http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_11B1773.pdf

2011B1773                            BL46XU㧗⪏㣗㺃పࢡ࣒ࣟᆺ Sn ῧຍࣇ࢙ࣛ࢖ࢺ⣔ࢫࢸࣥࣞࢫ㗰࡟࠾ࡅࡿ୙ാែ⓶⭷ࡢ໬Ꮫ≧ែゎᯒ
Analysis of Passivation Film Formed on Sn-added Ferritic Stainless Steelwith High Corrosion Resistance and Low Cr Contents⛙㔝 ṇ἞ a, 㝜ᆅ ᏹ b, ⏣ᮧ భ୍ a, ┒⏣ ᬛᙪ a, ඵᮌ ᩍ᫂ a, ྂᕝ Ύᚿ a
Masaharu Hatanoa, Hiroshi Ojib, Yuuichi Tamuraa, Tomohiko Moritaa, Noriaki Yagia, Kiyoshi Furukawaaa᪂᪥㚩ఫ㔠ࢫࢸࣥࣞࢫ㻔ᰴ㻕, b㻌㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮ aNippon Steel & Sumikin Stainless Steel Corporation, bJASRI

HAXPES ศᯒ࡟ࡼࡾࠊ16%Cr-0.3%Sn ࡢ୙ാែ⓶⭷ࢆศᯒࡋࠊᚤ㔞 Sn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡋࡓࠋᮏᐇ㦂࡛ࡣࠊOࠊFeࠊCr ࡢᙳ㡪ࢆཷࡅࡎග㟁Ꮚࡢ᳨ฟឤᗘࡀ኱ࡁ࠸ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࣝࢆ᥇ྲྀࡋࡓࠋSn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣ 3929㹼3931eV ࡟࠿ࡅ࡚ᗈࡀࡾࢆᣢࡗ᳨࡚ฟࡉ
ࢀࡓࠋࡇࢀࡼࡾࠊSn ࡣࠊ⾲㠃࠿ࡽ୙ാែ⓶⭷୰࡟࠾࠸࡚㔠ᒓ Sn ࡟ຍ࠼࡚ࠊ㓟໬≀ࡣ SnO2 ࡢ໬Ꮫ≧ែ࡛Ꮡᅾࡋ࡚࠸ࡿྍ⬟ᛶࡀ㧗࠸࡜᥎ᐹࡉࢀࡿࠋࡲࡓࠊ኱Ẽ⎔ቃୗ࡟࠾࠸࡚ Cr ࢆ୺య࡜ࡍࡿ㓟໬⓶⭷ࡀᡂ㛗ࡋࠊ୙ാែ⓶⭷୰࡛ࡢ Sn 㓟໬≀㻔SnO2㻕ࡢ⏕ᡂࡶ㐍⾜ࡋࡘࡘ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ࣮࣮࢟࣡ࢻ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ࡉࢀࡿࠋ㏆ᖺࠊᕼᑡඖ⣲࡛࠶ࡿ Ni ࡢ౯᱁㧗㦐ࢆ⫼ᬒ࡟ࠊSUS304 ࡜ SUS430 