Ꮫ 㒊 Ꮫ ⏕ᒸ㔝ከຍྐబ⸨⚟㤿

101 ◊ ✲ ά ື ሗ ࿌研 究 活 動 報 告

࠙◊✲ά ືሗ࿌ ࠚ ㉸⮫⏺ὶయ࣭཯ᛂ◊✲ศ㔝 㸦 㹼 㸧 ᩍ ᤵᶓᒣ༓᫛

ຓ ᩍႛ←෠⏣኱㍜

኱ Ꮫ 㝔 ⏕ᑠᯘಙஂ⃝ᒣᣅὒᶫᮏ㈗⠊

研 究 活 動 報 告 102

◊ ✲ ά ື ሗ ࿌

ࡓࠋࡲࡓࠊ್༙ ᖜ ࡣ

NH

4

Cl

ࢆ㖔໬๣࡜ ࡋ࡚⏝࠸ࡓ ሙ

ྜ3189 arcsec࡛࠶ ࡗ ࡓࡢ ࡟ᑐ ࡋࠊ

Zn Cl

2ࢆ㖔 ໬๣ ࡜ ࡋ࡚⏝࠸ࡓሙྜ

411.0 arcsec࡛࠶ࡾࠊ1᱆⛬ᗘῶᑡ ࡋ

ࡓࡇ࡜࠿ࡽࠊ⤖ᬗᛶࡀྥୖ ࡋ ࡓ ࡇ ࡜ ࡀ ♧ ၀ ࡉ ࢀ ࡓ ࠋ

ࡲࡓࠊ ⫱ᡂ⤖ ᬗࡢ ⤌ᡂศ ᯒࢆ ࡋࡓ࡜ ࡇࢁ ࠊ

Znࡀ୍

ᐃ 㔞 ྵ᭷ ࡉ ࢀ࡚ ࠸ࡿ ࡇ ࡜ࡀ ศ࠿ ࡗ ࡓࠋ ࡇ ࡢ⤖ ᯝࡣ ࠊ

࢔ ࣔ ࣀ ࢧ ࣮ ࣐ ࣝ ἲ ࡟ ࠾ ࠸ ࡚ 㖔 ໬ ๣ ᡂ ศ ࢆ ࢻ ࣮ ࣆ ࣥ ࢢ࡛ࡁࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

㸬 㓟ᛶ࢖࢜ ࣥᾮయ࣏ ࣐࣮ࣜゐ ፹ࡢ㛤Ⓨ

ゐ፹స⏝ࡀ࠶ࡿ ࢖࢜ࣥᾮయࢆከᏍ㉁ ᢸయ࡞࡝࡟ ≀⌮ⓗࡲࡓࡣ໬Ꮫⓗ࡟ᅛᐃ໬ࡍࡿ࢖࢜ ࣥᾮ యᅛᐃ໬ゐ፹ࡣ ᆒ୍⣔ゐ፹ࡢ㧗άᛶ࣭ 㧗㑅ᢥᛶ࡜ ᅛయゐ፹ࡢ ศ㞳࣭෌฼⏝ࡀᐜ᫆࡜࠸ࡗ ࡓ ୧ ᪉ࡢ≉㛗ࢆేࡏᣢࡘࡇ࡜࠿ࡽ 㠀ᖖ࡟ὀ ┠ࡉࢀ࡚࠸ ࡿ ࠋ࢖࢜ࣥᾮయࡣ⌧≧࡛ࡣ㧗౯࡛࠶ࡿ ࠺࠼

