࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢぢ࠿ࡅ⇕ఏᑟ⋡࡟ᑐࡍࡿ⤖ᬗ࡜࢞ࣛࢫࡢᒅᢡ⋡ᕪࡢᙳ㡪◊✲௦⾲⪅ ᮾிᕤᴗ኱Ꮫ ≀㉁⌮ᕤᏛ㝔 ຓᩍ 㐲⸨⌮ᜨඹྠ◊✲⪅ ᮾிᕤᴗ኱Ꮫ ≀㉁⌮ᕤᏛ㝔 ᩍᤵ 㡲బ໷⿱ඹྠ◊✲⪅ ⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ ୺ᖍ◊✲ဨ ᱓ཎṇྐ1㸬⥴ゝ ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡣ㸪⁐㗰ୖ㠃࡟ᩓᕸࡉࢀ㸪⁐㗰࡜㗪ᆺ㛫࡟౵ධࡋ㸪㗰ࡢ෭༷㏿ᗘࢆไᚚࡍࡿ௚㸪㗪∦/㗪ᆺ㛫ࡢ₶⁥㸪ࡲࡓ㗪∦ࡢ෌㓟໬㜵Ṇ࡞࡝ࡢᙺ๭ࡶᢸ࠺ࠋ㐃⥆㗪㐀࡛ࡣ㸪⦪๭ࢀ࡞࡝ࡢ㗪㐀Ḟ㝗ࢆ㜵ࡄࡓࡵ࡟㸪㗪∦ࡢ⦆෭༷ࡀ୙ྍḞ࡜࡞ࡾ㸪ᚑ᮶ࡼࡾ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢఏ⇕≉ᛶࡀ㔜せ࡜࡞ࡗ࡚࠸ࡿࠋࣇࣛࢵࢡࢫࣇ࢕࣒ࣝࡣ㸪⁐㗰ഃࡼࡾᾮᒙ㸪⤖ᬗᒙ࠾ࡼࡧ࢞ࣛࢫᒙ࠿ࡽᡂࡗ࡚࠾ࡾ㸪ࡑࡢཌࡉࡣᩘ mm ࡜ⷧ࠸ࠋࡇࡢࡓࡵ㸪⁐㗰࠿ࡽ㗪ᆺ࡬ࡢఏ⇕ࡣఏᑟ࠾ࡼࡧᨺᑕ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ㏆ᖺࡢ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡣ㸪㗰ࡢจᅛࡢึᮇ࠿ࡽ⤖ᬗ໬ࡍࡿࡼ࠺࡟タィࡉࢀ࡚࠸ࡿࠋ⤖ᬗ໬࡟ࡼࡗ࡚ఏᑟఏ⇕ࡣ኱ࡁࡃ࡞ࡿࡶࡢࡢᨺᑕఏ⇕ࢆ኱ᖜ࡟పῶ࡛ࡁࡿࡓࡵ㸪㗪∦ࡢ⦆෭༷࡟ࡘ࡞ࡀࡿࠋࡇࢀࡣ㸪㗪∦࠿ࡽࡢ㠀ᖖ࡟ᙉ࠸ᨺᑕගࢆࣇࣛࢵࢡࢫࡢ⤖ᬗ┦ࢆ⏝࠸࡚཯ᑕࡉࡏࡿࡇ࡜ࢆཎ⌮࡜ࡋ࡚࠸ࡿ 1-3)ࠋ
ࡉࡽ࡞ࡿ⦆෭༷ࡢࡓࡵ࡟ࡣ㸪ࣇࣛࢵࢡࢫࡢ⤌ᡂࢆㄪᩚࡍࡿࡇ࡜ࡀᣲࡆࡽࢀࡿࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢ୺ᡂศ࡛࠶ࡿࢩࣜࢣ࣮ࢺ⣔ࡢ⇕ఏᑟ⋡࡟ࡘ࠸࡚ㄪᰝࡍࡿ࡜㸪ࡑࡢ⤌ᡂ౫Ꮡᛶ࠾ࡼࡧᗘ౫Ꮡᛶࡣᑠࡉ࠸ࠋࡋࡓࡀࡗ࡚㸪⤌ᡂኚ໬࡟ࡼࡿఏᑟࡢ⇕ὶ᮰ࡣ࠶ࡲࡾኚ໬ࡋ࡞࠸ࡇ࡜ࡀண᝿࡛ࡁࡿ 4,5)ࠋ୍᪉࡛㸪ගᏛ≉ᛶ(཯ᑕ⋡㸪㏱㐣⋡࠾ࡼࡧ྾཰⋡࡞࡝)ࡣ⤌ᡂ࡟ࡼࡗ࡚኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕ㸪ᨺᑕఏ⇕ࡣ⤌ᡂ࡟ࡼࡗ࡚኱ࡁࡃኚ໬ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ౛࠼ࡤ㸪ࣇࣛࢵࢡࢫ࡟㑄⛣㔠ᒓ㓟໬≀ࡀྵࡲࢀ࡚࠸ࡿ࡜ࡁ࡟ࡣ㸪㑄⛣㔠ᒓ࢖࢜ࣥ࡟ࡼࡿ྾཰ࡀ࠶ࡿࡓࡵ࡟㸪ྍどගᇦ࡛ࡣ྾཰⋡ࡀቑຍࡍࡿࠋࡇࢀࡣ㸪㑄⛣㔠ᒓࡢ㘒యࡣ d 㟁Ꮚ㌶㐨㛫ࡢ㟁Ꮚ㑄⛣࡟ᇶ࡙ࡃග྾཰ࢆ㉳ࡇࡍࡓࡵ࡛࠶ࡿࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ࡟㓟໬㕲ࡣ୙ྍ㑊࡟ྵࡲࢀ㸪ࣇࣛࢵࢡࢫࡢගᏛ≉ᛶ࠾ࡼࡧᨺᑕఏ⇕ὶ᮰ࢆ኱ࡁࡃኚ໬ࡉࡏࡿࠋࡇࡢࡼ࠺࡞⫼ᬒࡼࡾ㸪Susa ࡽࡢࢢ࣮ࣝࣉ࡛ࡣ⁐㗰/࣮ࣔࣝࢻࣇࣛࢵࢡࢫ/㗪ᆺࡢᨺᑕ࣭ఏᑟఏ⇕ࣔࢹࣝࢆᵓ⠏ࡋ࡚㸪ࡑࡢᙳ㡪࡟ࡘ࠸࡚ࡣ௨ୗࡢࡼ࠺࡞▱ぢࡀᚓࡽࢀ࡚࠸ࡿࠋ(i) ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ୰ࡢ㓟໬㕲ࡣᨺᑕఏ⇕ࢆቑຍࡉࡏࡿຠᯝࡀ࠶ࡿࠋ(ᝏᙳ㡪ࢆ୚࠼ࡿ)6)(ii) ࣇࣛࢵࢡࢫ୰ࡢ㕲࢖࢜ࣥࡢ౯ᩘ࡟ࡼࡗ࡚ࡶᨺᑕఏ⇕ὶ᮰ࡣኚ໬ࡍࡿࠋ 㸵)(iii) ⤖ᬗ໬ࣇࣛࢵࢡࢫ࡟࠾࠸࡚㸪㓟໬㕲ࡣ࢞ࣛࢫ㒊ศ࡟ከࡃᏑᅾࡍࡿࠋ࢞ࣛࢫ㒊ศࡢ⤌ᡂࢆㄪᩚࡋ࡚ᒅᢡ⋡ࢆኚ໬ࡉࡏࡿࡇ࡜࡛㸪㓟໬㕲ྵ᭷ࣇࣛࢵࢡࢫ࡟࠾࠸࡚ࡶᨺᑕఏ⇕ࡢపῶࡀᮇᚅ࡛ࡁࡿࠋ8)⁐㗰࡟ᩓᕸࡉࢀ⁐⼥ࡋࡓ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡣ㸪ึᮇ࡟㓟໬㕲ࢆྵࢇ࡛࠸࡞࠸ሙྜ㸫㸫࡛ࡶ⁐㗰ࡼࡾ㓟໬㕲ࡀ୙ྍ㑊࡟⁐Ꮡࡍࡿࡓࡵ 9)㸪㓟໬㕲ࡢᙳ㡪ࡢపῶ᪉ἲࡀㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋ▱ぢ(iii)ࡣ㸪࢞ࣛࢫ࡜⤖ᬗࡢᒅᢡ⋡ᕪࡀ኱ࡁࡃ࡞ࡿ࡜ぢ࠿ࡅࡢ཯ᑕ⋡ࡀ㧗ࡃ࡞ࡿࡇ࡜ࢆ฼⏝ࡋࡓࡶࡢ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽ㸪ᮍࡔᐇ㦂ⓗ࡟ࡣ᳨ドࡉࢀ࡚࠸࡞࠸ࠋ
ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢఏ⇕≉ᛶ࡟ᑐࡍࡿ࢞ࣛࢫ࡜࢝ࢫࣆࢹ࢕ࣥࡢ
ᒅᢡ⋡ᕪࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ2㸬SiO2 ࡢᒅᢡ⋡࡟ᑐࡍࡿῧຍᡂศࡢᙳ㡪 ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡣ㸪SiO2-CaO-Al2O3-CaF2-Na2O ࡞࡝࠿ࡽᡂࡿࠋࡇࡇ࡛ࡣ㸪࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢᒅᢡ⋡࡟ᑐࡍࡿῧຍᡂศࡢᙳ㡪ࢆண᝿ࡍࡿࠋᒅᢡ⋡࡟ࡣຍᡂᛶࡀᡂࡾ❧ࡘࡓࡵ㸪 SiO2 ࢞ࣛࢫࡢᒅᢡ⋡࡟ᑐࡍࡿῧຍᡂศࡢᙳ㡪ࢆㄪᰝࡋࡓࠋ Fig.1 ࡟ SiO2-R2O㸦R=Li㸪Na, K, Cs, Rb㸧⣔ࡢἼ㛗 589 nm ࡟࠾ࡅࡿᒅᢡ⋡ࡢ⤌ᡂ౫Ꮡᛶࢆ♧ࡍࠋ10) SiO2-Na2O ⣔ࡢᒅᢡ⋡ࡀ᭱ࡶᑠࡉࡃ㸪K2O, Rb2OҮLi2O, Cs2O ࡢῧຍࡢ㡰࡟ᒅᢡ⋡ࡀ኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋK2O ࡜ Na2O ῧຍ࡟ࡼࡿᒅᢡ⋡ࡢኚ໬ࡣྠ⛬ᗘ࡛࠶ࡾ㸪ࡲࡓ Li2O ࡜ Rb2O ࡢᙳ㡪ࡶྠ⛬ᗘ࡛࠶ࡿࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ୰ࡢ⤖ᬗ┦࡛࠶ࡿ࢝ࢫࣆࢹ࢕ࣥࡢᒅᢡ⋡ࡣἼ㛗 589 nm ࡟࠾࠸࡚ 1.590-1.602 ࡜ሗ࿌ࡉࢀ࡚࠾ࡾ 11)㸪Fig.1 ࡛♧ࡋࡓᒅᢡ⋡ࡼࡾࡶ኱ࡁ࠸ࠋࡋࡓࡀࡗ࡚㸪࢝ࢫࣆࢹ࢕ࣥ࡜ࡑ
ࡢ࿘ᅖࡢ࢞ࣛࢫ࡜ࡢᒅᢡ⋡ᕪࢆ኱ࡁࡃࡍࡿ࡟ࡣ Na2O ࡲࡓࡣ K2O ῧຍࡀຠ⋡ⓗ࡛࠶ࡿࡇ࡜ࡀண᝿ࡉࢀࡿࠋࡇࢀࢆ᳨ドࡍࡿࡓࡵ࡟ᮏ◊✲࡛ࡣ㸪ᚑ᮶ࡢ Na2O ࢆྵࡴ࣮ࣔࣝࢻ
ࣇࣛࢵࢡࢫࡢᡂศࡢ࠺ࡕ㸪Na2O ࢆ Li2O ࡟⨨ࡁ᥮࠼㸪࣮ࣔࣝࢻࣇࣛࢵࢡࢫ࡜⤖ᬗ࡜ࡢᒅᢡ⋡ᕪࡢᑠࡉ࠸ࣇࣛࢵࢡࢫࢆస〇ࡋࡓࠋࡇࢀࡽࡢࣇࣛࢵࢡࢫࡢぢ࠿ࡅࡢ⇕ఏᑟ⋡࡟ᑐࡍࡿ⤖ᬗ/࢞ࣛࢫ┦㛫ࡢᒅᢡ⋡ᕪࡢᙳ㡪ࢆホ౯ࡍࡿࡇ࡜࡜ࡋࡓࠋ
㸫㸫Fig.1 Refractive index of SiO 2-R2O system at 589 nm10)3㸬ᐇ㦂᪉ἲ
ᇶᮏ࡜ࡍࡿᶍᨃ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ࡜ࡋ࡚㸪SiO2-CaO-Al2O3-CaF2-Na2O ࡟ Fe2O3
ࢆ 2mass%ྵࡴࡶࡢࢆ⏝࠸ࡓ(௨㝆㸪MF-Na2O ࡜࿧ࡪ)ࠋࡇࡢࣇࣛࢵࢡࢫࡢ࠺ࡕ㸪Na2O
ࢆ Li2O ࡛⨨ࡁ᥮࠼ࡓࡶࡢࡶస〇ࡋࡓ(௨㝆㸪MF-Li2O ࡜࿧ࡪ)ࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ୰
ࡢ࢞ࣛࢫ㒊ศࢆᶍᨃࡋࡓヨᩱࡶస〇ࡋࡓࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢᡂศ࠿ࡽ࢝ࢫࣆࢹ࢕
ࣥᡂศ(3CaO࣭2SiO2࣭CaF2)ࢆᘬ࠸࡚ṧࡗࡓ⤌ᡂࡀ࢞ࣛࢫ㒊ศࡢ⤌ᡂ࡟࡞ࡿ࡜⪃࠼ࡓ(ヨᩱྡ glass-Na2O ࠾ࡼࡧ glass-Li2O)ࠋィ⟬ୖ࡛ࡣ㸪MF-Na2O ࡜ MF-Li2O ࡢ⤖ᬗ┦ࡣ࠸ࡎࢀࡶ࢝ࢫࣆࢹ࢕࡛ࣥ࠶ࡿࡓࡵ㸪2 ࡘࡢヨᩱࡢ┦㐪ࡣ࢞ࣛࢫ┦ࡢ⤌ᡂࡢ㐪࠸࡜࡞ࡿࠋ௨ୖࡢヨᩱࡢస〇࡟ࡣ≉⣭ヨ⸆ࡢ SiO2㸪CaO㸪Al2O3, CaF2, Na2CO3 ࠾ࡼࡧ Li2CO3ࢆ⏝࠸ࡓࠋࡓࡔࡋ㸪CaO ࡣ≉⣭ヨ⸆ࡢ CaCO3 ࢆ 1323 K ࡟࡚ 43.2 ks 㛫⇕ศゎࡋ࡚స〇ࡋࡓࠋΰྜヨᩱࢆⓑ㔠ࡿࡘࡰ࡟ධࢀ㟁Ẽ⅔ෆ࡟࠾࠸࡚኱Ẽ୰㸪1673 K ࡛⁐⼥ಖᣢࡋࡓᚋ㸪┿㘷〇ࡢ㗪ᆺ࡟ὶࡋ㎸ࢇࡔࠋࡇࢀ࡟ࡼࡾ㸪ཌࡉ 5 mm㸪ᖜ 20 mm㸪㛗ࡉ 40 -50mm ࡢ࢞ࣛࢫヨᩱࢆᚓࡓࠋヨᩱ MF-Na2O ࡜ MF-Li2O ࡣࡉࡽ࡟ 660Υ࡟࠾࠸࡚ 30 min⇕ฎ⌮ࢆ⾜࠸㸪⤖ᬗ໬ࡉࡏ࡚స〇ࡋࡓࠋศᯒ࡛ࡣศගගᗘィ࠾ࡼࡧ࢚ࣜࣉࢯ࣓࣮ࢱࢆ⏝࠸࡚ගᏛᐃࡋ㸪㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾(SEM)ࢆ⏝࠸࡚⤌⧊ࢆほᐹ㸪X ⥺ᅇᢡ(XRD)ࢆ

