾏ ᫓᮶ a, ୕ᨵᮌ ᛭ᩯ a, ᯘ ຌ⿵ b, ᪥㧗 ᗣၿ b
Shigenari Hayashia, Yurika Yamanouchia, Haruki Utsumia, Reito Mizorogia, Kousuke Hayashib,
Yasuyoshi Hidakaba໭ᾏ㐨኱Ꮫ, b ᪥ᮏ〇㕲ᰴᘧ఍♫a
Hokkaido University, bNippon Steel Corporation.
⣧㕲ୖ࡟㧗 㓟໬࡛ᙧᡂࡍࡿ࢘ࢫࢱ࢖ࢺ⓶⭷䠄FeO䠅ࡢඹᯒኚែ᫬࡟ᑟධࡉࢀࡿ⓶⭷୰ࡢኚែᛂຊ࡜ࡑࡢ⓶⭷ཌࡉ᪉ྥศᕸࡢ᫬㛫ኚ໬ࢆ㧗 in-situ ᐃࡍࡿࡓࡵࡢᐇ㦂᮲௳ࡢ☜❧ࢆ┠ⓗ࡜ࡋ࡚ࠊணࡵ┦ኚែࡉࡏࡓ⓶⭷୰ࡢᐊ ࡟࠾ࡅࡿṧ␃ᛂຊࢆ sin2ȥ ἲࢆ⏝࠸࡚ ex-situ ᐃࡋࡓࠋ ᐃࡣࢩࣥࢳ࣮ࣞࢩࣙࣥ࢝࢘ࣥࢱ࣮࠶ࡿ࠸ࡣ PLATUS2M ࢆ⏝࠸࡚⾜ࡗࡓࠋࢩࣥࢳ࣮ࣞࢩࣙࣥ࢝࢘ࣥࢱ࣮ࢆ⏝࠸ࡓ ᐃ࡛ࡣࠊཌࡉ᪉ྥࡢᛂຊศᕸࢆ᫂☜࡟☜ㄆࡍࡿࡇ࡜ࡀ࡛ࡁࡓࡀࠊPLATUS2M ࢆ⏝࠸ࡓᐃ࠿ࡽࡣጇᙜ࡞⤖ᯝࢆᚓࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ⇕㛫ᅽᘏ㗰ᯈࠊ࢘ࢫࢱ࢖ࢺ⓶⭷ࠊඹᯒኚែࠊኚែᛂຊ⫼ᬒ࡜◊✲┠ⓗ㸸Ⅳ⣲㗰ᯈࡣࠊࢫࣛࣈ࡜࿧ࡤࢀࡿⅣ⣲㗰ሢࢆ 800°௚ ௨ୖࡢ ᗘᇦ࡟࡚⇕㛫ᅽᘏ࡟ࡼࡾᡤᐃࡢཌࡉ࡟ᘏఙࡋ〇㐀ࡉࢀࡿࠋࡇࡢ᫬ࠊ㗰ᯈ⾲㠃࡟⏕ᡂࡋࡓ㓟໬⓶⭷ࡣࠊᅽᘏᚋ࡟ࢥ࢖ࣝ≧࡟ᕳࡁྲྀࡽࢀࡓ㗰ᯈ࡜ඹ࡟ᚎ෭ࡉࢀ㯮Ⰽࡢගἑࢆᣢࡗࡓ⨾ほࢆᣢࡘ㯮⓶࡜࿧ࡤࢀࡿ㓟໬⓶⭷࡬࡜ኚ໬ࡍࡿࠋࡇࡢ㯮⓶ࡣࠊ㗰ᯈࡀᵝࠎ࡞ᕤᴗ〇ရ࡜ࡋ࡚౑⏝ࡉࢀࡿࡲ࡛ࡢᮇ㛫ࠊ⪏㣗ᛶࢆᢸ࠺୍᪉࡛ࠊᅽᘏ㗰ᯈࡢ࣓ࢵ࢟➼ࡢ⾲㠃ฎ⌮᫬࡟໬Ꮫฎ⌮➼࡛㝖ཤࡍࡿᚲせࡀ࠶ࡿࡓࡵࠊ໬Ꮫⓗ࡞㝖ཤᛶ࡟ඃࢀࡿࡇ࡜ࡶせồࡉࢀࡿࠋᚑࡗ࡚ࠊ㯮⓶㸦㓟໬⓶⭷㸧ࡢᐦ╔ᛶࠊ㝖ཤᛶࢆ㐺ษ࡟సࡾ㎸ࡴࡇ࡜ࡀ⇕㛫ᅽᘏ㗰ᯈࡢ⾲㠃ရ㉁ྥୖ࡟ࡣ୙ྍḞ࡛࠶ࡿࠋⅣ⣲㗰ᯈ⾲㠃࡟⇕㛫ᅽᘏ୰࡟ᙧᡂࡍࡿ㓟໬≀⓶⭷ࡣࠊ⾲㠃࠿ࡽ Fe2O3, Fe3O4, FeO ᒙ࠿ࡽᵓᡂࡉ