⏕ᡂ≀࡜ࡢศ㞳ࡀ㞴ࡋ࠸ࡇ࡜࠿ࡽࠊ⁐ ፹࠿ࡘゐ፹ ࡜ࡋ࡚኱㔞࡟౑⏝ࡍࡿࡓࡵ࡟ࡣゎỴࡋ ࡞ࡅ

ࢀࡤ࡞ࡽ࡞࠸ၥ㢟ࡀከ࠸ࠋ୍᪉࡛ࠊゐ ፹స⏝ࢆ♧ ࡍ ࢖࢜ࣥᾮయ࡟ࡣάᛶࡀ㧗ࡃ᭷⏝࡞ࡶ ࡢࡀ ከ࠸ࠋ࢖࢜ࣥᾮయᅛᐃ໬ゐ፹ࡣᑡ㔞ࡢ ࢖࢜ࣥᾮయ ࡛ ༑ศ࡞ゐ፹స⏝ࢆ♧ࡍࡇ࡜ࡀ࡛ࡁࠊ ࢥࢫ ࢺ㠃ࡸศ㞳ᅇ཰ࡢၥ㢟ࢆゎỴ࡛ࡁࡿྍ ⬟ᛶࡀ࠶ࡿ ࠋ ࡑࡇ࡛ࠊ㓟ᛶ࢖࢜ࣥᾮయࢆ㧗ศᏊ໬ ࡍࡿ