⏝࠸࡚┦ྠᐃࢆ⾜ࡗࡓࠋ㸫㸫4㸬⤖ᯝ
Fig.2 ࡟ヨᩱࡢ෗┿ࢆ♧ࡍࠋMF-Na2O ࡣ MF-Li2O ࡼࡾࡶࢃࡎ࠿࡟⥳Ⰽࢆ࿊ࡋ࡚࠸
ࡓࠋࡲࡓ㸪glass-Na2O ࡜ glass-Li2O ࡣ㏱࡛᫂࠶ࡾ㸪๓⪅ࡣࢃࡎ࠿࡟⥳Ⰽ㸪ᚋ⪅ࡣࢃࡎ࠿࡟ⲔⰍࢆ࿊ࡋ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚㸪MF-Na2O ࡢ⥳Ⰽࡣ࢞ࣛࢫ㒊ศࡢᙳ㡪࡜⪃࠼ࡽࢀ㸪࢞ࣛࢫ㒊ศࡢගᏛ≉ᛶࡀ⤖ᬗ໬ࣇࣛࢵࢡࢫࡢぢ࠿ࡅࡢගᏛ≉ᛶ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡇࢀࡽࡢⰍࡣ㸪㕲࢖࢜ࣥ࡟ࡼࡿ྾཰ࡀ࠶ࡿࡓࡵ࡟ぢࡽࢀࡿࡶࡢ࡛࠶ࡿࠋ

