カリウムアイオノマーの非線形誘電スペクトル

, 31, 1 (2007) 2 7

ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞

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㧔_{2006 ᐕ 9 ᦬ 15 ᣣฃઃ; 2006 ᐕ 11 ᦬ 15 ᣣฃℂ㧕}

Nonlinear Permittivities in Potassium Salt Ionomers of Ethylene Copolymer

Nobuyuki MAKI*

,

_{**, Sho CHO**, Yuu MORIMOTO**, Yoshiro TAJITSU**}

(Received September 15, 2006; Accepted November 15, 2006)

We report the frequency spectra of complex linear and nonlinear permittivities of potassium ionomer films prepared from poly (ethylene-co-methacrylic acid) in the frequency range from 1 kHz to 1 MHz, at room temperature. A characteristic conduction relaxation phenomenon was observed in the spectra, which suggested the existence of different ion conduction mechanisms between the high and low-frequency regions. We also found that the ratio of linear to nonlinear conductivities calculated from nonlinear permittivities was closely related to the elementary process of ionic transport. Furthermore, the ratio obtained from nonlinear measurements allowed an estimate of the important parameters which characterized ionic transport in ion-conducting polymers, such as the hopping distance of ion or the size of a connected cluster of the site capable of the ion hopping, without the need for any additional assumptions in potassium ionomer films. 