http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1944.pdf 2010B1944 BL46XU 㧗⪏㣗㺃పࢡ࣒ࣟᆺ Sn ῧຍࣇ࢙ࣛ࢖ࢺ⣔ࢫࢸࣥࣞࢫ㗰࡟࠾ࡅࡿ ୙ാែ⓶⭷ࡢ໬Ꮫ≧ែゎᯒ Analysis of Passivation Film Formed on the Sn-added Ferritic Stainless Steel with High Corrosion Resistance and Low Cr Contents ⛙㔝 ṇ἞ a, ᯇᒣ ᏹஅ a, ඵᮌ ᩍ᫂ a, ྂᕝ Ύᚿ a, 㝜ᆅ ᏹ b Masaharu Hatanoa, Hiroyuki Mastuyamaa, Noriaki Yagia, Kiyoshi Furukawaa, Hiroshi Ojib a ᪂᪥㚩ఫ㔠ࢫࢸࣥࣞࢫ㻔ᰴ㻕, b 㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮ aNippon Steel & Sumikin Stainless Steel Corporation, b JASRI ◳ X ⥺ග㟁Ꮚศගἲ࡟ࡼࡾࠊ14Cr-0.1Sn ࡢ୙ാែ⓶⭷ࢆศᯒࡋࠊᚤ㔞 Sn ࡢᏑᅾ࡜ࡑࡢ໬Ꮫ≧ែ ࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡋࡓࠋ⬺ฟゅࡢゅᗘศゎ ᐃ࠿ࡽࠊ୙ാែ⓶⭷࡬ࡢ Cr ⃰໬࡜ᚤ㔞࡞ࡀࡽ Sn ࡶ㔠ᒓ࡜㓟໬≀㻔SnO㻕ࡢ≧ែ࡛⃰໬ࡋ࡚࠸ࡿ࡜᥎ᐃࡉࢀࡿศᯒ⤖ᯝࡀᚓࡽࢀࡓࠋ௒ᅇᢳฟࡋࡓ Sn4d ࢫ࣌ࢡࢺࣝࡣࠊ୙ാែ⓶⭷࡟ྵࡲࢀࡿ㓟໬≀⏤᮶ࡢ O2s ࣆ࣮ࢡ࡜㔜␚ࡋ࡚ぢ࠼࡚࠸ࡿྍ⬟ᛶࡶ⪃ ࠼ࡽࢀࡿࡓࡵࠊSn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿヲ⣽࡞ศᯒ࡜ゎ㔘ࡣ௒ᚋࡢㄢ㢟࡛࠶ࡿࠋ ࣮࣮࢟࣡ࢻ㸸 ࢫࢸࣥࣞࢫࠊSnࠊ୙ാែ⓶⭷ࠊHAXPES ⫼ᬒ࡜◊✲┠ⓗ㸸 ࢫࢸࣥࣞࢫ㗰ࡣࠊCr ࡜ Ni ࢆῧຍࡋࡓ SUS304㻔18%Cr-8%Ni㻕ࠊNi ࢆྵ᭷ࡋ࡞࠸ SUS430㻔18%Cr㻕 ࡟௦⾲ࡉࢀࡿࠋ୧㗰✀ࡣࠊ⪏㣗ᛶ࡜ຍᕤᛶ࡟ඃࢀࡿ SUS304 ࡜ࠊᛶ⬟ࡣຎࡿࡶࡢࡢẚ㍑ⓗᏳ౯࡞ SUS430 ࡛ᐇ⏝ୖᴫࡡ౑࠸ศࡅࡽࢀ࡚࠸ࡿࠋNi ࡸ Cr ࡣᕼᑡඖ⣲࡛࠶ࡾࠊ㈨※ಖㆤ࡜⤒῭ᛶ࠿ࡽࠊ SUS304 ࡜ SUS430 ࡢ୰㛫㡿ᇦࢆ࢝ࣂ࣮ࡍࡿ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ⣔ࢫࢸࣥࣞࢫ㗰ࡢ㛤Ⓨ࡜ࡑࡢ㐺⏝ࡀ 㐍ࢇ࡛࠸ࡿࠋ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ⣔ࡣࠊSUS430LX ࡟௦⾲ࡉࢀࡿࡼ࠺࡟ 17%Cr ࡟࠾࠸࡚ C ࡸ N ➼ࡢ ୙⣧≀ඖ⣲ࢆపῶࡋ࡚⪏㣗ᛶ࡜ຍᕤᛶࢆ㧗ࡵࡓࢫࢸࣥࣞࢫ㗰࡛࠶ࡿࠋ㧗⪏㣗㺃పࢡ࣒ࣟᆺ Sn ῧຍ ࣇ࢙ࣛ࢖ࢺ⣔ࢫࢸࣥࣞࢫ㗰ࡣࠊࡇ࠺ࡋࡓ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ⣔ࡢ₻ὶࡢ୰࡛ Sn ࢆῧຍࡍࡿ࡜࠸࠺ୡ ⏺ึࡢ࢔ࣉ࣮ࣟࢳ࡟ࡼࡗ࡚㛤Ⓨ࣭ᐇ⏝໬ࡋࡓࠋྠ㗰ࡣࠊ0.1%ࡢᚤ㔞 Sn ῧຍ࡟ࡼࡗ࡚᪤Ꮡ㧗⣧ᗘࣇ ࢙ࣛ࢖ࢺ⣔࡜ྠ➼ࡢ⪏㣗ᛶࢆᢸಖࡋࠊCr 㔞ࢆ 14%ࡲ࡛పῶࡋࡓ┬㈨※ᆺࡢ᪂ࢫࢸࣥࣞࢫ㗰㻔௨ୗࠊ 14Cr-0.1Sn㻕࡛࠶ࡿ[1]ࠋ ࢫࢸࣥࣞࢫ㗰⾲㠃ࡢ⪏㣗ᛶᶵ⬟ࢆᢸ࠺୙ാែ⓶⭷ࡣ Cr ࡜ Fe ࢆ୺せᵓᡂඖ⣲࡜ࡋࠊࡑࡢ⭷ཌࡣ ᩘ nm ࡜ⷧ࠸ࠋᚑ᮶ࠊ≀⌮ゎᯒᡭἲ࡜ࡋ࡚ࡣࠊXPS ࡸ AES ࡀࡼࡃ▱ࡽࢀ࡚࠸ࡿࠋ14Cr-0.1Sn ࡛ Sn ࡟ࡼࡿ⪏㣗ᛶྥୖᶵᵓࢆ❧ドࡋ࡚࠸ࡃ࠺࠼࡛୙ാែ⓶⭷୰࡟࠾ࡅࡿ Sn ࡢᏑᅾ≧ែࢆ᫂ࡽ࠿࡟ࡍ ࡿࡇ࡜ࡣᴟࡵ࡚㔜せ࡛࠶ࡿࠋࣛ࣎ XPS ἲ࡛ࡣࠊ14Cr-0.1Sn ࡛୙ാែ⓶⭷୰࡟ᚤ㔞࡟ྵࡲࢀࡿ Sn ࡢᏑᅾ≧ែࢆᢕᥱࡍࡿࡇ࡜ࡣ኱ኚᅔ㞴࡛࠶ࡿࠋ◳ X ⥺࡛ບ㉳ࡉࢀࡿග㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡣ 8 keV ࡛࠶ࡾࠊ ࣛ࣎ XPS ἲ㻔AlKȘ⥺ࡢሙྜࠊ⣙ 1.5 keV㻕࡜ẚ㍑ࡋ࡚ෆẆ㟁Ꮚࡢศᯒ⮬⏤ᗘࡣᗈࡀࡾࠊ ᚤ㔞 Sn ࡢ᳨ฟឤᗘࡶྥୖࡍࡿࡶࡢ࡜ᮇᚅࡉࢀࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ◳ X ⥺ග㟁Ꮚศගἲ࡟ࡼ ࡾࠊࢫࢸࣥࣞࢫ㗰⾲㠃ࡢ୙ാែ⓶⭷ࢆศᯒࡋࠊᚤ㔞 