ࡇ࡜࡛ศ㞳ࢆᐜ᫆࡟ࡋࡓゐ፹ࢆ㛤Ⓨࡍ ࡿࠋ

㓟ᛶ࢖࢜ࣥᾮయ࣏࣐࣮ࣜࡢྜᡂ㸸

[VSBI][Tf] 25 mmol

࡟࢔ࢭࢺࢽࢺࣜࣝ

15 ml

ࢆ⁐፹࡜ࡋ࡚

ຍ࠼ࠊ❅⣲ࣂࣈࣜࣥࢢࡋࡓࠋḟ࡟AIBN 0.25 mmolࢆຍ࠼ࠊ❅⣲㞺ᅖẼୗ࡟࠾࠸࡚60Υ࡛24

h

཯ᛂࡉࡏ㓟ᛶ࢖࢜ࣥᾮయ࣏࣐࣮ࣜࢆྜᡂࡋࡓࠋ

࢚ࢫࢸ ࣝ໬཯ ᛂ 㸸 ᇶ㉁ ࡜ࡋ࡚ ࣓ࢱ ࣀ࣮ࣝ

0.10 mol

࠾ࡼ ࡧ㓑 㓟

0.05 mol

ࠊ ゐ፹࡜ ࡋ࡚ 㓟ᛶ࢖

࢜ࣥᾮయ࣏࣐࣮ࣜ

0.19 g

ࢆຍ࠼

60

Υ࡛཯ᛂࡉࡏ ࡓࠋᡤᐃࡢ᫬㛫ࡈ࡜࡟࢞ࢫ ࢡ࣐ࣟࢺࢢࣛࣇ࢕

࣮࡟ࡼࡾ㌿໬⋡ࢆồࡵࡓࠋ

ᅗ

4

࡟㓟ᛶ࢖࢜ࣥᾮయ࣏࣐࣮ࣜࢆゐ፹ ࡜ࡋࡓ࢚ ࢫࢸࣝ໬཯ᛂࡢ㌿໬⋡ࡢ⤒᫬ኚ໬ࢆ♧ ࡍࠋ ڦ࡛ ♧ ࡍ ࡢ ࡣ 㓟 ᛶ ࢖ ࢜ ࣥ ᾮ య ࣔ ࣀ ࣐ ࣮ ࢆ ゐ ፹

࡜ࡋ࡚⏝࠸ࡓ⤖ᯝ࡛࠶ࡿࠋ㓟ᛶ࢖࢜ࣥᾮయࢆ㧗 ศᏊ໬ࡋ࡚ࡶࠊゐ፹άᛶࢆ♧ࡋࠊ

90%

ࡢ㌿໬⋡

ࢆᚓࡓࠋ཯ᛂ㏿ᗘࡣ㓟ᛶ࢖࢜ࣥᾮయࣔࣀ࣐࣮ࢆ

ゐ፹࡟ࡋࡓሙྜࡀୖᅇࡗࡓࠋࡇ ࢀࡣࠊ㓟ᛶ࢖࢜

ࣥᾮయࣔࣀ࣐࣮ࡣᇶ㉁࡟⁐ゎࡋࠊᆒ୍⣔ゐ፹࡜

ࡋ࡚స⏝ࡍࡿࡓࡵ࡛࠶ࡿࠋ㓟ᛶ࢖࢜ࣥᾮయ࣏ࣜ

࣐࣮ࡣᇶ㉁࡟⁐ゎࡋ࡞࠸ࡓࡵࠊࢁ㐣࡟ࡼࡾᐜ᫆

࡟ศ㞳࡛ࡁࡿࡇ࡜ࡀ฼Ⅼ࡛࠶ࡿ ࠋ௒ᚋࠊ㓟ᛶ࢖

࢜ ࣥ ᾮ య ࡢ ࢟ ࣕ ࣛ ࢡ ࢱ ࣜ ࢮ ࣮ ࢩ ࣙ ࣥ ࡸ ࣜ ࢧ ࢖ ࢡࣝᛶ࡟ࡘ࠸᳨࡚ウࡋ࡚࠸ࡃணᐃ࡛࠶ ࡿࠋ

[VSBI][Tf]: 3-vin yl-1-(4-sulfobutyl)imidazolium trifluoromethanesulfonate

0 10 20 30 40 50 60 70 80 90 100

0 1 2 3 4 5 6

Conversion [%]

Reaction time [h]

㓟ᛶIL䝰䝜䝬䞊ゐ፹ 㓟ᛶIL䝫䝸䝬䞊ゐ፹

ᅗ

4࢚ࢫࢸࣝ໬཯ᛂࡢ㌿໬⋡ࡢ⤒᫬ኚ ໬

ᅗ

3

⫱ᡂ

GaN

⤖ᬗࡢ

XRC

 ᐃ⤖ ᯝ

103 研 究 活 動 報 告

◊㻌 ✲㻌 ά㻌 ື㻌 ሗ㻌 ࿌

࠙◊✲άືሗ࿌ࠚ άᛶ཯ᛂሙ࣭ྜᡂ◊✲ศ㔝 䠄

2011

䠊

1

䡚

2011

䠊

12

䠅㻌

ᩍ ᤵ㻌 㻦㻌 ᒣ᰿㻌 ஂ඾㻌

෸ 㻌 㻌 ᩍ 㻌 㻌 ᤵ㻌 㻦㻌 ᒣ⏣㻌 㧗ᗈ㻌

ຓ ᩍ㻌 㻦㻌 ᳃ᡞ㻌 ᫓ᙪ㻌

Ẹ㛫➼ඹྠ◊✲ဨ㻌 䠖㻌 㛗㇂ᕝ㻌 ᬛᬕ㻌

኱ Ꮫ 㝔 ⏕㻌 㻦㻌 Ᏻす㻌 ῟䠈Ⳣ㔝 බ㈗䠈㧗Ⲵ ┤ᶞ䠈㛛㛫 ೺ྖ㻌

㻌 㻌 㻌

㻌

ᮏ◊✲ศ㔝䛷䛿䚸άᛶ㔠ᒓ཯ᛂሙ䜢฼⏝䛧䛯㠀㓟໬≀⣔䝉䝷䝭䝑䜽䝇䜔㔠ᒓ㛫໬ྜ≀䛾ྜᡂ䛚䜘䜃ᅛ┦

཯ᛂἲ䛻䜘䜛ከඖ⣔᪂つ↓ᶵ໬ྜ≀䛾᥈⣴䛸䚸䛭䜜䜙䛾ᵓ㐀ゎᯒ䜔≉ᛶホ౯䛻䛴䛔䛶◊✲άື䜢⾜䛳䛶䛔 䜛䚹

2011

ᖺ䛾◊✲άື䛸䛧䛶䛿䚸௨ୗ䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䚹

㻌

1D$O6L ࢆ฼⏝ࡋࡓ 0Q̺$O̺6L ⣔໬ྜ≀ࡢప ྜᡂ࡜⇕㟁≉ᛶ

3

ඖ⣔䛾㔠ᒓ䜿䜲໬≀

Mn(AlxSi1-x)2 (0.37 ” x ” 0.45)