1䋮䋮 ߪߓ߼ߦ 䉝䉟䉥䊉䊙䊷䈫䈲䋬⇹᳓ᕈ䈱㜞 ಽሶਥ㎮䈮ዋ㊂䈱䉟䉥䊮 ၮ䉕ዉ౉䈚䈢㜞ಽሶ䈱✚⒓䈪䈅䉎䋮䈭䈎䈪䉅䉣䉼䊧䊮䉝䉟䉥䊉 䊙䊷䈲䋬䊖䉴䊃㜞 ಽ ሶ 䈪䈅䉎ૐ ኒ ᐲ 䊘䊥䉣䉼䊧䊮䈱ᕈ ⢻ 䉕଻ ᜬ䈚䈭䈏䉌䋬㊄ዻ䉟䉥䊮᨞ᯅ䈮⿠࿃䈜䉎ൻቇ⊛䊶‛ℂ⊛䈭‛ ᕈ䈏ઃਈ䈘䉏䈩䈍䉍䋬Ꮏᬺ⊛䈮䉅ᐢ䈒೑↪䈘䉏䈩䈇䉎䊒䊤䉴䉼 䉾䉪䈪䈅䉎䋮 䉝䉟䉥䊉䊙䊷䈱㜞ᰴ᭴ㅧ䈮㑐䈚䈩䈲䋬⇹᳓ᕈ䈱㜞ಽሶ䊙 䊃䊥䉾䉪䉴ਛ䈪䋬ⷫ᳓ᕈ䈱㊄ዻ䉟䉥䊮ၮ䈏ಝ㓸䈚䋬૗䉌䈎䈱᭴ ㅧ 䉕 ᒻ ᚑ 䈜 䉎 䈖 䈫 䈏 ᒰ ೋ 䉋 䉍 ᜰ ៰ 䈘 䉏 䈩 䈐 䈢 䋮_{1968ᐕ 䈮䈲} Longworth䈫Vaughan䈏䌘✢࿁᛬䊌䉺䊷䊮䉕ၮ䈮 㽲䊘䊥䉣䉼 䊧䊮䈱䊤䊜䊤⚿᥏㗔ၞ䋬㽳䊘䊥䉣䉼䊧䊮䈱㕖᥏㗔ၞ䋬෸䈶䋬㽴 䉟䉥䊮ಝ㓸ㇱ 䈱䋳䈧䈱㗔ၞ䈎䉌䈭䉎䋳⋧ 䊝䊂䊦䉕ឭ᩺䈚䈩䈇 䉎1)䋮࿑䋱䈮䋬_{Longworth╬䈱ឭ᩺䈚䈢䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷䈱} 3⋧䊝䊂䊦䉕␜䈜䋮 ⃻࿷䉅䈦䈫䉅ᐢ䈒⹺䉄䉌䉏䈩䈇䉎䉝䉟䉥䊉䊙䊷䈱㜞ᰴ᭴ㅧ䊝 䊂䊦䈲䋬_{1990ᐕ䈮Eisenberg, Hird, Moore䈏ឭ᩺䈚䈢䊝䊂䊦} 䋨_{EHM䊝䊂䊦䋩䈪䈅䉎}2)䋮_{EHM䊝䊂䊦䈪䈲䋬䊙䊦䉼䊒䊧䉾䊃䈫⒓} 䈘䉏䉎㕒㔚⊛䈮ಝ㓸䈚䈢䉟䉥䊮ಝ㓸૕䈱ᦨዊන૏䈏䋬䈘䉌䈮 ಝ㓸䈚䈢䋬䉟䉥䊮䉪䊤䉴䉺䊷䈱᭎ᔨ䈏ឭ᩺䈘䉏䈩䈇䉎䋮䊙䊦䉼 䊒䊧䉾䊃䈱䉁䉒䉍䈪䈲䋬䉟䉥䊮ಝ㓸ജ䈱ᓇ㗀䈪䋬㜞ಽሶ㎮ㆇേ 䈱᧤❈䈘䉏䈢㗔ၞ䈏ሽ࿷䈜䉎䋮䉝䉟䉥䊉䊙䊷ਛ䈱䊙䊦䉼䊒䊧 䉾䊃䈏Ⴧട䈜䉎䈫䋬㓞ធ䈜䉎䊙䊦䉼䊒䊧䉾䊃䈱ㆇേ᧤❈㗔ၞ䈲 ㊀䈭䉍䋬䈘䉌䈮ᄢ䈐䈭ㆇേ᧤❈㗔ၞ䉕ᒻᚑ䈜䉎䋮䈖䈱ᄢ䈐䈭ㆇ േ᧤❈㗔ၞ䉕䋬_{Eisenberg䉌䈲䉟䉥䊮䉪䊤䉴䉺䊷䈫ฬઃ䈔䈢䋮䉟} 䉥䊮䉪䊤䉴䉺䊷䈱ሽ ࿷ 䈲䋬䉝䉟䉥䊉䊙䊷䈱ജ ቇ ⊛ ᕈ ⾰ 䈫⺃ 㔚 ⊛ᕈ⾰䈮ᄢ䈐䈭ᓇ㗀䉕ਈ䈋䈩䈇䉎䈫䈘䉏䈩䈍䉍䋬ജቇ⊛᜼േ 䈮䈧䈇䈩䈲䋬䈖䉏䉁䈪ᄙ䈒䈱ႎ๔䈏䈘䉏䈩䈇䉎3,4)䋮䈚䈎䈚䋬䉝 ࠠ࡯ࡢ࡯࠼㧦㕖✢ᒻ⺃㔚䉴䊕䉪䊃䊦䇮䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䇮 ዉ㔚ᕈ䇮䉟䉥䊮ಝ㓸ㇱ * ਃ੗䊶䊂䊠䊘䊮 䊘䊥䉬䊚䉦䊦ᩣᑼળ␠㩷 䊁䉪䊆䉦䊦䉶䊮 䉺䊷 䋨_{299-0108 ජ⪲⋵ᏒේᏒජ⒳ᶏጯ6䋩}