ࢀࡿࡀࠊࡑࢀࡽࡢ࠺ࡕ FeO ࡀཌࡉࡢ 95%௨ୖࢆ༨ࡵࡿ FeO ୺యࡢ㓟໬≀࡛࠶ࡿࠋFeO ࡣ 570°௚ ௨ୗ࡛ࡣ୙Ᏻᐃ┦࡜࡞ࡿࡓࡵࠊᚎ෭୰࡟ඹᯒ཯ᛂ䠄FeOĺFe+Fe3O4䠅࡟ࡼࡾศゎࡋࠊࡇࢀࡀ㯮⓶࡜࡞ࡿࠋ㯮⓶ࡢ≉ᛶࡣࠊࡑࡢ⤌⧊࡟ࡼࡾỴࡲࡿࡓࡵࠊ㓟໬⓶⭷ࡢ┦ኚែᶵᵓࡀᗈࡃ᳨ウࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊ㓟໬⓶⭷ࡢᐦ╔ᛶ࡟ࡣࠊ⓶⭷୰ࡢṧ␃ᛂຊࡀᙉࡃᙳ㡪ࢆ୚࠼ࡿࠋ㓟໬⓶⭷୰ࡢṧ␃ᛂຊ࡟ࡣࠊ㓟໬⓶⭷ࡢᡂ㛗࡟క࠺ᡂ㛗ᛂຊࠊຍ⇕෭༷࡟క࠺⇕ᛂຊ࡟ຍ࠼ࠊୖ㏙ࡋࡓ┦ኚែ࡟క࠺ኚែᛂຊࡀ࠶ࡾࠊ㓟໬⓶⭷ࡢᐦ╔ᛶࢆ⌮ゎࡍࡿࡓࡵ࡟ࡣࠊ୍㐃ࡢ〇㐀㐣⛬࡟࠾࠸࡚ࠊ⓶⭷୰࡟࡝ࡢࡼ࠺࡞ᛂຊࡀᑟධࡉࢀࠊࡑࢀࡀ࡝࠺ኚ໬ࡍࡿ࠿ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ㔜せ࡜࡞ࡿࠋࡇࢀࡽࡢᛂຊࡢ࠺ࡕࠊẚ㍑ⓗప ࡟࠾࠸࡚ඹᯒኚែ࡟ࡼࡾᑟධࡉࢀࡿኚែᛂຊࡣࠊࡑࡢᚋࡢᛂຊ⦆࿴ࡀᮇᚅฟ᮶࡞࠸ࡇ࡜࠿ࡽࠊᐦ╔ᛶ࡟ᙉ࠸ᙳ㡪ࢆ୚࠼ࡿ࡜࡜ࡶ࡟ࠊ⓶⭷ࡢཌࡉ᪉ྥ࡟࠾ࡅࡿᛂຊศᕸࡣࠊ⓶⭷ࡢᶵᲔⓗ≉ᛶ࡟ᙉ࠸ᙳ㡪ࢆ୚࠼ࡿ஦ࡀண᝿ࡉࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ㓟໬⓶⭷ࡢ┦ኚែ୰ࡢṧ␃ᛂຊ࡜ࡑࡢ᫬㛫ኚ໬ࡣ ᐃࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲ࡢ᭱⤊┠ᶆࡣࠊ㧗 ┦ኚែ୰࡟࠾ࡅࡿᛂຊኚ໬ࢆ in-situ ᐃ࡟ࡼࡾྲྀᚓࡍࡿࡇ࡜࡟࠶ࡿࠋᮏㄢ㢟࡛ࡣࠊࡑࡢᐇ㦂ᢏ⾡ࢆ☜❧ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊࡲࡎࡣ⓶⭷୰ࡢṧ␃ᛂຊࡢ⓶⭷ཌࡉ᪉ྥ