20 mm

MF-Na2O

MF-Li2O

glass-Na2O

glass-Li2 O

Fig.2 Photographs of samples

Fig.3 ࡟࢞ࣛࢫ㒊ศᶍᨃヨᩱࡢᒅᢡ⋡ࡢᐃ⤖ᯝࢆ࢝ࢫࣆࢹ࢕ࣥࡢᒅᢡ⋡࡜࡜ࡶ࡟♧ࡍࠋ ᐃࡣ 0.3-1.7 μm ࡢἼ㛗⠊ᅖ࡛⾜ࡗࡓࠋヨᩱ glass-Na2O ࡢᒅᢡ⋡ࡣ glass-Li2Oࡼࡾࡶᑠࡉ࠸ࠋࡉࡽ࡟㸪࢝ࢫࣆࢹ࢕ࣥ࡜ࡢᒅᢡ⋡ᕪࡣ glass-Na2O ࡢ᪉ࡀ኱ࡁ࠸ࠋࡇࡢ⤖ᯝࡣ㸪2.⠇࡟࠾ࡅࡿ SiO2 ࢞ࣛࢫࡢᒅᢡ⋡࡟ᑐࡍࡿ R2O ࡢᙳ㡪ホ౯࡜ྠࡌഴྥ࡛࠶ࡾ㸪Fe2O3 ࢆྵࡴከᡂศ⣔࡛࠶ࡗ࡚ࡶ㸪ᒅᢡ⋡ࡢຍᡂᛶ࡟ᇶ࡙࠸ࡓ⪃࠼᪉ࡀ㐺⏝࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

1.7glass-Na2Oglass-Li 2O

Refractive index, ncusipidine

1.6

1.5

1.4

0.5

1Wavelength/ Pm

1.5

Fig.3 Measured refractive index for glass-Na2O and glass-Li2O samples㸫㸫Fig.4 ࡟ MF-Na2O ࡜ MF-Li2O ࡢ⤖ᬗ໬ࣇࣛࢵࢡࢫࡢぢ࠿ࡅ཯ᑕ⋡ࢆ♧ࡍࠋᐃࡣ