Technical Center, DuPont Mitsui Polychemicals Co., LTD. 6 Chigusa-kaigan, Ichihara-shi, Chiba-ken 299-0108, JAPAN

** 㑐⷏ᄢቇᄢቇ㒮 Ꮏቇ⎇ⓥ⑼ (564-8680㩷 ᄢ㒋ᐭ็ ↰Ꮢጊᚻ↸㩷_3-3-35)

Graduate School of Engineering, Kansai University, 3-3-35 Yamate, Suita, Osaka 564-8680, Japan 1 [email protected] 㫧 㫧 㫧 㫧 㫧 㫧 㫧 㫧 㫧 㫧 㫧 㫧㫧 㫧 㫧 㫧 㫧_㫧 㫧 㫧 㫧 㪺㫉㫐㫊㫋㪸㫃㫃㫀㫅㪼㩷㫇㪿㪸㫊㪼 㪸㫄㫆㫉㫇㪿㫆㫌㫊㩷㫇㪿㪸㫊㪼 㫀㫆㫅㫀㪺㩷㪸㪾㪾㫉㪼㪾㪸㫋㪼㫊 Fig.1 The structure model of ethylene ionomer as proposed

by Longworth et al 1)_. J. Inst. Electrostat. Jpn.

3 ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞㧔’ િⴕࠄ㧕 䉟䉥䊉䊙䊷䈱⺃㔚⊛᜼േ䈲㕖Ᏹ䈮ዊ䈘䈭䉅䈱䈪䈅䉎䈫੍᷹䈘 䉏䉎䈖䈫䈎䉌䋬⺃㔚⊛᜼േ䈮㑐䈜䉎ႎ๔䈲଀䈲ዋ䈭䈇5)䋮 䈫䈖䉐䈪䋬䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷䈱㊄ዻ䉟䉥䊮䈲䋬੝㋦䈅䉎 䈇䈲䊅䊃䊥䉡䊛䈏৻⥸⊛䈪䈅䉎䈏䋬䉦䊥䉡䊛䉕㊄ዻ䉟䉥䊮䈫䈜䉎 䉝䉟䉥䊉䊙䊷_{(䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷)䈲䋬䉝䉟䉥䊉䊙䊷᮸⢽⥄૕} 䈏ዉ㔚ᕈ䉕␜䈜䈖䈫䈏ႎ๔䈘䉏䈩䈇䉎6)䋮䈖䈱․㐳䈮ᵈ⋡䈚䈩䋬 䈖䈖_{10ᐕ⒟䈱㑆䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈲Ꮺ㔚㒐ᱛ᧚ᢱ䈫䈚䈩䋬} 㔚ሶㇱຠ൮ⵝ╬䈱Ꮏᬺಽ㊁䈮䈍䈇䈩ᐢ䈒೑↪䈘䉏䈩䈇䉎7䋩䋮 ᚒ䇱䈲䋬એ೨䈮䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱㔚⩄᜼േ䈱⋥ធ ⊛ 䈭 ᛠ ី 䈏 น ⢻ 䈭 䊌 䊦 䉴 㕒 㔚 ᔕ ജ ᴺ _(Pulsed Eleotroacoustic Method) 8-10䋩_{䉕↪䈇䈢ⓨ㑆㔚⩄ಽᏓ䈱᷹ቯ} 䉕ⴕ䈦䈩䈇䉎䋮ᓧ䉌䉏䈩䈇䉎ઍ⴫⊛䈭⚿ᨐ䉕䋬࿑_{2,3䈮␜䈜䋮} 䈖䉏䈲৻⥸⊛䈭⛘✼ᕈ䊒䊤䉴䉼䉾䉪䈪䈅䉎⋥㎮⁁ૐኒᐲ䊘䊥 