ศᕸࢆࠊSPring-8 ࡢ 0 ḟඖ᳨ฟჾࢆ⏝࠸ࡓᖹ⾜ගᏛ⣔࡟ࡼࡿ౵ධ῝ࡉไᚚ sin2ȥ ἲࢆ⏝࠸࡚ ᐃࡋࠊヨᩱ㛫ࡢ㐪࠸ࢆ㆑ู࡛ࡁࡿᐇ㦂᮲௳㸦X ⥺࢚ࢿࣝࢠ࣮ࠊ౑⏝ࡍࡿᅇᢡࣆ࣮ࢡ➼㸧ࢆ᳨ウࡋࡓ
ᚋࠊ2 ḟඖ᳨ฟჾࢆᛂ⏝ࡋࡓ౵ධ῝ࡉไᚚ sin2ȥ ἲ࡟ࡼࡾྠࡌヨᩱࢆ ᐃࡋࠊ0 ḟඖ᳨ฟჾ࡟ࡼࡿ౵ධ῝ࡉไᚚ sin2ȥ ἲ࡟ࡼࡿ ᐃ࡛ᚓࡓ⤖ᯝ࡜ྠ➼ࡢࢹ࣮ࢱࢆᚓࡿࡇ࡜ࡢ࡛ࡁࡿᐇ㦂᮲௳ࢆ☜❧ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ࠿ࢆ᳨ウࡋࡓࠋ䠉㻝㻠㻜䠉ᐇ㦂㸸ヨᩱ࡟ࡣ⣧㕲ୖ࡟ணࡵ 700°௚, 15 min ࡛ཌࡉ⣙ 40 ȝm ࡢ㓟໬⓶⭷ࢆᙧᡂࡋࠊࡑࡢᚋࠊ380°௚ ࠾ࡼࡧ420°௚ ࡛␗࡞ࡿ᫬㛫┦ኚែࡉࡏࡓヨᩱࢆ⏝࠸ࡓࠋ ᐃ࡛ࡣࠊBL19B2 ࡢከ㍈ᅇᢡィࢆ⏝࠸ࠊ2 ✀㢮ࡢ ȥゅไᚚ᪉ἲ㸦୪ഴἲ㸸Ȧ ㍈ไᚚࠊഃഴἲ㸸Ȥ ㍈ไᚚ㸧ࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾ ȥ ゅኚ᭦᫬ࡢᮦᩱ࡬ࡢ
X ⥺౵ධ῝ࡉࡢኚ໬ࢆ௵ពࡢ῝ࡉ୍࡛ᐃ࡟ಖࡘࡼ࠺࡟ไᚚࡋ࡚ࠊ౵ධ῝ࡉไᚚ sin2ȥ ἲ࡟ࡼࡾ⓶⭷୰ࡢᛂຊ ᐃࢆ⾜ࡗࡓࠋ࡞࠾ࠊIn-situ ᐃࡢࡓࡵࡢ஧ḟඖ᳨ฟჾࡢ౑⏝ࡢࡓࡵ࡟ࡣࠊᅇᢡゅࢆᑠࡉࡃࡍࡿᚲ
せࡀ࠶ࡿࡓࡵࠊX ⥺ࡢ࢚ࢿࣝࢠ࣮ࡣ㏱㐣ᛶࡢ㧗࠸ 30 keV ࢆ⏝࠸ࡓࠋཷගഃࡣࢯ࣮࣮ࣛࢫࣜࢵࢺ㸦Ⓨᩓゅ⣙ 0.13°㛤ཱྀࢧ࢖ࢬ 515 mm㸧ࢆ⏝࠸ࠊNaI ࢩࣥࢳ࣮ࣞࢩࣙࣥ࢝࢘ࣥࢱ࣮࡛ᅇᢡ X ⥺ࢆ᳨ฟࡋࡓࠋヨᩱ࡟↷ᑕࡍࡿࣅ࣮࣒ࢧ࢖ࢬࡣࢫࣜࢵࢺ࡟ࡼࡾ 50.2 mm ࡟ᩚᙧࡋࡓࠋࡲࡓࠊ஧ḟඖ ᐃ࡛ࡣࠊPLATUS2M ࢆ⏝࠸ࡓࠋ࣓࢝ࣛ㛗ࡣ 660 mm, 㟢ග᫬㛫ࢆ 60 s ࡜ࡋ࡚ヨᩱ࡬ࡢධᑕゅࢆ 0.5~10°ࡲ࡛ኚ໬ࡉࡏ࡚ࠊᅇᢡ X ⥺ࢆ஧ḟඖ᳨ฟࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸ࢩࣥࢳ࣮ࣞࢩࣙࣥ࢝࢘ࣥࢱ࣮ࢆ⏝࠸ࡓᛂຊ ᐃ࡛ࡣࠊFigs. 