蚕シルク繊維から成る高強度繊維の微結晶構造解析 - SPring

2011A1710
BL40B2
⺋ࢩࣝࢡ⧄⥔࠿ࡽᡂࡿ㧗ᙉᗘ⧄⥔ࡢᚤ⤖ᬗᵓ㐀ゎᯒ
Analysis of crystallite structure in high strength re-Bombyx mori silk fiber
by SAXS/WAXD simultaneous measurements
ᰩᒣ ┤ே a, ᒾ⏣ 㜿భ⨾ a, ๓㔝 㝯 a, ➉ෆ ᏹ඘ a, ୰஭ Ꮥ᠇ a, Ⲩᕝ ♸ኴ a
బࠎᮌ ᅬ b, Ḉ஭ ఙ୍ b
a
Naoto Kuriyama , Ayumi Iwataa, Takashi Maenoa, Hiromitsu Takeuchia
Takanori Nakaia, Yuta Arakawaa, Sono Sasakib, Shinichi Sakuraib
a
a
㇏⏣ྜᡂ㻔ᰴ㻕, b ி㒔ᕤⱁ⧄⥔኱Ꮫ,
Toyoda Gosei. Co. Ltd., b Kyoto Institute of Technology,
㇏⏣ྜᡂ㻔ᰴ㻕࡛ࡣࠊࣂ࢖࣮࢜࣋ࢫ࣐ࢸࣜ࢔࡛ࣝ࠶ࡿࢩࣝࢡࢆ⏝࠸ࡓ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋࡑࡢ᳨ウ
㐣⛬࡟࠾࠸࡚ࠊ⇕ฎ⌮࡟ࡼࡗ࡚ᘬᙇ◚᩿ᙉᗘࡢቑຍࡀ☜ㄆࡉࢀࡓࠋࡑࡢ⌮⏤ࢆ SPring-8㻌 BL40B2
࡟࡚ᵓ㐀ゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊ⤖ᬗᵓ㐀ࡢ㐪࠸ࡀ☜ㄆࡉࢀࡓࠋ
࣮࣮࢟࣡ࢻ㸸 ෌⏕ࢩࣝࢡ⧄⥔ࠊࣇ࢕ࣈࣟ࢖ࣥࠊ⇕ฎ⌮ࠊᚤ⤖ᬗ
⫼ᬒ࡜◊✲┠ⓗ㸸