䉣䉼䊧䊮_{(LLDPE)䈫䋬ઍ⴫⊛䈭䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱ⓨ㑆㔚} ⩄ಽᏓ䈱᷹ቯ⚿ᨐ䉕␜䈜䋮䈭䈍䋬࿑䈱❑ゲᣇะ䈲㔚⩄ኒᐲ ಽ Ꮣ 䉕␜ 䈚䋬ᮮ ゲ ᣇ ะ 䈲⹜ ᢱ 䈱ෘ 䉂ᣇ ะ 䉕␜ 䈜䋮䉁䈢䋬ฝ ஥䈏ᱜᭂ஥䋬Ꮐ஥䈲⽶ᭂ஥䈮ኻᔕ䈚䋬਄ᣇ䈱ᮨᑼ࿑䈲䊐䉞 䊦䊛ᢿ㕙䉕␜䈜䋮࿑_{2䈮␜䈜LLDPE䈱႐ว䋬ᱜᭂ஥䈱ታ㔚} ⩄䋬෸䈶⽶ᭂ஥䈱ታ㔚⩄䈏᷹ⷰ䈘䉏䈢䋮䈭䈍䋬ಽ⸃⢻䈱ᓇ 㗀䈪ᱜ䊶⽶㔚ᭂ䈱ㄭற䈮⺃ዉಽᭂ䈲᷹ⷰ䈘䉏䈩䈇䈭䈇䋮䈖䉏 䈮ኻ䈚䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈪䈲࿑_{3䈮␜䈜䉋䈉䈮䋬ᱜᭂ஥䈱} ታ㔚⩄䈲᷹ⷰ䈘䉏䈢䈏䋬⽶ᭂ஥䈱ታ㔚⩄䈲᷹ⷰ䈘䉏䈝䋬ᱜ ᭂ஥䈮ᄢ䈐䈭⽶䈱㔚⩄ಽᏓ䈏᷹ⷰ䈘䉏䈢䋮䈖䈱᷹ቯ⚿ᨐ䈲䋬 LLDPE䈱ⓨ㑆㔚⩄ಽᏓ䈫ᄢ䈐䈒⇣䈭䉍䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷 䈱㔚⇇ਅ䈮䈍䈔䉎⷗䈎䈔਄䈱㔚⩄⒖േ䉕␜ໂ䈚䈩䈇䉎䈖䈫䉕 ႎ๔䈚䈩䈇䉎11)䋮䈚䈎䈚䈭䈏䉌䋬↪䈇䈢᷹ቯⵝ⟎䈱ಽ⸃⢻䈏 10㱘m䈪䈅䉎䈢䉄䋬䊚䉪䊨䈭㗔ၞ䈪䈱㔚⩄᜼േ䈮㑐䈜䉎ᖱႎ 䉁䈪䈲ᓧ䉌䈭䈎䈦䈢䋮 ৻ᣇ䋬㜞ಽሶ䈱⎇ⓥ䈪䈲⺃㔚䉴䊕䉪䊃䊨䉴䉮䊏䊷䈱ᚻᴺ䉕 㚟૶䈚䈢⎇ⓥ䈏䋬㔚⩄⒖േ䈮㑐䈜䉎᦭⋉䈭ᖱႎ䉕ਈ䈋䈩䈇 䉎䋮䈚䈎䈚䈭䈏䉌䋬⺃㔚䉴䊕䉪䊃䊨䉴䉮䊏䊷᷹ቯ䈱ᄙ䈒䈲ශട㔚 ⇇ 䈮㔚 ᵹ䈏Ყ ଀ 䈜䉎㗔 ၞ䋬හ 䈤✢ᒻ 㗔 ၞ䈮㒢䉌䉏䈩䈇䈢䋮 ↰ ኪ 䈲䋬ᓥ ᧪ 䈱✢ ᒻ 㗔 ၞ 䈱ዉ 㔚 䉴䊕䉪䊃䊦䈱⎇ ⓥ 䉕䋬㕖 ✢ ᒻ㗔ၞ䈮䉁䈪᜛ᒛ䈜䉎䈖䈫䈏䋬⺃㔚᜼േ䈱⸃᣿䈮ᄢᄌ᦭ല 䈪䈅䉎䈖䈫䉕␜䈚䈩䈐䈢12)䋮 ᚒ䇱䈲䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䉕↪䈇䈢✢ᒻ䈱⺃㔚䉴䊕䉪䊃䊦 䈱♖ኒ᷹ቯ䉕ⴕ䈇䋬_{Longworth䋬Eisenberg╬䈮䉋䉍ឭ᩺䈘䉏} 䈩䈇䉎㜞 ᰴ ᭴ ㅧ 䊝䊂䊦䈮䉋䉍੍ ᷹ 䈘䉏䈩䈐䈢㔚 ⩄ ᜼ േ 䈮ኻ ᔕ䈜䉎䈫ᕁ䉒䉏䉎⺃㔚✭๺⃻⽎䉕䈲䈛䉄䈩⷗಴䈚䋬ႎ๔䈚䈢 13䋩_{䋮੹࿁䋬ᚒ䇱䈲䋬⺃㔚᷹ቯ䉕㕖✢ᒻ䈮䉁䈪⊒ዷ䈘䈞䋬䈖䈱} ✭๺᜼േ䈱䉋䉍⹦⚦䈭ᖱႎ䉕ᓧ䉎䈼䈒ታ㛎䉕ⴕ䈇䋬᦭⋉䈭⚿ ᨐ䉕ᓧ䈢䈱䈪ႎ๔䈜䉎䋮 2䋮䋮 ታ 㛎 2.1 ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯᮸⢽ 䉝䉟䉥䊉䊙䊷䈱⵾ㅧ䊒䊨䉶䉴䈮䈲䋬ṁⲢᴺ䈫Ṣቯᴺ䈏䈅䉎 䈏䋬ᧄᬌ⸛䈪䈲᛼಴ᯏ䈮䉋䉎ṁⲢᴺ䉕↪䈇䈢14)䋮䉁䈝䋬䊖䉴䊃 㜞 ಽ ሶ 䈫 䈚 䈩 䋬 䉣 䉼 䊧 䊮_{85wt% 䈫 䋬 䊜 䉺 䉪 䊥 䊦 ㉄} 㪝㫀㫃㫄䇭㪫㪿㫀㪺㫂㫅㪼㫊㫊