䛿䚸㔠ᒓཎᩱ䜢㧗 䛷⁐⼥཯ᛂ䛥䛫䛯ᚋ䚸ప 䛷㛗

᫬㛫䜰䝙䞊䝹䛩䜛䛣䛸䛷ྜᡂ䛥䜜䠈

x = 0.38

䛾ヨᩱ䛻䛴䛔䛶⇕㟁≉ᛶ䛜ሗ࿌䛥䜜䛶䛔䛯䚹ᮏ◊✲䛷䛿䚸㔠ᒓ㛫

໬ྜ≀

NaAlSi

䜢⏝䛔䛶

Mn(AlxSi1-x)2

䜢ప 䛷ྜᡂ䛩䜛䛣䛸䜢ヨ䜏䚸䛭䛾

⇕㟁≉ᛶ䜢ホ౯䛧䛯䚹

Mn

䠈

NaAlSi

䠈

Si

䛾ΰྜཎᩱ⢊ᮎ䠄

Mn:Al:Si = 0.95:y:2.05-y (y = 0.80, 0.85, 0.90)

䠅䛾ᅽ⢊ᡂᆺయ䜢

1173 K, 12 h

䛷ຍ⇕

䛩䜛䛣䛸䛷䚸ᅛ⁐య

Mn(AlxSi1-x)2+į (0.37 ” x ” 0.40, į = 0.04~0.08)

䛜ྜᡂ 䛥䜜䛯䚹໬Ꮫศᯒ䛾⤖ᯝ䚸䛣䜜䜙䛾ヨᩱ䛻ྵ䜎䜜䜛

Na

㔞䛿

0.4 wt.%

௨ୗ

䛷䛒䛳䛯䚹ྜᡂ䛥䜜䛯ᅛ⁐య䛾⢊ᮎ䜢⏝䛔䛶䝟䝹䝇㏻㟁↝⤖ἲ䛷↝⤖

య䜢స〇䛧䚸⇕㟁≉ᛶ

(

↓ḟඖᛶ⬟ᣦᩘ

, ZT)

䛾 ᗘ౫Ꮡᛶ䜢ㄪ䜉䛯⤖

ᯝ䜢

Fig. 1

䛻♧䛩䚹

y

㻌

=

㻌

0.85

䛾⤌ᡂ䛾ཎᩱ䛛䜙స〇䛥䜜䛯ヨᩱ䛜䚸

622 K

䛷᭱䜒㧗䛔↓ḟඖᛶ⬟ᣦᩘ

ZT = 0.15

䜢♧䛧䛯䚹䛣䛾್䛿䚸ཎᩱ䜢㧗  ⁐⼥䛥䛫䛯ᚋ䛻㛗᫬㛫䛾䜰䝙䞊䝹ฎ⌮

(1075 K, 150 h)

䜢⾜䛺䛳䛶ྜ

ᡂ䛥䜜䛯

Mn(Al0.38Si0.62)2

䛾ሗ࿌್

(ZT = 0.14)

䛸䜋䜌ྠ䛨䛷䛒䛳䛯䚹

1D6L ⼥ᾮࢆ฼⏝ࡋࡓ 1E6L

⢊ᮎࡢప ྜᡂ

௨๓䛾◊✲䛷

ȕ-FeSi2

䜔

MoSi2

䛾ప ྜᡂ䛻ຠᯝ䛜䛒䛳䛯

Na–Si

⼥ᾮ䜢฼⏝䛧䛯ྜᡂἲ䜢⏝䛔䛶䚸㧗  ᵓ㐀ᮦᩱ䛺䛹䜈䛾ᛂ⏝䛜ᮇᚅ䛥䜜䛶䛔䜛

NbSi2

䛾ྜᡂ䜢ヨ䜏䛯䚹୍⯡䛻

NbSi2

䛾ྜᡂ䛻䛿䜰䞊䜽⁐ゎἲ䛺䛹 䛾㧗 䝥䝻䝉䝇䛜ᚲせ䛸䛥䜜䜛䛜䚸ᮏ◊✲䛷䛿䠈

Nb

⢊ᮎ䜢

Na–Si

⼥ᾮ䛸

䛸䜒䛻

900~1100 K

䛷

24~48 h

ຍ⇕䛩䜛䛣䛸䛷䚸

NbSi2

䛾༢┦⢊ᮎヨᩱ䛜

ྜᡂ䛥䜜䛯䚹

Fig. 2

䛻

1000 K

䛷

12 h

ຍ⇕䛧䛶ᚓ䜙䜜䛯

NbSi2

⢊ᮎ䛾

SEM

ീ䜢♧䛩䚹

NbSi2

⢊ᮎ䜢ᵓᡂ䛩䜛⢏Ꮚ䛿⢏ᚄ

1~20

䃛

m

䛾ゅᙇ䜚 䛾䛒䜛୙つ๎ᙧ≧⢏Ꮚ䛷䚸ຍ⇕ ᗘ䜔᫬㛫

,Na

䛾ῧຍ㔞䜢ኚ䛘䛶䜒䚸 䛭䛾ᙧែ䜔኱䛝䛥䛿䜋䛸䜣䛹ኚ໬䛧䛺䛛䛳䛯䚹䛣䛾

NbSi2

⢊ᮎ䛾⢏ᚄ䛿 ཎᩱ䛻౑⏝䛧䛯

Nb

⢊ᮎ䠄

< 75

䃛

m

䠅䛾䛭䜜䜘䜚䜒ᑠ䛥䛟䚸䜎䛯ᙧែ䜒኱䛝 䛟␗䛺䜛䛣䛸䛛䜙䚸ཎᩱ䛾

Nb

⢊ᮎ⢏Ꮚ䛜

Na–Si

⼥ᾮ୰䛾

Si

䛸཯ᛂ䛧䛶

Fig. 1 ZT values of the samples prepared from the compositions of Mn:Al:Si = 0.95:y:2.05-y with y = 0.80㻌(circles), 0.85 (triangles), 0.90 (squares). The broken line shows the reported values of Mn(Al0.38Si0.62)2.

Fig. 2 SEM image of the NbSi2 powder prepared by heating Nb powder with a Na–Si melt at 1100 K for 12 h.

20 µm

研 究 活 動 報 告 104

Fig. 3 Crystal structure of Mg5NbO3(BO3)3.

'()*+,-./012345678923:;<6=>[email protected] wt%L MN.OPQRSTU5NbSi2VWU123:

!

!"#$ %&'()*+,- ./ 01234"

!

XYZ[\Si]^5_`abcdeOfghSi]^5ijklmn opVqr92se+:NatucSivw/1x3yOwz5Nav800 {900ºC.=|1x+6}~V]^)*+€69O‚5,-.5Si 5

ƒo„…v†‡3:fghˆD "‰ŠK‹Œ "L65Ž ".O

ƒoyc‘’+Si]^E5“g”•hv‰–B3]…O—5Table 1 c˜*™šcOigh}~›DEcœ2+ Fe vFžr6*+Ÿ 5“g

”5•hVONa v¡¢]^)yF£B ¤¥*+€6V¦9cm§

3¨©cOª«¬­c®*+ƒo„…Vb¢ Oigh Si Ec¯4Ÿ 

œ2se3Fe5•hF1897 ppm91.25 ppm.¤¥B3:ƒo5 ,-.]^Ec°±²23NaK83.22 ppmLFO]^v1500 ºC.t /1x+€6.0.03 ppm.i¤1x+€6V.¢3:

5!" 6789: ;<₌;">?@>A"?;"B"#CD"E$A29FG01HIJKL(MNO"

5 ³5´µ¶(Nb⁵⁺)3F·¸·¹(Ta⁵⁺)(µ¸vœº<)”cFO»

.M⁵⁺–O^2¼ ½5Z¾«$ª«c™+¿À|Áv˜*45V%&12se+¨

 ".FOMgO–M2O5–B2O3 (M = Nb, Ta)Ãc‘esOÄÅ<‘™Æ<)

”ÇÈ5ÉÇUÊÀv 1370 °C .ËÌ*+€6c™±O ÍεÏÐÄÅ<

Ñ5Ò]^vWUB3:Ò]^ÓÔÕÖ/–5]…O€29FO×Ø^ÃÙ Ú½ÛÜPnma (No. 62)ÙÝÞRßÜa = 9.3682(3) Å, b = 9.4344(2) Å, c = 9.3379(3) Å (M = Nb)‘™Æa = 9.3702(3) Å, b = 9.4415(3) Å, c = 9.3301(2) Å (M = Ta)ÙMg5MO3(BO3)3 (M = Nb, Ta).à12+ÊÕÖ5)W”.OFig. 3

c˜*™šmáâÅãäå(l(Mg3TiO2(BO3)2) Êæç5èÕÖvé*+€6V˜123:5 ³5¬­êëvœ

ºáâÅãäå(lÊæç5èÕÖF€2.c%&Fm O ".WU123ìí5)W”Vîrs5ï .ð+: M = Nb 5Ÿ]^CD.FO»c‘es270 nm 5ñòÁc™±ó470 nm côâõvöí¶÷

âømùúŒ|ÁVûü123:

=!"PQRSTU V$.W _XYE/YZ[_\>_]\29FG01HIJKL(MNO"

 "‰Š.FOýþ CaO–Al2O3–SnO2 Ã.ÍÎ)W” Ca2Sn2Al2O9 vÿHBO‚5]^ÕÖV Na2Ti2Si2O9 (ramsayite)6ÊÕÖ.ð+€6v%&B3:Ca2Sn2Al2O95Sn⁴⁺5‹ vTi⁴⁺.!"*+€6vC

#36€$OCaO–Al2O3–TiO2–SnO25 4 U‰Ã.%â&älÕÖvé*+'wÀvÿHB3:€5'wÀF 1370 ºC.WU12O‚5TUFCa3Sn3 xTixAl2O12Ùx = 0.6~1.4.à123:Ò]^‘™ÆÇÈCD5XÔ ÕÖ/–5]…OSn⁴⁺6 Ti⁴⁺V 6 ()*(l(16a)6 4 ()*(l(24d)5e+2c4,+€6V˜123:

250~260 nm5-.Ôñòc™±ù/Œ5|ÁVû0123:

unit^ppm Table 1 !Results of GDMS analysis for Si powder and a Si grain.

Element

294.52 41.57 54.10 94.45 150.32 307.73 1897.23 Al

P Ca Ti Cr Mn Fe

5.90 3.28 1.68 0.02 1.60 0.49 1.25

Raw Si powder"

Refined Si grain"

105 研 究 活 動 報 告

◊㻌 ✲㻌 ά㻌 ື㻌 ሗ㻌 ࿌

ᅗ䠍㻌 AlGaN ⷧ⭷䛾 (a) 䝞䞁䝗➃Ⓨග䛾್༙඲

ᖜ䚸 (b)S 䝟䝷䝯䞊䝍䚸 (c)300K 䛸 8K 䛾᭷ຠ

_R

䛸 300K 䛾᭷ຠ

_NR

࠙◊✲άືሗ࿌ࠚ 㔞Ꮚᵓ㐀ᙧᡂᇶᯈ ! ࢹࣂ࢖ࢫホ౯◊✲ศ㔝

ドキュメント内 研究業績・活動報告2011 (ページ 104-108)