ᡃࡀᅜࡢ㣴⺋⏘ᴗࡣࠊ2005 ᖺẚ 31.7 %ῶ࡜⦰ᑠഴྥ࡟࠶ࡿࠋ୍᪉ࠊ㧗ᙉᗘ⧄⥔ࡢ㟂せࡣ㧗ࡲࡾ
ࡘࡘ࠶ࡿࡶࡢࡢ኱༙ࡣ▼Ἔ࡟౫Ꮡࡋ࡚࠸ࡿ⌧≧ࡶ࠶ࡿࠋ
ࡶࡋࠊ
⺋ࢩࣝࢡ⧄⥔ࡢᙉᗘࡀቑຍࡍࢀࡤࠊ
⬺▼Ἔ⧄⥔࡜ࡋ࡚♫఍ⓗ࡟ཷࡅධࢀࡽࢀࡿࡢࡳ࡞ࡽࡎࠊᅜෆࡢ㣴⺋⏘ᴗ࡬㈉⊩࡛ࡁࡿࠋࡑࡢⅭ࡟
ࡣ⧄⥔୰ࡢ⤖ᬗ㓄ྥᗘࢆ኱ᖜ࡟ቑຍࡉࡏࡿᚲせࡀ࠶ࡾࠊࡑࡢ⢭ᐦᵓ㐀ゎᯒᡭẁ࡜ࡋ࡚ SPring-8 ࢆ
฼⏝ࡋࡓࠋ
⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
ձ⇕ฎ⌮࡟ࡼࡿ≀ᛶኚ໬
ኳ↛ࢩࣝࢡ⧄⥔࠾ࡼࡧ෌⏕ࢩࣝ
ࢡ⧄⥔ࡢ⇕ฎ⌮࡟ࡼࡿຊᏛᙉᗘࡢ
ኚ໬ࢆᅗ 1 ࡟♧ࡍࠋኳ↛ࢩࣝࢡ⧄
⥔ࡣึᮇࡢᘬᙇ◚᩿ᙉᗘࡣ㧗࠸
ࡀࠊ⇕ฎ⌮࡟ࡼࡗ࡚పୗࡋ࡚࠸ࡗ
ࡓࠋ୍᪉ࠊ෌⏕ࢩࣝࢡ⧄⥔࡛ࡣࠊ
ึᮇࡢᘬᙇ◚᩿ᙉᗘࡣኳ↛ࢩࣝࢡ
⧄⥔࡜ẚ㍑ࡋ࡚ప࠸ࡀࠊ⇕ฎ⌮࡟
ࡼࡗ୍࡚᪦ᘬᙇ◚᩿ᙉᗘࡢྥୖࡀ
ㄆࡵࡽࢀࡓࠋࡇࢀࡣࠊෆ㒊ࡢ⤖ᬗ
ᵓ㐀ࡢኚ໬࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽ
ᘬᙇ◚᩿ᙉᗘ䠄㻹㻼㼍䠅
ᐇ㦂㸸
ᕷ㈍ࡢ⧛࠿ࡽ⬺ࢭࣜࢩࣥᕤ⛬ࢆ⤒࡚ࣇ࢕ࣈࣟ࢖ࣥ⧄⥔ࢆྲྀࡾฟࡋࡓࠋࡑࡢࡲࡲࢧࣥࣉࣝ࡜ࡋࡓ
ࡶࡢࢆኳ↛ࢩࣝࢡ⧄⥔࡜࿧ࡪࡇ࡜࡟ࡍࡿࠋኳ↛ࢩࣝࢡ⧄⥔ࡢ୍㒊ࢆ⁐ゎࠊ෾⤖஝⇱ࢆᐇ᪋ᚋ HFIP
䠄࣊࢟ࢧࣇࣝ࢜ࣟ࢖ࢯࣉࣟࣃࣀ࣮ࣝ䠅⁐ᾮ࡟෌⁐ゎࡋࠊ࢚ࢱࣀ࣮ࣝࢆจᅛᵴ࡜ࡋࡓ‵ᘧ⣳⣒ࢆ⾜࠺
ࡇ࡜࡛⧄⥔ࢆᚓࡓ[1]ࠋࡇࡢ⧄⥔ࢆࠊ✵Ẽ㞺ᅖẼୗ࡟࡚ᡭື࡛ 3 ಸ࡟ᘏఙࡋࡓࠋࡇࢀ࡟ࡼࡗ࡚ᚓࡽ
ࢀࡓ⧄⥔ࢆ෌⏕ࢩࣝࢡ⧄⥔࡜࿧ࡪࡇ࡜࡟ࡍࡿࠋ