ࡢ୰㛫㡿ᇦࢆ࢝ࣂ࣮ࡍࡿ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ⣔ࢫࢸࣥࣞࢫ㗰㻔௨ୗࠊ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ㻕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㗰࡛࠶ࡿࠋ᪂ࢫࢸࣥࣞࢫ㗰ࡣࠊ㧗⣧ᗘࣇ࢙ࣛ࢖ࢺ⣔ࡢ₻ὶࡢ୰࡛ᚤ㔞 Sn ῧຍ࡟ࡼࡾࣞ࢔࣓ࢱ࡛ࣝ࠶ࡿ Cr ࢆ⠇ῶࡋ࡚⪏㣗ᛶࢆⓎ⌧ࡉࡏࡿࡇ࡜ࢆ≉㛗࡜ࡋ࡚࠸ࡿࠋࡇࢀࡲ࡛ࠊSUS430LX ࡜ྠỈ‽ࡢ⪏㣗ᛶࢆ᭷ࡍࡿ 14%Cr-0.1%SnࠊSUS304 ࡢ⪏㣗ᛶ㡿ᇦࢆ࢝ࣂ࣮ࡋᚓࡿ 16%Cr-0.3%Sn ࢆ㛤Ⓨ࣭ᐇ⏝໬ࡋ࡚࠸ࡿ[1]ࠋࢫࢸࣥࣞࢫ㗰⾲㠃ࡢ⪏㣗ᛶᶵ⬟ࡣ⭷ཌᩘ nm ࡢ୙ാែ⓶⭷ࡀᢸࡗ࡚࠾ࡾࠊ᪂ࢫࢸࣥࣞࢫ㗰ࡢ⪏㣗ᛶⓎ⌧ᶵᵓࢆ❧ドࡋ࡚࠸ࡃ࠺࠼࡛୙ാែ⓶⭷୰࡟࠾ࡅࡿ Sn ࡢ໬Ꮫ≧ែࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣᴟࡵ࡚㔜せ࡛࠶ࡿࠋඛࡢ HAXPES ࡛ࡣࠊSn ࡢ໬Ꮫ≧ែࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊS/B ẚ࡜ ᐃ᮲௳ࡀẚ㍑ⓗⰋ࠸࡜ᛮࢃࢀࡓ 4d ‽఩࡟╔┠ࡋ࡚ศᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊSn4d ࢫ࣌ࢡࢺࣝࡣ 22.8 eV
࠿ࡽ 26 eV ࡢ㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ࡟࠿ࡅ࡚ᗈࡀࡾࢆᣢࡗ࡚࠸ࡓ[2]ࠋศᯒࢫ࣌ࢡࢺࣝࡢゎᯒ࠿ࡽࠊSn4d ࢫ࣌ࢡࢺࣝࡣࠊ୙ാែ⓶⭷୰࡟ྵࡲࢀࡿ㓟໬≀⏤᮶ O2s ࣆ࣮ࢡ࡜㔜␚ࡋ࡚ぢ࠼࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿ[2]ࠋࡑࡇ࡛௒ᅇࡣࠊSn ࡢ໬Ꮫ≧ែࡢゎᯒ⢭ᗘࢆྥୖࡉࡏࡿࡓࡵ࡟ࠊ௚ඖ⣲ࡢࢫ࣌ࢡࢺࣝࡢᙳ㡪ࢆཷࡅࡎࠊග㟁Ꮚ᩿㠃✚ࡀẚ㍑ⓗ኱ࡁ࠸ 2s ཬࡧ 2p ‽఩࡟╔║ࡋࡓࠋ2s ཬࡧ 2p ‽఩ࡢ ᐃࡣࠊࣛ࣎ XPS ἲ㻔AlKĮ ⥺ࠊ⣙ 1.5 keV㻕࡛ࡣ୙ྍ⬟࡛࠶ࡾࠊ
HAXPES㻔8 keV㻕ࡢ≉㛗ࢆά࠿ࡍࡇ࡜࡟⧅ࡀࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊHAXPES ࡟ࡼࡾࠊࢫࢸࣥࣞࢫ㗰⾲㠃ࡢ୙ാែ⓶⭷࡟࠾࠸࡚ୖ㏙ࡋࡓศᯒࢆヨ⾜ࡋࠊᚤ㔞 Sn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗᢳฟࢆ┠ⓗ࡜ࡋࡓࠋᐇ㦂㸸‽ഛࡋࡓヨᩱࡣࠊᕤᴗ⏕⏘ࡋࡓ 16%Cr-0.3%Sn ࡢ 0.6 mm ཌ〇ရᯈ࡛࠶ࡾࠊศᯒ⾲㠃ࡣ JIS ‽ᣐ