Sn ࡢᏑᅾ࡜ࡑࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗᢳฟࢆ ┠ⓗ࡜ࡋࡓࠋ ᐇ㦂㸸 ‽ഛࡋࡓヨᩱࡣࠊᕤᴗ⏕⏘ࡋࡓ 14Cr-0.1Sn ࡢ 0.4 mm ཌ〇ရᯈ㻔JIS ‽ᣐ No.2B㻕࡛࠶ࡿࠋSn ࡢ໬ Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗᢳฟࡢࡓࡵࠊ㔠ᒓ Sn ᯈ㻔⣧ᗘ 99.9%㻕࡜◊✲⏝ヨ⸆ SnO2 ⢊ᮎࢆᶆ‽ヨᩱ࡜ࡋࡓࠋ ᑦࠊࢫࢸࣥࣞࢫ㗰࡜㔠ᒓ Sn ᯈࡢ⓶⭷ཌࡉࡣࠊࣛ࣎ AES ἲࡢࢫࣃࢵࢱ࣮࡟ࡼࡾ 2㹼3 nm ࡛࠶ࡿࡇ ࡜ࢆ☜ㄆࡋࡓࠋ ヨᩱࡢศᯒࡣࠊBL46XU ࡢ◳ X ⥺ග㟁Ꮚศග⿦⨨㻔VG-SCIENTA 〇 R-4000㻕࡛ᐇ᪋ࡋࡓࠋධᑕ X ⥺ࡢ࢚ࢿࣝࢠ࣮ࡣ 7939 eV ࡜ࡋࠊ14Cr-0.1Sn ࡣ Cr 2p,1sࠊFe 2p,1sࠊO1sࠊSn 4d,2sࠊC 1sࠊ㔠ᒓ Sn ᯈ࡜ SnO2 ࡣࡑࢀࡒࢀ O1sࠊSn 4d,2sࠊC 1s ࡢࢫ࣌ࢡࢺࣝࢆ཰㞟ࡋࡓࠋග㟁Ꮚࡢ⬺ฟゅᗘ㻔TOA㻕ࡣࠊ 80,55,30 ᗘ࡛ ᐃࡋࡓࠋ ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸⾲ 1 ࡟ᮏᐇ㦂࡛⏝࠸ࡓບ㉳࢚ࢿࣝࢠ࣮㻔hȤ=7939 eV㻕࡛ほ ྍ⬟࡞ Cr ࡜ Sn ࡢෆẆ‽఩ࡢ᮰⦡࢚ ࢿࣝࢠ࣮㻔EB㻕ࢆ♧ࡍࠋ౛࠼ࡤࠊCr ࡢሙྜࠊ㟁Ꮚࡢ᮰⦡࢚ࢿࣝࢠ࣮ࡀ㠀ᖖ࡟኱ࡁ࠸ 1s ‽఩ࡶ⌮ㄽୖ ᳨ฟྍ⬟࡛࠶ࡿࠋᮏᐇ㦂࡛ࡣࠊ㏻ᖖࣛ࣎ XPS ἲ᳨࡛ฟࡍࡿ 2p ‽఩࡟ຍ࠼ࠊෆẆ㟁Ꮚࡢศᯒ⮬⏤ ᗘࢆ☜ㄆࡍࡿࡓࡵ࡟ 1s ‽఩ࡢࢫ࣌ࢡࢺࣝࢆ᥇ྲྀࡋࡓࠋ ᅗ 1 ࡟ࠊࢫࢸࣥࣞࢫ㗰⾲㠃࠿ࡽ᳨ฟࡉࢀࡓ Cr2p ࡜ Cr1s ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ2p ࢫ࣌ࢡ ࢺࣝࡣࠊ2p1/2 ࡜ 2p3/2 ࡢࢫࣆࣥ㌶㐨ศ⿣࡜ࠊ㓟໬≀㻔Cr-O㻕࡜㔠ᒓ㻔Met.Cr㻕ࡢ໬Ꮫࢩࣇࢺ࡟ࡼࡾࡑࢀࡒ ࢀ 2 ᮏ࡟ศ࠿ࢀࡿࠋ௚᪉ࠊ1s ࢫ࣌ࢡࢺࣝࡣࠊࢫࣆࣥ㌶㐨ศ⿣ࢆకࢃ࡞࠸ࡓࡵ༢୍ࣆ࣮ࢡ࡜࡞ࡾࠊ 