ኳ↛ࢩࣝࢡ⧄⥔࡜෌⏕ࢩࣝࢡ⧄⥔ࡣࠊ80 Υ࡛ᡤᐃࡢ᫬㛫⇕ฎ⌮ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ⧄⥔࡟ࡘ࠸
࡚ࠊᘬᙇ㏿ᗘ 10 mm/minࠊࢳࣕࢵࢡ㛫㊥㞳 10 mm ࡟࡚ᘬᙇヨ㦂ࢆ⾜ࡗࡓࠋ
ࡉࡽ࡟ࠊᘬᙇヨ㦂๓ࡢ⧄⥔ࢆ 20 ᮏ⛬ᗘ᮰ࡡ࡚ྎ⣬࡟ᅛᐃࡋࠊSPring-8䠄BL40B2䠅࡟࡚ᐊ ୗࠊἼ
㛗 1 Åࠊ࣓࢝ࣛ㛗 25 mmࠊ㟢ග᫬㛫 30sec ࡟࡚ᗈゅ X ⥺ᅇᢡ䠄WAXD䠅ീࢆ ᐃࡋࡓࠋ
㻠㻡㻜
㻠㻜㻜
㻟㻡㻜
㻟㻜㻜
㻞㻡㻜
㻞㻜㻜
㻝㻡㻜
ኳ↛䝅䝹䜽⧄⥔
෌⏕䝅䝹䜽⧄⥔
㻜
㻡㻜㻜
⇕ฎ⌮᫬㛫䠄㼔㻕
㻝㻜㻜㻜
ᅗ 1. ᐃࢧࣥࣉࣝࡢᘬᙇ◚᩿ᙉᗘࡢኚ໬
ࢀࠊ㧗ḟᵓ㐀ゎᯒࢆᐇ᪋ࡋࡓࠋ
ղྛࢧࣥࣉࣝࡢ㧗ḟᵓ㐀ゎᯒ
ᅗ 2 ࡟ࡣࠊኳ↛ࢩࣝࢡ⧄⥔࡜ࠊ෌⏕ࢩࣝࢡ⧄
⥔ࡢࡑࢀࡒࢀ⇕ฎ⌮๓ࡢ WAXD ീࢆ♧ࡍࠋ
෌⏕
ࢩࣝࢡ⧄⥔ࡢ᪉ࡀ㉥㐨ୖ࡟ᙉࡃฟ࡚࠸ࡿ䠄200䠅
㠃࠿ࡽࡢᅇᢡࣆ࣮ࢡ[1]ࡀࡼࡾᙉࡃฟ࡚࠸ࡿࡶ
ࡢࡢࠊ඲యⓗ࡟཯ᑕࢫ࣏ࢵࢺࡀ୙㩭࡛᫂࠶ࡿࠋ
ࡇࡢ஦࠿ࡽࠊ⇕ฎ⌮๓࡟࠾࠸࡚ࡣࠊ෌⏕ࢩࣝࢡ
⧄⥔୰ࡢᚤ⤖ᬗࡀኳ↛ࢩࣝࢡ⧄⥔୰ࡢࡑࢀࡼࡾ
ᑠࡉ࠸ࡇ࡜ࡀఛ࠼ࡿࠋ
ḟ࡟ࠊ2 ḟඖ WAXD ീࢆ෇⎔ᖹᆒࡋ࡚ 1 ḟඖ
໬ࡋࠊᩓ஘࣋ࢡࢺࣝࡢ኱ࡁࡉ q㻌㻔= 4 / Ȣsin㸹
ࡇࡇ࡛ ࡣ X ⥺ࡢἼ㛗ࠊ ࡣᅇᢡゅ㻕࡟ᑐࡋ࡚ᅇ
ᢡᙉᗘࢆࣉࣟࢵࢺࡋࡓ㸦ᅗ 3㸧ࠋ
ᅗ 2. ⇕ฎ⌮๓ࡢ WAXD ⏬ീ
㸦ᕥ㸸ኳ↛ࢩࣝࢡ ྑ㸸෌⏕ࢩࣝࢡ㸧
ᅗ 3. ୍ḟඖᩓ஘ᙉᗘ᭤⥺ࡢ⇕ฎ⌮࡟ࡼࡿኚ໬
ᕥ㸸ᮍฎ⌮ኳ↛ࢩࣝࢡ⧄⥔ ྑ㸸෌⏕ࢩࣝࢡ⧄⥔ࡢ⇕ฎ⌮㐣⛬࡟࠾ࡅࡿኚ໬
ᅗ 4. ෌⏕ࢩࣝࢡ⧄⥔ࡢ୍ḟඖᩓ஘ᙉᗘ᭤⥺ᣑ኱ᅗ