No.2B ࡟ຍ࠼ࠊ#600 ◊☻࡜#600 ◊☻ᚋ 2 ࢝᭶኱Ẽ᭚㟢ࡋࡓヨᩱ⾲㠃࡜ࡋࡓࠋSn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗᢳฟࡢࡓࡵࠊ㔠ᒓ Sn ᯈ㻔⣧ᗘ 99.9%㻕࡜◊✲⏝ヨ⸆ SnO2 ཬࡧ SnO ⢊ᮎࢆᶆ‽ヨᩱ࡜ࡋࡓࠋ
ヨᩱࡢศᯒࡣࠊBL46XU ࡢ◳ X ⥺ග㟁Ꮚศග⿦⨨㻔VG-SCIENTA 〇 R-4000㻕࡛ᐇ᪋ࡋࡓࠋධᑕ X ⥺ࡢ࢚ࢿࣝࢠ࣮ࡣ 7939 eV ࡜ࡋࠊ16%Cr-0.3%Sn ࡣ Cr 1sࠊFe 1sࠊO1sࠊSn 2sࠊ2pࠊ㔠ᒓ Sn ᯈ࡜ SnO2
ཬࡧ SnO ⢊ᮎࡣࡑࢀࡒࢀ Sn 2p ࡢࢫ࣌ࢡࢺࣝࢆ཰㞟ࡋࡓࠋග㟁Ꮚࡢ⬺ฟゅᗘ㻔TOA㻕ࡣࠊ80ࠊ40 ᗘ࡛ ᐃࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸⾲ 1 ࡟ HAXPES㻔hȤ=7939 eV㻕࡟ࡼࡿ Sn ࡢග㟁Ꮚ᩿㠃✚㻔cross section㻕ࢆࣛ࣎ XPS㻔AlKĮࠊ
hȞ=1500 eV㻕࡜ẚ㍑ࡋ࡚♧ࡍ[3]ࠋ3d ࡢ cross section ࡣࠊࣛ࣎ XPS ࡛ 0.344 ࡟ᑐࡋ࡚ࠊග㟁Ꮚ࢚ࢿࣝࢠ࣮ࡀ኱ࡁࡃ࡞ࡿ࡟ᚑ࠸ᛴ⃭࡟ῶᑡࡋࠊHAXPES ࡛ࡣ 0.0012 ࡜ 2 ᱆పୗࡍࡿࠋ୍᪉ࠊ2s ཬࡧ 2p
ࡢ cross section ࡣࠊ3p ࡸ 3d ࡜ẚ㍑ࡋ࡚ 1 ᱆኱ࡁ࠸ࠋࡇࢀࡼࡾࠊᮏᐇ㦂࡛ࡣࠊHAXPES ࡛ cross section
ࡀẚ㍑ⓗ኱ࡁ࠸ 2s ࡜ 2p ‽఩ࡢࢫ࣌ࢡࢺࣝࢆ᥇ྲྀࡋࡓࠋ
ᅗ 1 ࡟ࠊ〇ရᯈ⾲㠃࠿ࡽ᳨ฟࡉࢀࡓ Sn2s ࡜ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ᮰⦡࢚ࢿࣝࢠ࣮ࡣࠊ2s ‽఩ 4465eVࠊ2p3/2 ‽఩ 3929 eV ࡛࠶ࡾࠊOࠊFeࠊCr ࡢᙳ㡪ࡣཷࡅ࡞࠸ࡇ࡜ࢆ☜ㄆࡋࡓ[4]ࠋNo.2B ⾲㠃࠿ࡽࠊSn2s ࡜ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ᳨ฟࡍࡿࡇ࡜ࡀฟ᮶
ࡓࠋࡇࡇ࡛ࠊ2p3/2 ࡢග㟁Ꮚᙉᗘࡣࠊྠ୍ ᐃ᮲௳ୗ࡟࠾࠸࡚ࠊSn2s ࡢ 3㹼4 ಸ࡜኱ࡁ࠸ࠋࡇࢀࡼࡾࠊ⥆ࡃศᯒ࡛ࡣࠊග㟁Ꮚࡢ᳨ฟឤᗘࡀ኱ࡁ࠸ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࣝࢆ᥇ྲྀࡍࡿࡇ࡜࡟ࡋࡓࠋ
⾲ 1㸬Sn ࡢග㟁Ꮚ᩿㠃✚ࠊcross section /Mbrn
2s
HAXPES 1.0E-02
AlKĮ