0.3-2.6 μm ࡢἼ㛗࡛⾜ࡗࡓࠋἼ㛗 0.3-0.6 μm ࠾ࡼࡧ 1.2-2.6 μm ࡢ⠊ᅖ࡛ࡣ MF-Na2O
ࡢ཯ᑕ⋡ࡀ㧗࠸ࠋ㕲ࡢ⼥Ⅼ࡟࠾ࡅࡿᨺᑕࡢࣆ࣮ࢡἼ㛗ࡣ 1.6 μm ࡛࠶ࡾ㸪ࡇࡢἼ㛗ࡢ࿘ᅖ࡟࠾࠸࡚ࡶ MF-Na2O ࡢ཯ᑕࡀ኱ࡁ࠸ࠋFig.3 ࡢ⤖ᯝ࡜ྜࢃࡏࡿ࡜㸪࢞ࣛࢫ࡜⤖ᬗࡢᒅᢡ⋡ᕪࡢ኱ࡁ࠸ MF-Na2O ࡢ᪉ࡀぢ࠿ࡅࡢ཯ᑕ⋡ࡀ኱ࡁࡃ࡞ࡾ㸪ᨺᑕఏ⇕ࡀపῶ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋ
 Fig.4 ࡛ࡣ㸪Ἴ㛗 0.6-1.2 μm ࡢ⠊ᅖ࡛ࡣ MF-Li2O ࡢ⤖ᬗ໬ࣇࣛࢵࢡࢫࡢ᪉ࡀぢ࠿ࡅ཯ᑕ⋡ࡀ኱ࡁࡃ࡞ࡗ࡚࠸ࡿࠋࡇࡢཎᅉࢆㄪᰝࡍࡿࡓࡵ࡟ SEM ࡟ࡼࡿ⤌⧊ほᐹࢆ⾜ࡗࡓࠋReflectivity, Ra / %100
MF-Na 2O
MF-Li2O

80
6040
200500

1000
1500
2000
Wavelength, O / nm2500
Fig.4 Apparent reflectivity of MF-Na2O and MF-Li2O crystallised samples

Fig.5 ࡟ྛヨᩱࡢ BSE ീࢆ♧ࡍࠋ࠸ࡎࢀࡢヨᩱ࡟࠾࠸࡚ࡶⓑࡃぢ࠼ࡿࡢࡀ⤖ᬗ┦ࡢ࢝ࢫࣆࢹ࢕࡛ࣥ࠶ࡾ㸪ࡑࡢ࿘ᅖࡢ⃰࠸⅊Ⰽࡢ㒊ศࡣ࢞ࣛࢫ┦࡛࠶ࡿࠋMF-Li2O ࡛ࡣⷧ࠸⅊Ⰽࡢ⤖ᬗ┦ࡶぢࡘ࠿ࡗࡓࠋ⏬ീฎ⌮࡟ࡼࡾ㸪࢝ࢫࣆࢹ࢕ࣥࡢᖹᆒ⢏ᚄ࡜⤖ᬗ໬⋡ࢆ⟬ฟࡋࡓ࡜ࡇࢁ㸪ヨᩱ MF-Na2O ࡛ࡣ㸪ᖹᆒ⢏ᚄ 1.8μm࣭⤖ᬗ໬⋡ 68%࡟ᑐࡋ㸪MF-Li2O ࡛ࡣ⤖ᬗ⢏ᚄ 1 μm࣭⤖ᬗ໬⋡ 84%(66%࢝ࢫࣆࢹ࢕ࣥ࠾ࡼࡧ 18%(4Li2O࣭
SiO2࣭CaO))࡜ᚓࡽࢀࡓࠋヨᩱ MF-Na2O ࡢ཯ᑕࡢせᅉࡣ㸪࢝ࢫࣆࢹ࢕ࣥ࡜࢞ࣛࢫ⏺
㠃࡟࠾ࡅࡿ཯ᑕ࡜⪃࠼ࡽࢀࡿࠋ୍᪉㸪ヨᩱ MF-Li2O ୰ࡢ 2 ࡘ┠ࡢ⤖ᬗ┦ 4Li2O࣭SiO2࣭CaO ࡣ࢞ࣛࢫ㒊ศ࡜ࡢᡂศࡀఝ࡚࠸ࡿࡓࡵ㸪࢞ࣛࢫ࡜⤖ᬗ㛫ࡢᒅᢡ⋡ᕪࡣᑠࡉ࠸࡜ண᝿ࡉࢀࡿࠋࡋࡓࡀࡗ࡚㸪ヨᩱ MF-Li2O ࡟࠾࠸࡚ࡶࡑࡢ཯ᑕࡢせᅉࡣ࢝ࢫࣆࢹ࢕ࣥ࡜࢞ࣛࢫ࡜ࡢᒅᢡ⋡ᕪ࡟ࡼࡿ⏺㠃࡛ࡢ཯ᑕ࡜⪃࠼ࡽࢀࡿࠋヨᩱ MF-Li2O ୰ࡢ⤖ᬗ⢏ᚄࡣ㸪㸫㸫

1 μm ࡛࠶ࡾ㸪Fig.4 ࡟࠾࠸࡚཯ᑕ⋡ࡀ኱ࡁࡃᐃࡉࢀࡓἼ㛗(0.6-1.2 μm)࡜୍⮴ࡋ࡚࠸ࡿࠋࡇࢀࡣ࣑࣮ᩓ஘࡟ࡼࡗ࡚ぢ࠿ࡅࡢ཯ᑕ⋡ࡀ኱ࡁࡃ࡞ࡗࡓࡇ࡜ࢆ⾲ࡋ࡚࠸ࡿࠋࡇ
ࡢࡼ࠺࡞ほⅬ࠿ࡽ Fig.4 ࢆぢࡿ࡜ 1.8 μm ࡟࠾ࡅࡿ MF-Na2O ࡢ཯ᑕ⋡ࡶ㧗ࡃ࡞ࡗ࡚࠾ࡾ㸪࣑࣮ᩓ஘ࡢᙳ㡪ࡀ⾲ࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡍ࡞ࢃࡕ㸪ᚑ᮶ࡢ Na2O ῧຍࡢ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ࡛ࡣ࢝ࢫࣆࢹ࢕ࣥ࡜࢞ࣛࢫ⏺㠃ࡢ཯ᑕ࠾ࡼࡧ࣑࣮ᩓ஘ࡢ୧᪉ࡢⅬ࠿ࡽぢ࠿ࡅࡢ཯ᑕ⋡ࡀ㧗ࡃ࡞ࡿࡼ࠺࡟タィࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