1, 2 ࡟♧ࡍࡼ࠺࡟㓟໬⓶⭷୰ࠊFe3O4┦୰ࡢཌࡉ᪉ྥࡢᛂຊศᕸࡀ᫂░࡟ほᐹࡉࢀࠊࡑࡢᛂຊศᕸࡣ┦ኚែ᫬㛫࡟౫Ꮡࡋ࡚␗࡞ࡗࡓࠋ
᏶඲࡟┦ኚែࡉࡏࡓヨᩱ䠄380°௚, 60 min, Fig. 1䠅࡛ࡣࠊ᩿㠃⤌⧊ほᐹ࠿ࡽࡣ⓶⭷ࡢ࡯ࡰ඲యࡀඹᯒ
ኚែࡋ࡚࠾ࡾࠊFe3O4 ୰ࡢᛂຊศᕸࡣࠊ⾲㠃࠿ࡽᅽ⦰ᛂຊࡀస⏝ࡋ࡚࠸ࡿࡀࠊX ⥺౵ධ῝ࡉࡀ῝ࡃ࡞ࡿ⓶⭷ෆ㒊࡛ࡼࡾ኱ࡁࡃ࡞ࡾࠊࡉࡽ࡟ X ⥺ࡢ౵ධ῝ࡉࡀ῝ࡃ࡞ࡿ࡜⦆࿴ࡉࢀࡿഴྥࢆ♧ࡍࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊࡇࡢഴྥࡣࠊ⏝࠸ࡓ㠃ᣦᩘ䠄448䠅,䠄044䠅ඹ࡟࡯ࡰྠࡌ࡛࠶ࡗࡓࠋ୍᪉ࠊ▷᫬㛫┦ኚែࡉࡏࡓヨᩱ䠄380°௚, 5 min, Fig. 2䠅࡛ࡣࠊFeO ┦୰ࡢඹᯒኚែࡣࡲࡔጞࡲࡗ࡚࠾ࡽࡎࠊ⓶⭷⾲㠃ࡢ Fe3O4 ┦ࡀෆ᪉࡬ᡂ㛗ࡍࡿ࡜࡜ࡶ࡟ FeO ᒙୖ㒊࡟ Fe3O4 ᯒฟ≀ࡀᙧᡂࡋ࡚࠸ࡓࠋ䠄448䠅㠃࠿ࡽồࡵࡓᛂຊ࠿ࡽࡣࠊࡇࡢ⓶⭷ࡢ⾲㠃㏆ഐ࡟ࡣṧ␃ᛂຊࡣⓎ⏕ࡋ࡚࠾ࡽࡎࠊX ⥺ࡢ౵ධ῝ࡉࡀ῝ࡃ࡞ࡿ࡟ࡘࢀࠊᅽ⦰ᛂຊࡀᑟධࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊࡼࡾ X ⥺ࡢ౵ධ῝ࡉࡀ῝࠸⓶⭷ෆ㒊࡟࡚ࠊᅽ⦰ᛂຊࡣ⦆࿴ࡉࢀࡿഴྥࢆ♧ࡋࡓࠋ୍᪉ࠊ䠄044䠅㠃ࢆ⏝࠸ࡓゎᯒ⤖ᯝ࠿ࡽࡣࠊࡼࡾ኱