ᅗ 3 ࡢ⤖ᯝ࠿ࡽࠊኳ↛ࢩࣝࢡ⧄⥔ࡣ෌⏕ࢩࣝࢡ⧄⥔࡜ẚ࡭࡚㗦࠸ࣆ࣮ࢡࡀ࠸ࡃࡘ࠿ぢࡽࢀࡓࠋ
Scherrer ࡢᘧ㸦ᘧ 1㸧࡟ࡼࡿ࡜ࠊࣆ࣮ࢡࡀࡼࡾࢩ࣮ࣕࣉ࡟࡞ࡿ࡯࡝ᚤ⤖ᬗࢧ࢖ࢬࡀቑຍࡋ࡚࠸ࡃࡇ
࡜࡟࡞ࡿⅭࠊኳ↛ࢩࣝࢡ⧄⥔ࡢ᪉ࡀࡼࡾᚤ⤖ᬗࢧ࢖ࢬࡀ኱ࡁ࠸஦ࡀ᥎ ࡉࢀࡓࠋ
L=K 㸭㸦cos㸧 ࣭࣭࣭䠄1䠅
㸦L㸸ᚤ⤖ᬗࡢ኱ࡁࡉ K㸸ᐃᩘ 㸸Ἴ㛗 㸸ࣆ࣮ࢡࡢ್༙ᖜ 㸸ᅇᢡゅ㸧
෌⏕ࢩࣝࢡ⧄⥔ࡢ⇕ฎ⌮๓ᚋࡢࣆ࣮ࢡ࡟ࡘ࠸࡚ࡣࠊq = 1.0㹼2.0 nm-1 ࡢ㡿ᇦࢆᣑ኱ࡍࡿ࡜
㸦ᅗ 4㸧ࠊ
⇕ฎ⌮ࢆᐇ᪋ࡋ࡚࠸ࡃࡇ࡜࡟ࡼࡾࢩ࣮ࣕࣉ࡞ࣆ࣮ࢡ࡟ኚ໬ࡍࡿ஦ࡀศ࠿ࡗࡓࠋᘧ 1 ࠿ࡽࠊ෌⏕ࢩ
ࣝࢡ⧄⥔ࢆ⇕ฎ⌮ࡍࡿ஦࡟ࡼࡗ࡚ࡶࠊᚤ⤖ᬗࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡿࡶࡢ࡜᥎ ࡛ࡁࡿࠋ
௨ୖࡢ஦࠿ࡽࠊ෌⏕ࢩࣝࢡ⧄⥔ࡣ⇕ฎ⌮࡟ࡼࡗ࡚ᚤ⤖ᬗࡢᡂ㛗ࡀ♧၀ࡉࢀᅗ 1 ࡢᘬᙇヨ㦂⤖ᯝ
࡜┦㛵ࡋ࡚࠸ࡿࡼ࠺࡟ᛮࢃࢀࡿࡀࠊ⇕ฎ⌮࡜࡜ࡶ࡟ඛ㗦໬ࡋࡓ࡜ゝ࠼࡝ࡶࠊ෌⏕ࢩࣝࢡ⧄⥔ࡣኳ
↛ࢩࣝࢡ⧄⥔࡜ẚ㍑ࡍࡿ࡜ᅇᢡࣆ࣮ࢡࡀࡲࡔࡲࡔ୙᫂░࡛࠶ࡿ஦࠿ࡽࠊHFIP ࡟࡚ฎ⌮ࡋ࡚ᚓࡓ⧄
⥔ࡣࡉࡽ࡟ᚤ⤖ᬗࡢᡂ㛗ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀᮇᚅ࡛ࡁࠊࡦ࠸࡚ࡣࠊᘬᙇ◚᩿ᙉᗘࡢࡉࡽ࡞ࡿቑຍ
ࡀᮇᚅ࡛ࡁࡿࠋ
௒ᚋࡢㄢ㢟㸸
ᚤ⤖ᬗࢧ࢖ࢬࡢゎᯒࡢࡳ࡞ࡽࡎࠊ
ᚤ⤖ᬗࡢ㓄ྥࡢゎᯒࡶ⾜࠸ࠊ
ᵓ㐀ไᚚࡢᣦ㔪ࢆ☜❧ࡋ࡚࠸ࡃࠋ
ཧ⪃ᩥ⊩㸸
[1] Z.H.Zhu, K.Ohgo, T.Asakura, eXPRESS Polymer Letters, 2, 885-889, 㻔2008㻕