(b) MF-Li2O(a) MF-Na2O

㼏㼡㼟㼕㼜㼕㼐㼕㼚㼑㼓㼘㼍㼟㼟㼓㼘㼍㼟㼟㻠㻸㼕㻞㻻䞉㻿㼕㻻㻞䞉㻯㼍㻻㼏㼡㼟㼕㼜㼕㼐㼕㼚㼑
5 μm

5 μm
Fig.5 SEM images for samples: (a) MF-Na2O and (b) MF-Li2O

5㸬⪃ᐹ⤖ᬗ໬ࣇࣛࢵࢡࢫࡢぢ࠿ࡅࡢ⇕ఏᑟ⋡ࡣ, Nakada ࡽ 12)ࡢࣔࢹࣝࢆ㐺⏝ࡋ࡚⟬ฟࡋࡓࠋࣔࢹࣝࡢᶍᘧᅗࢆ Fig. 6 ࡟♧ࡍࠋ

Fig. 6 Schematic of temperature distribution applied in this studyィ⟬᮲௳ࡣ௨ୗࡢ࡜࠾ࡾ࡛࠶ࡿࠋ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢ㧗ഃࡣᅛయᒙ࡛࠶ࡾ㸪పഃࡣ࢞ࣛࢫᒙ࡜ࡋ㸪ཌࡉࡢྜィࡣ 1 mm ࡜ࡋࡓࠋ⁐㗰/ࣇࣛࢵࢡࢫ⏺㠃࠾ࡼࡧࣇࣛࢵ㸫㸫ࢡࢫ/㗪ᆺ⏺㠃ࡢᗘࡣࡑࢀࡒࢀ 1388 K ࠾ࡼࡧ 772 K ࡜ࡋ㸪࢚࢔ࢠࣕࢵࣉࡢᙳ㡪ࡣ⪃៖ࡋ࡞࠿ࡗࡓࠋࡑࢀࡒࢀࡢᒙ࡟࠾࠸࡚⇕ࡣఏᑟ࠾ࡼࡧࡩࡃᑕ࡛ఏࢃࡿࠋࡇࡢ࡜ࡁ㸪ఏᑟ࠾ࡼࡧᨺᑕ⇕ὶ᮰ࡣ௨ୗࡢᘧ࡛୚࠼ࡽࢀ㸪ᐃᖖ≧ែ࡛ࡣྛᒙ࡟࠾ࡅࡿ⥲ᣓ⇕ὶ᮰ࡀ୍⮴ࡍࡿࠋ‫ݍ‬ୡ୭୬ୢ୳ୡ୲୧୴ୣ ൌ ߣୡ୭୬ୢ୳ୡ୲୧୴ୣ ቆ‫ݍ‬୰ୟୢ୧ୟ୲୧୴ୣ ൌ୍ܶ െ ୍୍ܶቇ݀(1)݊ଶ ߪ൫୍ܶସ െ ୍୍ܶସ ൯ͲǤ͹ͷߙ݀ ൅ ߝ୍ିଵ ൅ ߝ୍୍ିଵ െ ͳ(2)ࡇࡇ࡛㸪q, O, T, n, V, D, d ࠾ࡼࡧHࡣࡑࢀࡒࢀ⇕ὶ᮰㸪⇕ఏᑟ⋡㸪ᗘ㸪ᒅᢡ⋡㸪

Stefan-Boltzmann ᐃᩘ㸪྾཰ಀᩘ㸪ཌࡉ ࠾ࡼࡧᨺᑕ⋡ ࢆ♧ࡋ࡚࠸ࡿࠋ ୗ௜ࡁࡢconductive, radiative, I ࠾ࡼࡧ II ࡣࡑࢀࡒࢀఏᑟ㸪ᨺᑕ㸪㧗ഃ࠾ࡼࡧపഃࢆ♧ࡋ࡚࠸ࡿࠋィ⟬ࡣ㸪MF-Na2O ࠾ࡼࡧ MF-Li2O ࡟ࡘ࠸࡚⾜ࡗࡓࠋTable 1 ࡟ィ⟬࡟౑⏝ࡋࡓ≀ᛶ್ࢆ♧ࡍࠋ⤖ᬗ໬ࣇࣛࢵࢡࢫ(MF-Na2O ࠾ࡼࡧ MF-Li2O)ࡢ཯ᑕ⋡ࡣ㸪⤖ᯝ࡜ࡋ࡚྾཰ಀᩘ(D)ࢆኚ໬ࡉࡏࡿ࡜ࡋ࡚ྲྀࡾධࢀࡽࢀ࡚࠸ࡿࠋ྾཰ಀᩘࡣ
࠿ࡽ⟬ฟࡋࡓࠋ⤖ᬗᒙ࡜࢞ࣛࢫᒙࡢ⏺㠃