㓟໬≀㻔Cr-O㻕࡜㔠ᒓ㻔Met.Cr㻕ࡢ໬Ꮫࢩࣇࢺࢆ☜ㄆࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋCr-O ᙉᗘ࡜ẚ㍑ࡋࡓ Met.Cr ᙉᗘࡣ 1s ‽఩ࢆ᳨ฟࡍࡿࡇ࡜࡛᱁ẁ࡟ᑠࡉࡃ࡞ࡿࠋࡍ࡞ࢃࡕࠊෆẆ㟁Ꮚ࡛࠶ࡿ 1s ‽఩ࡢࢫ࣌ࢡ ࢺࣝࢆ᥇ྲྀࡍࡿࡇ࡜࡛ࠊ⾲㠃ឤᗘࡀ᱁ẁ࡟ቑ኱ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ ⾲ 1㸬ග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ᮰⦡࢚ࢿࣝࢠ࣮ /EB㻔eV㻕 Cr 1s 2s 2p 1/2 2p 3/2 3s 3p 1/2 3p 3/2 5989 696 584 574 74 42 42 4465 4156 3929 885 757 715 Sn Cr2p 3d 3/2 3d 5/2 4s 4p 1/2 4p 3/2 4d 3/2 4d 5/2 493 485 137 84 84 25 24 Cr1s 2p 3/2 Cr-O Met.Cr Met.Cr Cr-O 593 Intensity Intensity 2p 1/2 Cr-O 587 581 575 Binding energy /eV 569 Met.Cr 5999 5994 5989 Binding energy /eV 5984 ᅗ 1㸬⬺ฟゅ 80°ࡢ Cr2p ࡜ Cr1s ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝ Sn ࡢ୙ാែ⓶⭷࠾ࡼࡧ⾲㠃࡬ࡢ⃰໬ᣲື࡟ಀࡿ᝟ሗࢆᢳฟࡍࡿࡓࡵ࡟ࠊ⬺ฟゅᗘࢆᑠࡉࡃࡋ࡚ ⾲㠃ឤᗘࢆቑ኱ࡉࡏࡿゅᗘศゎ ᐃࢆ⾜ࡗࡓࠋᮏᐇ㦂࡛ࡣࠊග㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡀ᭱ࡶ㧗ࡃࠊ ศᯒឤᗘࡢ㧗࠸ Sn4d ‽఩࡟╔┠ࡋࠊゅᗘศゎ ᐃࢆᐇ᪋ࡋࡓࠋᅗ 2 ࡣࠊSn4d ࡢࢫ࣌ࢡࢺࣝศᯒ ⤖ᯝࢆ♧ࡋ࡚࠸ࡿࠋ㏻ᖖࠊග㟁Ꮚᙉᗘࡣࠊ⬺ฟゅ㻔TOA㻕ࡢゅᗘຠᯝ࡟ࡼࡾపゅഃ࡟࠿ࡅ࡚ῶ⾶ࡍࡿࠋ Sn4d ࡢග㟁ᏊᙉᗘࡣࠊTOA=80°࠿ࡽ 55°࡟࠿ࡅ࡚Ṥ࡝పୗࡋ࡞࠸≉㛗ࢆ᭷ࡋࡓࠋ ග㟁Ꮚᙉᗘࡢ TOA ౫Ꮡᛶ࡟ࡘ࠸࡚ࠊ80°ࢆᇶ‽࡟ࡋ࡚つ᱁໬ࡋࡓ⤖ᯝࢆᅗ 3 ࡟♧ࡍࠋFe㻔Fe-O㻕 ࡢග㟁ᏊᙉᗘࡣࠊTOA=80°࠿ࡽ 30°࡟࠿ࡅ࡚༢ㄪ࡟పୗࡋࡓࠋ୍᪉ࠊCr㻔Cr-O㻕ࡢᙉᗘపୗࡣ TOA=30° ࡟࠾࠸࡚ Fe ࡼࡾࡶᑠࡉࡃࠊ୙ാែ⓶⭷࡬ࡢ Cr ⃰໬ࡀ࠺࠿ࡀ࠼ࡿࠋSn4d ࡢᙉᗘపୗࡣࠊ୙ാែ⓶ ⭷ࡢ୺せᵓᡂඖ⣲࡛࠶ࡿ Fe ࡸ Cr ࡜ẚ㍑ࡋ࡚ TOA=55°࡛ᑠࡉࡃࠊTOA=30°࡛ Fe ࡼࡾࡶᑠࡉ࠸ࠋ ࡇࢀࡼࡾࠊSn ࡣᚤ㔞࡞ࡀࡽ୙ാែ⓶⭷࠿ࡽ㗰⾲㠃࡬⃰໬ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ Sn ࡢ୙ാែ⓶⭷࠾ࡼࡧ⾲㠃࡛ࡢ໬Ꮫ≧ែ㻔㔠ᒓࠊ㓟໬≀ࡢ౯ᩘ㻕࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡍࡿࡓࡵ࡟ࠊ ᶆ‽ヨᩱࡢศᯒࢆ⾜ࡗࡓࠋᅗ 4 ࡣࠊ㔠ᒓ Sn ࡜ SnO2 ࡢ 4d ࢫ࣌ࢡࢺࣝࢆ♧ࡋ࡚࠸ࡿࠋMet.Sn ࡢࢫ ࣌ࢡࢺࣝࡣ 24 eV㻔4d5/2㻕࡜ 25 eV㻔4d3/2㻕࡟఩⨨ࡋࠊSnO2 ࡢࢫ࣌ࢡࢺࣝ఩⨨ࡣ 26㹼27 eV ࡟఩⨨ࡍࡿࠋ SnO ࡜ SnO2 ࡢ᮰⦡࢚ࢿࣝࢠ࣮ᕪࡣ 0.7eV[2]࡛࠶ࡾࠊSnO ࡣ 25㹼26 eV ࡟఩⨨ࡍࡿࡶࡢ࡜ุ᩿ࡉࢀ ࡿࠋ ࢫࢸࣥࣞࢫ⾲㠃࠿ࡽᚓࡽࢀࡓ Sn4d ࢫ࣌ࢡࢺࣝࢆᅗ 5 ࡟♧ࡍࠋSn4d ࢫ࣌ࢡࢺࣝࡣࠊ22.8 eV ࡟఩ ⨨ࡋ㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ㻔㹼26 eV㻕࡟࠿ࡅ࡚ᗈࡀࡾࢆᣢࡗ࡚࠸ࡿࠋࢫ࣌ࢡࢺࣝࡢᙧ≧࠿ࡽࠊSn ࡣ㔠 ᒓ࠿ࡽ㓟໬≀㻔SnO㻕ࡢΰྜ≧ែ࡛Ꮡᅾࡍࡿࡇ࡜ࡀ᥎ᐹࡉࢀࡿࡶࡢࡢࠊᶆ‽ヨᩱ࡜ẚ㍑ࡋ࡚ Met.Sn ࡢࢫ࣌ࢡࢺࣝ఩⨨ࡣ 1.2㹼2.2 eV ࢩࣇࢺࡋ࡚࠸ࡿࡇ࡜࡟࡞ࡿࠋ 1.0 Sn4d Normarized Intensity Intensity 30deg 55deg 0.8 0.6 Nomaraized TOA=80deg 0.4 Fe-O Cr-O Sn4d 0.2 80deg 0.0 32.0 28.0 24.0 20.0 Binding energy /eV 0 16.0 20 40 60 TOA /deg 