2p3s

3p4s

3d4p

5s

4d5p

2.8E-022.0E-03
4.7E-02

4.1E-03
0.192

4.2E-04
1.1E-02

1.2E-03
0.344

7.7E-04
3.5E-02

5.9E-05
1.2E-03

1.8E-04
3.7E-022.0E-05
7.7E-04

Sn2p3/2

Intensity /cps,5㽢103

Intensity /cps,5㽢103

Sn2s620000255000
4475

4470
4465
4460
Binding Energy /eV4455

3936

3931
3926
Binding Energy /eV3921

ᅗ 1㸬⬺ฟゅ 80°ࡢ Sn2s ࡜ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝSn ࡢ໬Ꮫ≧ែ㻔㔠ᒓࠊ㓟໬≀ࡢ౯ᩘ㻕࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡍࡿࡓࡵ࡟ࠊᶆ‽ヨᩱࡢศᯒࢆ⾜ࡗࡓࠋᅗ 2 ࡣࠊ㔠ᒓ Sn ࡜ SnO2 ཬࡧ SnO ࡢ 2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ♧ࡋ࡚࠸ࡿࠋ㔠ᒓ Sn ࡢࢫ࣌ࢡࢺ
ࣝࡣ 3929 eV ࡟఩⨨ࡋࠊSnO2 ࡣ㔠ᒓ Sn ࡼࡾ㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ࡬ࢩࣇࢺࡋ࡚ 3931 eV ௜㏆࡟᳨ฟࡉࢀࡓࠋ୍᪉ࠊSnO ࡣ 3931eV ௜㏆࡛ SnO2 ࡼࡾഹ࠿࡟㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ࡟఩⨨ࡋࡓࠋSnO ࡜SnO2 ࡢ᮰⦡࢚ࢿࣝࢠ࣮ᕪࡣ 0.7 eV[5]࡛࠶ࡾࠊ
SnO2 ࡼࡾ౯ᩘࡢᑠࡉ࠸ SnO ࡣ 3929㹼3931 eVࡢ⠊ᅖ࡟᳨ฟࡉࢀࡿࡇ࡜ࢆண ࡋࡓࠋSnO ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣࠊ㟁Ẽఏᑟᛶࢆᣢࡓ࡞࠸ࡓࡵ࡟ࠊࢳ࣮ࣕࢪ࢔ࢵࣉ࡟ࡼࡗ࡚㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ࡬ࢩࣇࢺࡍࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋ௬࡟ࠊࢳ࣮ࣕࢪ࢔ࢵࣉ࡟ࡼࡿࣆ࣮ࢡ఩⨨ࡢࢩࣇࢺࡀཎᅉࡢሙྜࠊ ᐃ୰࡟⤒᫬ኚ໬ࢆ♧ࡍࡣࡎ࡛࠶ࡿࠋࡑࡇ࡛ࠊ
SnO ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ ᐃ୰㻔ග㟁Ꮚࡢ✚⟬ 5 ᅇ㻕ࡢ⤒᫬ኚ໬ࢆ☜ㄆࡋࡓࠋSnO ග㟁Ꮚࢫ࣌ࢡࢺ
ࣝࡢ⤒᫬ኚ໬ࢆᅗ 3 ࡟♧ࡍࠋSnO ࡢࢫ࣌ࢡࢺࣝࡣ 3931 eV ࡟఩⨨ࡋࠊ ᐃ୰ࡢ⤒᫬ኚ໬ࢆ♧ࡉ࡞࠿ࡗࡓࠋ
ᅗ 2 ཬࡧ 3 ࡢ⤖ᯝ࠿ࡽࠊSn 㓟໬≀ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣ 3931 eV ௜㏆࡟఩⨨ࡋࠊSnO ࡣ SnO2࡜ẚ㍑ࡋ࡚ప᮰⦡࢚ࢿࣝࢠ࣮ഃ࡟᳨ฟࡉࢀ࡞࠿ࡗࡓࠋSn ࡢ୙ാែ⓶⭷࠾ࡼࡧ⾲㠃࡛ࡢ໬Ꮫ≧ែ࡟ಀࡿ᝟ሗࢆᢳฟࡍࡿࡓࡵ࡟ࠊ⬺ฟゅᗘ㻔TOA㻕ࢆᑠࡉࡃࡋࡓゅᗘศゎ ᐃࢆ⾜ࡗࡓࠋᮏᐇ㦂࡛ࡣࠊSn2p3/2 ග㟁Ꮚࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࠊTOA=80°࡜⬺ฟ῝ࡉࡀࡑࡢ 6 ๭⛬ᗘ࡜࡞ࡿ TOA=40°࡜ࡋࡓࠋᅗ 4 ࡣࠊ〇ရᯈ⾲㠃࠿ࡽ᳨ฟࡉࢀࡓ Sn2p3/2 ග㟁Ꮚࢫ࣌ࢡࢺࣝࡢゅᗘศゎ ᐃ⤖ᯝࢆ♧ࡋ࡚࠸ࡿࠋ㏻ᖖࠊග㟁Ꮚᙉᗘࡣࠊ⬺ฟゅ㻔TOA㻕ࡢゅᗘຠᯝ࡟ࡼࡾపゅഃ࡟࠿ࡅ࡚኱ࡁࡃῶ⾶ࡍࡿࠋSn2p3/2 ࡢග㟁ᏊᙉᗘࡣࠊTOA=80°࠿ࡽ 40°࡟࠿ࡅ࡚పୗࡍࡿࡇ