ᐃࡋࡓ㏱㐣⋡ᗘࢆ 923 K(ࣇࣛࢵࢡࢫࡢ⤖ᬗ໬⥲ᣓ⇕ὶ᮰࠾ࡼࡧࣇࣛࢵࢡࢫࡢཌࡉࢆồࡵࡓࠋࡉࡽ࡟㸪ᗘ)࡜ࡋ࡚㸪ᗘᕪ࠿ࡽ௨ୗࡢᘧࢆ⏝࠸࡚ࣇࣛࢵࢡࢫ඲యࡢぢ࠿ࡅࡢ⇕ఏᑟ⋡ࢆ⟬ฟࡋࡓࠋȟܶ‫ ݍ‬ൌ ‫ݍ‬ୡ୭୬ୢ୳ୡ୲୧୴ୣ ൅ ‫ݍ‬୰ୟୢ୧ୟ୲୧୴ୣ ൌ ߣୟ୮୮ ൬ ൰݀(3)ᚓࡽࢀࡓぢ࠿ࡅࡢ⇕ఏᑟ⋡(Oapp)ࡣ MF-Na2O ࠾ࡼࡧ MF-Li2O ࡑࢀࡒࢀ 1.88 Wm-1K-1
࠾ࡼࡧ 1.92 Wm-1K-1 ࡛࠶ࡗࡓࠋMF-Li2O ࡢ᪉ࡀぢ࠿ࡅ⇕ఏᑟ⋡ࡀ㧗ࡃᚓࡽࢀࡓࠋࡍ
࡞ࢃࡕ㸪ࡣࡌࡵ࡟ண

ࡋࡓ㏻ࡾ MF-Li2O ࡢぢ࠿ࡅࡢ཯ᑕ⋡ࡀప࠸ࡓࡵ࡟⁐㗰࠿ࡽࡢᨺᑕගࡀ⤖ᬗᒙࢆ㏱㐣ࡋ࡚㗪ᆺ࡬ఏࢃࡿᙳ㡪ࡀ኱ࡁࡃ࡞ࡿࠋࡇࢀࡣ㸪⤖ᬗᒙ࡟࠾ࡅࡿ⤖ᬗ࡜࢞ࣛࢫࡢᒅᢡ⋡ᕪࡀᑠࡉ࠸ࡇ࡜ࢆせᅉ࡜ࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽ㸪ࡑࡢぢ࠿ࡅ⇕ఏᑟ⋡ࡢኚ໬ࡣ⣙ 2%௨ୗ࡜ᑠࡉ࠸ࠋ
MF-Na2O ࡼࡾࡶ⦆෭༷ᛶ⬟ࡢ㧗࠸ࣇࣛࢵࢡࢫࢆタィࡍࡿ࡟ࡣ㸪࢞ࣛࢫ┦ࡢᒅᢡ⋡ࢆᑠࡉࡃࡍࡿᚲせࡀ࠶ࡿࠋࡑࡢୗ㝈ࡢᒅᢡ⋡ࡣ SiO2 ࡢࡶࡢ࡟࡞ࡿࠋFig.1 ࡜ Fig.3 ࢆྜࢃࡏ࡚⪃࠼ࡿ࡜㸪589 nm ࡟࠾ࡅࡿᒅᢡ⋡ࡣ glass-Li2O > glass-Na2O > SiO2 ࡢ㡰࡟ᑠࡉࡃ࡞ࡾ㸪glass-Na2O ࡜ SiO2 ࡢᒅᢡ⋡ᕪࡣ glass-Li2O ࡜ glass-Na2O ࡢᕪࡼࡾࡶᑠࡉ࠸ࠋࡋࡓࡀࡗ࡚㸪⤖ᬗ໬࣮ࣔࣝࢻࣇࣛࢵࢡࢫ୰ࡢ࢞ࣛࢫ┦ࡀ SiO2 ࡟࡞ࡗࡓ࡜ࡋ࡚ࡶࡑࡢぢ࠿ࡅ⇕ఏᑟ⋡ࡢపῶࡣ 2㸣௨ୗ࡜ண᝿ࡉࢀࡿࠋࡲࡓ㸪ࡉࡽ࡟ぢ࠿ࡅࡢ⇕ఏᑟ⋡ࢆᑠࡉࡃࡍࡿࡓࡵ࡟ࡣ㸪⤖ᬗ࡜࢞ࣛࢫ┦ࡢᒅᢡ⋡ᕪࡢ฼⏝࡟ຍ࠼࡚㸪⤖ᬗ⢏ᚄࡢไᚚ࡟ࡼࡿ࣑࣮ᩓ஘ࡢ฼⏝ࢆྜࢃࡏ࡚⏝࠸ࡿᚲせࡀ࠶ࡿࠋୖࡢゎᯒࡀࡑࡢࡲࡲᐇ㝿ࡢ࣮ࣔ㸫㸫ࣝࢻࣇࣛࢵࢡࢫ࡟㐺⏝࡛ࡁࡿࢃࡅ࡛ࡣ࡞࠸ࡓࡵ㸪௒ᚋ㸪ぢ࠿ࡅ⇕ఏᑟ⋡ࢆ኱ࡁࡃኚ໬ࡉࡏࡿࡼ࠺࡞ᡂศࢆぢฟࡋ㸪ࡑࡢᙳ㡪ࢆᐇ㦂ⓗ࡟ㄪᰝࡋ࡚࠸ࡃᚲせࡀ࠶ࡿࠋ
Table