ࡁ࡞ᅽ⦰ᛂຊ್ࡀ ᐃࡉࢀࠊࡑࢀࡣࠊ60 min ┦ኚែᚋࡢヨᩱ࡜࡯ࡰྠࡌ್ࢆ♧ࡋࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ≉࡟ࠊ⓶⭷⾲㠃࡟ᙧᡂࡋࡓ Fe3O4 ᒙࡢ┦ኚែ࡟క࠺ᡂ㛗࠾ࡼࡧ FeO ᒙୖ㒊௜㏆ࡢ Fe3O4 ᯒฟ≀ࡣ᪉఩౫Ꮡᛶࢆᣢࡘࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ䠄a䠅䠄b䠅
Fe3O4

ඹᯒ+Fe3O4 ᯒฟ≀䠄a䠅Fig. 1 700°௚, 15min ࡛ ᙧ ᡂࡋࠊ380°௚ ࡛ 60 min ┦ኚែࡏࡓ㓟໬⓶⭷ࡢᐃ⤖ᯝ㻌䠄a䠅ᛂຊ್䠄b䠅᩿㠃⤌⧊䠄b䠅
Fe3O4Fe3O4 ᯒฟ≀䠉㻝㻠㻝䠉

Fig. 2 700°௚, 15min ࡛ ᙧ ᡂࡋࠊ380°௚ ࡛ 5 min ┦ኚែࡉࡏࡓ㓟໬⓶⭷ࡢᐃ⤖ᯝ䠄a䠅ᛂຊ್䠄b䠅᩿㠃⤌⧊஧ḟඖ᳨ฟჾࢆ⏝࠸ࡓሙྜࡢᛂຊ ᐃ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊ⌧ᅾࠊゎᯒࢆ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࡀࠊணഛゎᯒࡢ⤖ᯝ࠿ࡽࡣࠊゅᗘศゎ⬟ྥୖࡢࡓࡵࠊヨᩱୖࡢ↷ᑕ㠃✚ࢆ⤠ࡗࡓࡓࡵࠊ⓶⭷ෆࡢṧ␃ᛂຊࡢ㠃ෆศᕸࡢ୙ᆒ୍ᛶࢆᖹᆒ໬࡛ࡁ࡚࠸࡞࠸ྍ⬟ᛶࡀㄆࡵࡽࢀ࡚࠾ࡾࠊPLATUS2M ࢆ⏝࠸ࡓ
in-situ ᐃࡣᅔ㞴࡜࡞ࡿྍ⬟ᛶࡀ࠶ࡿࠋ௒ᚋࠊࡉࡽ࡟ヲ⣽࡞ゎᯒࢆ㐍ࡵࠊᐇ㦂ᡭἲࡢ☜❧ࢆ⾜࠺ࠋ௒ᚋࡢㄢ㢟㸸 ௒ᅇࡢ PLATUS2M ࢆ⏝࠸ࡓ ᐃ࡛ࡣࠊゅᗘศゎ⬟ࢆ☜ಖࡍࡿࡓࡵࠊヨᩱୖࡢ↷ᑕ㠃✚ࢆ⤠ࡗࡓࡓࡵ⓶⭷ࡢṧ␃ᛂຊ࡟⏕ࡌ࡚࠸ࡿ࡜ண᝿ࡉࢀࡿ㠃ෆศᕸࡢ୙ᆒ୍ᛶࢆᖹᆒ໬ฟ᮶࡚࠸࡞࠸ྍ⬟ᛶࡀㄆࡵࡽࢀࡓࠋ௒ᚋࠊ᭦࡞ࡿヲ⣽࡞ゎᯒࢆ㐍ࡵࡿᚲせࡀ࠶ࡿࡀࠊ௒ᚋࠊin-situᐃࡢࡓࡵ࡟ࡣࠊ
౑⏝ࡍࡿ X ⥺ࡢ࢚ࢿࣝࢠ࣮ࢆ Fe K ྾཰➃┤ୗࡢ 7 keV ࡟ࡍࡿ࡜࡜ࡶ࡟ࠊ཯ᑕ㓄⨨࡛ࡢ᳨ฟჾࡢタ⨨ࠊṧ␃ᛂຊࡢ㠃ෆ୙ᆒ୍ᛶࢆᖹᆒ໬ࡍࡿࡓࡵࡢᡭἲࢆ⪃᱌ࡍࡿᚲせࡀ࠶ࡿ࡜ᛮࢃࢀࡿࠋ䠉㻝㻠㻞䠉