80 100 ᅗ 2㸬Sn4d ࡢゅᗘศゎࢫ࣌ࢡࢺࣝ ᅗ 3㸬ග㟁Ꮚᙉᗘࡢ⬺ฟゅ㻔TOA㻕౫Ꮡᛶ Sn4d 1. Met.Sn 2. SnO 3. SnO2 Sn4d SnO2 Intensity (b)SnO2 Met.Sn 4d 5/2 4d 3/2 Intensity 3 2 1 Sn-O 4d 3/2 4d 5/2 (a)Sn 32.0 28.0 24.0 20.0 Binding energy /eV 16.0 32.0 28.0 24.0 20.0 Binding energy /eV 16.0 ᅗ 4㸬ᶆ‽ヨᩱࡢ Sn4d ග㟁Ꮚࢫ࣌ࢡࢺࣝ ᅗ 5㸬14Cr-0.1Sn ࡢ Sn4d ග㟁Ꮚࢫ࣌ࢡࢺࣝ ࢫ࣌ࢡࢺࣝ఩⨨ࡀࢩࣇࢺࡍࡿ୍ᅉ࡜ࡋ࡚ࠊᖏ㟁ຠᯝࡀᣲࡆࡽࢀࡿࠋᖏ㟁ຠᯝ࡟ࡼࡿࢫ࣌ࢡࢺࣝ ఩⨨ࡢࢩࣇࢺࡣࠊởᰁ≀㉁࡛࠶ࡿ C1s ࡢࣆ࣮ࢡ఩⨨࠿ࡽ⡆౽࡟☜ㄆࡍࡿࡇ࡜ࡀฟ᮶ࡿ[3]ࠋᅗ 6 ࡣࠊ 14Cr-0.1Sn ࡜㔠ᒓ Sn ࡟࠾ࡅࡿ C1s ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ♧ࡋ࡚࠸ࡿࠋࡇࢀࡼࡾࠊC1s ࡢࢫ࣌ࢡࢺ ࣝࡣ 284.5㹼284.8 eV ࡟఩⨨ࡋࠊ ᅗ 5 ࡛ㄆࡵࡽࢀࡓ 1.2㹼2.2 eV ࡟ཬࡪࢫ࣌ࢡࢺࣝ఩⨨ࡢࢩࣇࢺࡣᖏ 㟁ຠᯝ࡟ࡼࡾㄝ࡛᫂ࡁ࡞࠸ࠋࡲࡓࠊ௚ඖ⣲ࢫ࣌ࢡࢺࣝࡢᙳ㡪࡜ࡋ࡚ࠊ23 eV ௜㏆࡟⌧ࢀࡿࡇ࡜ࡀ▱ ࡽࢀ࡚࠸ࡿ㓟໬≀⏤᮶ࡢ O2s ࣆ࣮ࢡ[4]࡜㔜␚ࡋ࡚ぢ࠼࡚࠸ࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ ୙ാែ⓶⭷ࡣ 2㹼3 nm ࡜ⷧࡃࠊࣂࣝࢡᩄឤ࡞ TOA=80°࡛ࡑࡢᙉᗘࡀ኱ࡁ࠸⌮⏤ࢆㄝ᫂ࡍࡿࡇ࡜ࡶ ᐜ࡛᫆࡞࠸ࠋᚑࡗ࡚ࠊ௒ᅇᢳฟࡋࡓ Sn4d ࢫ࣌ࢡࢺࣝࡣࠊ୙ാែ⓶⭷࠿ࡽ㗰⾲㠃࡟࠾ࡅࡿ Sn ࡢ໬ Ꮫ≧ែࢆ཯ᫎࡋ࡚࠸ࡿྍ⬟ᛶࡶྰᐃ࡛ࡁ࡞࠸ࠋ C1s Intensity (b)Sn (a)14Cr-0.1Sn 290.0 285.0 280.0 Binding energy /eV ᅗ 6㸬14Cr-0.1Sn ࡢ C1s ග㟁Ꮚࢫ࣌ࢡࢺࣝ ࡲ࡜ࡵ㸸 ◳ X ⥺ග㟁Ꮚศගἲ࡟ࡼࡾࠊ14Cr-0.1Sn ࡢ୙ാែ⓶⭷ࢆศᯒࡋࠊᚤ㔞 Sn ࡢᏑᅾ࡜ࡑࡢ໬Ꮫ≧ែ ࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡋࡓࠋ ୙ാែ⓶⭷ࡢ୺せᵓᡂඖ⣲࡛࠶ࡿ Cr ࡣࠊෆẆ㟁Ꮚ 1s ‽఩ࢆ᳨ฟࡍࡿࡇ࡜࡛ࠊࡑࡢ⾲㠃ឤᗘࡀ ᱁ẁ࡟ቑ኱ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ⬺ฟゅࡢゅᗘศゎ ᐃ࠿ࡽࠊ୙ാែ⓶⭷࡬ࡢ Cr ⃰໬࡜ᚤ㔞࡞ࡀ ࡽ Sn ࡶ㔠ᒓ࡜㓟໬≀㻔SnO㻕ࡢ≧ែ࡛⃰໬ࡋ࡚࠸ࡿ࡜᥎ᐃࡉࢀࡿศᯒ⤖ᯝࡀᚓࡽࢀࡓࠋ௒ᅇᢳฟࡋ ࡓ Sn4d ࢫ࣌ࢡࢺࣝࡣࠊ୙ാែ⓶⭷࡟ྵࡲࢀࡿ㓟໬≀⏤᮶ࡢ O2s ࣆ࣮ࢡ㻔23 eV ௜㏆㻕࡜㔜␚ࡋ࡚ぢ ࠼࡚࠸ࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࣂࣝࢡᩄឤ࡞ TOA=80°࡛ࡑࡢᙉᗘࡀ኱ࡁ࠸⌮⏤ࢆㄝ ᫂ࡍࡿࡇ࡜ࡶᐜ࡛᫆࡞ࡃࠊ୙ാែ⓶⭷࠿ࡽ㗰⾲㠃࡟࠾ࡅࡿ Sn ࡢ໬Ꮫ≧ែࢆ཯ᫎࡋ࡚࠸ࡿྍ⬟ᛶࡶ ྰᐃ࡛ࡁ࡞࠸ࠋ ௒ᚋࡢㄢ㢟㸸 ௒ᅇᢳฟࡋࡓ Sn4d ࢫ࣌ࢡࢺࣝࡢప࢚ࢿࣝࢠ࣮ഃ࡬ࡢࢩࣇࢺࡣࠊ୙ാែ⓶⭷࡟ྵࡲࢀࡿ㓟໬≀⏤ ᮶ O2s ࣆ࣮ࢡ࡜㔜␚ࡋ࡚ぢ࠼࡚࠸ࡿྍ⬟ᛶࡶྰᐃ࡛ࡁ࡞࠸ࡓࡵࠊSn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿヲ⣽࡞ศ ᯒ࡜ゎ㔘ࡣ௒ᚋࡢㄢ㢟࡛࠶ࡿࠋ୙ാែ⓶⭷࠾ࡼࡧ⾲㠃࡬ࡢ Cr,Sn ࡢ⃰໬ࢆ᳨ウࡍࡿࡓࡵ࡟ࠊග㟁 Ꮚࡢ⬺ฟゅᗘ࡜⬺ฟ῝ࡉࢆᐃ㔞ⓗ࡟ᢕᥱࡍࡿࡇ࡜ࡶᚲせ࡛࠶ࡿࠋ ཧ⪃ᩥ⊩㸸 [1] NIKKEI MONOZUKURI, Sep, 20, 㻔2010㻕. [2] NIST XPS DATABASE [3] ⾲㠃ศᯒ, ᰴᘧ఍♫࢔ࢢࢿ, 227-229, 㻔1990㻕㻚 [4] “Handbook of X-ray Photoelectron Spectroscopy a Reference Book of Standard Spectra for Identification and Interpretation of XPS Data “ Ed. J. Chastain and R. C. King, Jr ULVAC-PHI / Physical Electronics USA