1

Thermophysicalproperties

used,derivedapparent

thermalconductivity of solid mould flux and thickness of glassy layer
MF-Na2O

MF-Li2O

D (crystallised)/m-1

956

715

D (glassy)/m-1

193

150

n(crystallised)

1.5913,14,15)

1.5913,14,15)n(glassy)

1.48

1.54

O (crystallised)/Wm-1K-11.5912,13)

1.5912,13)

O (glassy)/Wm-1K-1

1.2513,16)

1.2513,16)H(liquid/crystallised)1

1

H(crystallised/glassy)

1

1

H(glassy/air gap)

0.527

0.527

Oapp/Wm-1K-1

1.88

1.92

dglass /mm

0.169

0.164

D: absorption coefficient or extinction coefficient, n: refractive index,
O: thermal conductivity, H: emmisivity, dglass: thickness of glass䡕 layer6㸬⤖ゝ࣮ࣔࣝࢻࣇࣛࢵࢡࢫࡢఏ⇕≉ᛶ࡟ᑐࡍࡿ࢞ࣛࢫ࡜࢝ࢫࣆࢹ࢕ࣥࡢᒅᢡ⋡ᕪࡢᙳ㡪ࢆ᫂ ࡽ ࠿ ࡟ ࡍ ࡿ ࡓ ࡵ ࡟ 㸪 ᚑ ᮶ ࡢ ࣇ ࣛ ࢵ ࢡ ࢫ ⤌ ᡂ ࡟ ᇶ ࡙ ࠸ ࡓ
SiO2-CaO-Al2O3-CaF2-Na2O-Fe2O3 ⣔ ࡜ ࡇ ࡢ Na2O ࢆ Li2O ࡟ ⨨ ࡁ ᥮ ࠼ ࡓ
SiO2-CaO-Al2O3-CaF2-Li2O-Fe2O3 ⣔ࡢẚ㍑ࢆ⾜ࡗࡓࠋNa2O ࢆ Li2O ࡟⨨ࡁ᥮࠼ࡿ࡜㸪⤖ᬗ໬ࣇࣛࢵࢡࢫ୰ࡢ࢞ࣛࢫ┦ࡢᒅᢡ⋡ࡣ኱ࡁࡃ࡞ࡾ㸪⤖ᬗ┦࡛࠶ࡿ࢝ࢫࣆࢹ࢕ࣥ࡜ࡢᒅᢡ⋡ᕪࡣᑠࡉࡃ࡞ࡿࠋ⤖ᯝ࡜ࡋ࡚⤖ᬗ໬ࣇࣛࢵࢡࢫࡢぢ࠿ࡅࡢ཯ᑕ⋡ࡣపୗࡋ㸪ࣇࣛࢵࢡࢫ඲య(⤖ᬗᒙ࡜࢞ࣛࢫᒙ࠿ࡽᡂࡿ)ࡢぢ࠿ࡅࡢ⇕ఏᑟ⋡ࡣ⣙ 2㸣኱ࡁࡃ࡞ࡿࠋ௨ୖࡼࡾ㸪⤖ᬗ࡜࢞ࣛࢫ┦ࡢᒅᢡ⋡ᕪࡀ࣮ࣔࣝࢻࣇࣛࢵࢡࢫ඲యࡢఏ⇕≉ᛶ࡟ࡶᙳ㡪㸫㸫ࢆཬࡰࡍࡇ࡜ࡀ♧ࡉࢀࡓࠋㅰ㎡ ᮏ◊✲ࡣ㸪බ┈㈈ᅋἲே JFE21 ୡ⣖㈈ᅋࡼࡾᢏ⾡◊✲ຓᡂ(2016 ᖺᗘ)ࡢᨭ᥼ࢆཷࡅ
࡚ᐇ᪋ࡉࢀࡲࡋࡓࠋᚰࡼࡾឤㅰ⏦ࡋୖࡆࡲࡍࠋࡲࡓ㸪ศගගᗘィࡢ฼⏝࡟ࡈ༠ຊ࠸ࡓࡔࡁࡲࡋࡓᮾிᕤᴗ኱Ꮫ⛉Ꮫᢏ⾡๰ᡂ◊✲㝔ඛᑟཎᏊຊ◊✲ᡤ࣭㮚ᑿᗣ୍ᮁ෸ᩍᤵ࠾
ࡼࡧᮏ◊✲ࢆࢧ࣏࣮ࢺࡋ࡚ࡃࡔࡉࡗࡓᮾிᕤᴗ኱Ꮫ≀㉁⌮ᕤᏛ㝔ᮦᩱ⣔Ꮫ⏕ࡢ㝞リⱝࡉࢇ࡟ᚚ♩⏦ࡋୖࡆࡲࡍࠋཧ⪃ᩥ⊩1) M. Hanao, M. Kawamoto, M. Hara, T. Murakami, H. Kikuchi and K. Hanazaki:

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