㪫㫀㫄㪼㩿㫄㫊㪅㪀

㪄㪌㪅㪇㪜㪂㪈 㪇㪅㪇㪜㪂㪇 㪌㪅㪇㪜㪂㪈

㪚

㪿

㪸㫉

㪾㪼

䇭

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㪼

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㪂㪈㫂㪭

㪣㪣㪛㪧㪜㩷㪝㫀㫃㫄

㪸㫅㫆㪻㪼

㪺㪸㫋㪿㫆㪻㪼

Fig.2 Charge distribution of LLDPE film.

㪝㫀㫃㫄㩷㪫㪿㫀㪺㫂㫅㪼㫊㫊 㪫㫀㫄㪼㩿㫄㫊㪅㪀 㪄㪈㪅㪌㪜㪂㪉 㪇㪅㪇㪜㪂㪇 㪈㪅㪌㪜㪂㪉 㪚 㪿 㪸㫉 㪾㪼 䇭 㪛 㪼 㫅 㫊㫀 㫋㫐 㩿㪚 㪆 㫄 㪊 㪀

㪸㫅㫆㪻㪼

㪺㪸㫋㪿㫆㪻㪼

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㪧㫆㫋㪸㫊㫊㫀㫌㫄㩷㪠㫆㫅㫆㫄㪼㫉㩷

㪝㫀㫃㫄

ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞㧔’ િⴕࠄ㧕 (CH2=C(CH3)COOH䋬ಽ ሶ ㊂ 86.1)15wt%䉕䋬㜞 ࿶ 䊤䉳䉦䊦 ㊀ ว ᴺ 䈮 䉋 䉍 ㊀ ว 䈚 䋬 䉣 䉼 䊧 䊮 䍃 䊜 䉺 䉪 䊥 䊦 ㉄ ౒ ㊀ ว ૕ (E-15MAA)䉕ᓧ䈢䋮ᰴ䈮䋬㊄ዻ䉟䉥䊮Ḯ䈫䈚䈩䉦䊥䉡䊛Ⴎ䉕↪ ᗧ䈚䋬_{E-15MAA䈫䉦䊥䉡䊛Ⴎ䉕䋬E-15MAAਛ䈱䊜䉺䉪䊥䊦㉄䈫} 䉦䊥䉡䊛_{(K䋬ේሶ㊂39.1)䈏䊝䊦Ყ䈪䋬40%(E-15MAA-0.4K)䋬} 60%(E-15MAA-0.6K)䋬80%(E-15MAA-0.8K)䈫䈭䉎䉋䈉䈮੍ 䉄䊑䊧䊮䊄䈚䋬_{140㷄䈎䉌260㷄䈮⸳ቯ䈚䈢᛼಴ᯏ䉕↪䈇䈩䋬} ṁⲢਛ๺෻ᔕ䈮䉋䉍䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䉕ᓧ䈢䋮࿑_4䈮䉣䉼 䊧䊮䍃䊜䉺䉪䊥䊦㉄౒㊀ว૕䈫䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱ൻቇ᭴ㅧ 䉕␜䈜䋮