࡜࡞ࡃࠊⱝᖸቑຍࡍࡿഴྥࢆ♧ࡋࡓࠋࡑࡢࡓࡵࠊSn ࡣ⾲㠃࠿ࡽ୙ാែ⓶⭷࡟࠿ࡅ࡚Ꮡᅾ☜⋡ࡀ㧗࠸ࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋTOA=40°ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣࠊ3929㹼3931 eV ࡟࠿ࡅ࡚ᗈࡀࡾࢆᣢࡗ࡚࠸
ࡿࠋࡇࢀࡼࡾࠊSn ࡣࠊ⾲㠃࠿ࡽ୙ാែ⓶⭷୰࡟࠾࠸࡚㔠ᒓ Sn ࡟ຍ࠼࡚ࠊ㓟໬≀ࡣ SnO2 ࡢ໬Ꮫ≧ែ࡛Ꮡᅾࡋ࡚࠸ࡿྍ⬟ᛶࡀ㧗࠸࡜᥎ᐹࡉࢀࡿࠋ   Sn2p3/2

Sn

1st
2nd
3rd
4th
5th

SnO

Intensity /cps,106

Intensity /cps,106Sn2p3/2
        SnO
 2 

SnO

10000

80003936

3931
3926
Binding Energy /eV3936

3921

ᅗ 2㸬ᶆ‽ヨᩱࡢ Sn2p3/2 ග㟁Ꮚࢫ࣌ࢡࢺࣝ

3931
3926
Binding Energy /eV3921

ᅗ 3㸬SnO ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝ⤒᫬ኚ໬

SnO2 Sn

TOA=80㼻
TOA=40㼻

Cr1s

Intensity /cps,5㽢103

Intensity /cps,㽢106

Sn2p3/2

620000
3936

3931
3926
Binding Energy /eVᅗ 4㸬Sn2p3/2 ࡢゅᗘศゎࢫ࣌ࢡࢺࣝ
⬺ฟゅ㸸80°㻔㯮㻕, 40°㻔㉥㻕

3921#600,1day#600,2month

1000005999

Cr-O Met.Cr

5994
5989
Binding Energy /eV5984

ᅗ 5㸬Cr1s ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝ
⬺ฟゅ㸸80°, ◊☻ 1 ᪥㸸㯮㸪◊☻ 2 ࢝᭶㸸㉥኱Ẽ⎔ቃୗ࡟࠾ࡅࡿ୙ാែ⓶⭷ࡢ⏕ᡂ㐣⛬ࢆ☜ㄆࡍࡿࡓࡵ࡟ࠊ〇ရᯈ⾲㠃ࡢ୙ാែ⓶⭷ࢆ#600◊☻࡛㝖ཤࡋࠊࡑࡢ⤒᫬ኚ໬ࢆ HAXPES ศᯒࡋࡓࠋ
ᅗ 5 ࡣࠊ◊☻ᚋ 1 ᪥ཬࡧ 2 ࢝᭶኱Ẽ᭚㟢ࡋࡓ⾲㠃ࡢ Cr1s ග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ♧ࡋ࡚࠸ࡿࠋඛࡢ
HAXPES ศᯒ࠿ࡽࠊCr ࡣෆẆ㟁Ꮚ 1s ‽఩ࢆ᳨ฟࡍࡿࡇ࡜࡛ࠊ⾲㠃ឤᗘࡀ᱁ẁ࡟ቑ኱ࡍࡿࡇ࡜ࢆ
☜ㄆࡋ࡚࠸ࡿ[2]ࠋ1s ࢫ࣌ࢡࢺࣝࡣࠊࢫࣆࣥ㌶㐨ࢆకࢃ࡞࠸ࡓࡵ༢୍ࣆ࣮ࢡ࡜࡞ࡾࠊ㓟໬≀㻔Cr-O㻕
࡜㔠ᒓ㻔Met.Cr㻕ࡢࢣ࣑࢝ࣝࢩࣇࢺࢆ☜ㄆࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋ◊☻ᚋ 1 ᪥࡛ࡣࠊCr-O ࡜ Met.Cr ࡢᙉᗘࡣྠ⛬ᗘ࡛ẕᆅ㻔Met.Cr㻕ࡢᙳ㡪ࢆ኱ࡁࡃ཯ᫎࡋࠊ୙ാែ⓶⭷ࡀⷧ࠸ࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋ୍᪉ࠊ
2 ࢝᭶኱Ẽ᭚㟢ᮦ࡛ࡣࠊMet.Cr ࡢᙉᗘࡀపῶࡋ࡚ Cr-O ࡢᙉᗘẚ⋡ࡀୖ᪼ࡋ࡚࠾ࡾࠊ୙ാែ⓶⭷ࡢᡂ㛗࡟ࡼࡾࡑࡢཌࡉࡀቑࡋ࡚࠸ࡿࡶࡢ࡜ゎ㔘࡛ࡁࡿࠋ

SnO2 Sn

#600,1day#600,2monthIntensity /cps,5㽢103

Sn2p3/2

870000
3936

3931
3926
Binding Energy /eVᅗ 6㸬Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝ

3921⬺ฟゅ㸸40°, ◊☻ 1 ᪥㸸㯮㸪◊☻ 2 ࢝᭶㸸㉥ ᅗ 6 ࡣࠊSn2p3/2 ග㟁Ꮚࢫ࣌ࢺࣝࡢ⤒᫬ኚ໬ࢆ♧ࡋ࡚࠸ࡿࠋ⬺ฟゅࡣࠊ⾲㠃ឤᗘࡢ㧗࠸ 40°࡛ ᐃࡋࡓࠋ◊☻ᚋ 1 ᪥࡛
ࡣࠊ3929 eV ௜㏆࡟ග㟁Ꮚࢫ࣌ࢡࢺࣝࡀ
᳨ฟࡉࢀࠊSn ࡣ㔠ᒓ≧ែࡢᏑᅾẚ⋡ࡀ㧗࠸ࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊ2 ࢝᭶኱Ẽ᭚㟢ᮦ࡛ࡣࠊ3929㹼3931 eV ࡟࠿ࡅ࡚ࣈ࣮ࣟࢻ࡞ග㟁Ꮚࢫ࣌ࢡࢺࣝ࡬࡜ኚ໬
ࡋ࡚࠾ࡾࠊSn ࡣࠊ㔠ᒓ≧ែ࠿ࡽ㓟໬≀
㻔SnO2㻕࡬࡜≧ែኚ໬ࡋࡘࡘ࠶ࡿ஦ࡀ♧၀ࡉࢀࡿࠋ ௨ୖ࠿ࡽࠊ኱Ẽ⎔ቃୗ࡟࠾࠸࡚ Cr ࢆ୺య࡜ࡍࡿ㓟໬⓶⭷ࡀᡂ㛗ࡋࠊᙜヱࢫࢸࣥࣞࢫ㗰࡛ࡣ୙ാែ⓶⭷୰࡛ࡢ Sn 㓟໬≀㻔SnO2㻕ࡢ⏕ᡂࡶ㐍⾜ࡋࡘࡘ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲ࡜ࡵ㸸
HAXPES ศᯒ࡟ࡼࡾࠊ16%Cr-0.3%Sn ࡢ୙ാែ⓶⭷ࢆศᯒࡋࠊᚤ㔞 Sn ࡢ໬Ꮫ≧ែ࡟㛵ࡍࡿ᝟ሗࢆᢳฟࡋࡓࠋᮏᐇ㦂࡛ࡣࠊOࠊFeࠊCr ࡢᙳ㡪ࢆཷࡅࡎග㟁Ꮚࡢ᳨ฟឤᗘࡀ኱ࡁ࠸ Sn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࣝࢆ᥇ྲྀࡋࡓࠋᶆ‽ヨᩱࡢศᯒ࠿ࡽࠊ㔠ᒓ Sn ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣ 3929 eV ࡟఩⨨ࡋࠊSnO2 ࡣ 3931 eV ௜㏆࡟᳨ฟࡉࢀࡓࠋ୍᪉ࠊSnO ࡣ SnO2 ࡼࡾഹ࠿࡟㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ᳨࡛ฟࡉࢀࡓࠋࢫࢸࣥࣞࢫ⾲㠃ࡢศᯒ࠿ࡽࠊSn2p3/2 ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣ 3929㹼3931 eV ࡟࠿ࡅ࡚ᗈࡀࡾࢆᣢࡗ᳨࡚ฟࡉࢀࡓࠋࡇ
ࢀࡼࡾࠊSn ࡣࠊ⾲㠃࠿ࡽ୙ാែ⓶⭷୰࡟࠾࠸࡚㔠ᒓ Sn ࡜㓟໬≀ࡣ SnO2 ࡢ໬Ꮫ≧ែ࡛Ꮡᅾࡋ࡚࠸ࡿྍ⬟ᛶࡀ㧗࠸࡜᥎ᐹࡍࡿࠋࡲࡓࠊ኱Ẽ⎔ቃୗ࡟࠾࠸࡚ Cr ࢆ୺య࡜ࡍࡿ㓟໬⓶⭷ࡀᡂ㛗ࡋࠊ୙ാែ⓶⭷୰࡛ࡢ Sn 㓟໬≀㻔SnO2㻕ࡢ⏕ᡂࡶ㐍⾜ࡋࡘࡘ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ௒ᚋࡢㄢ㢟㸸௒ᅇᢳฟࡋࡓ SnO ᶆ‽ヨᩱࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡣࠊSnO2 ࡼࡾഹ࠿࡟㧗᮰⦡࢚ࢿࣝࢠ࣮ഃ᳨࡛ฟࡉࢀࡓࠋ㓟໬≀ࡢ౯ᩘ࠿ࡽࡋ࡚ᚑ᮶࡜␗࡞ࡿ⤖ᯝ࡛࠶ࡾࠊࡑࡢཎᅉ࡜ゎ㔘ࡣㄢ㢟࡛࠶ࡿࠋࣛ࣎ XPS࡜ࡢ┦㛵ࡶ☜ㄆࡢ࠺࠼⪃ᐹࢆ῝ࡵࡿࠋ௒ᅇᚓࡽࢀࡓᐇ⏝㗰ࡢ⤖ᯝ࡟ࡘ࠸࡚ࠊSn ῧຍ㔞ࡢ㧗࠸ࣔࢹࣝྜ㔠࡛ࡑࡢ☜࠿ࡽࡋࡉࢆ᳨ドࡍࡿࡇ࡜ࡀ௒ᚋࡢㄢ㢟࡜⪃࠼ࡿࠋཧ⪃ᩥ⊩㸸
[1] ౛࠼ࡤ, NIKKEI MONOZUKURI, Sep, 20, 㻔2010㻕.
[2] SPring-8 㔜Ⅼ⏘ᴗ฼⏝ㄢ㢟ሗ࿌᭩ 2010B1944.
[3] JJ. Yeh and I. Lindau, Atom. Data.Nucl.DataTable, 32, 1-155, 㻔1985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[5] NIST XPS DATABASE