૞ ᚑ 䈚 䈢_{E-15MAA 䋬 E-15MAA-0.4K 䋬 E-15MAA-0.6K 䋬} E-15MAA-0.䋸K䉕↪䈇䈩䋬180㷄䈮⸳ቯ䈚䈢䉟䊮䊐䊧䊷䉲䊢䊮 䊐䉞䊦䊛ᚑᒻᯏ䈮䉋䉍䋬䈠䉏䈡䉏_{50㱘mෘ䈱䊐䉞䊦䊛䉕૞ᚑ䈚} 䈢䋮 2.2 ᷹ቯ⹜ᢱ ૞ᚑ䈚䈢ฦ䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䊐䉞䊦䊛䈮䋬㔚ᭂ䈫䈚䈩㊄䉕 ⫳⌕䈚䈩䋬⺃ 㔚䉴䊕䉪䊃䊦᷹ቯ↪䈱⹜ ᢱ䈫䈚䈢15)䋮䉦䊥䉡䊛䉝 䉟䉥䊉䊙䊷䊐䉞䊦䊛䈲䊋䊦䉪䈱ዉ㔚ᕈ䈏ૐ䈇䈢䉄䋬⴫㕙ᣇะ 䈮ᵹ䉏䉎㔚ᵹ䈱ᓇ㗀䉕ឃ㒰䈚䈭䈒䈩䈲䈭䉌䈭䈇䋮䈖䈱䈢䉄䋬᷹ ቯ⹜ᢱ䈮䈲䉧䊷䊄㔚ᭂ䉕⸳䈔䈢䋮䉁䈢䋬⹜ᢱෘ䉂䈮ኻ䈚䈩ᄢ 䈐䈭㔚ᭂ㕙Ⓧ䈫䈜䉎䈖䈫䈪䋬㔚⇇䈏ဋ৻䈮⹜ᢱ䈮ශട䈘䉏䉎 䉋䈉䈮䈚䈢䋮 2.3 㕖✢ᒻ᷹ቯࠪࠬ࠹ࡓߩᡷༀ 䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䊐䉞䊦䊛䈱⺃㔚᷹ቯ䋬ዉ㔚᷹ቯ䈮䈲䋬 ↰ኪ╬䈏㐿⊒䈚䈩䈐䈢✢ᒻ෸䈶㕖✢ᒻⶄ⚛⺃㔚䊶ዉ㔚᷹ቯ ⵝ⟎䉕↪䈇䈢䋮ⵝ⟎䈱⹦⚦䈲ᣢႎ12䋩䈱ઁ䈪䈅䉎䈱䈪䋬◲න 䈮એਅ䈮ේℂ䉕䉁䈫䉄䉎䋮 ᧄ䉲䉴䊁䊛䈪䈲䋬⹜ᢱ䈮ᝄ᏷_E0 䈱ᱜᒏᵄ䋬

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(1) 䉕ශ ട 䋬䈠 䈱ᔕ ╵ 㔚 ⩄䌄_{(t)(ᔕ╵㔚ᵹI(t))䉕䉼䊞䊷䉳䉝䊮䊒} 䋨෸䈶㔚ᵹ䉝䊮䊒૬↪䋩䈪ᬌ಴䈜䉎䋮ᬌ಴䈘䉏䈢_{D(t)䋨䉁䈢䈲} 㔚ᵹ_{I(t)䋩 䈫䋬ශട㔚⇇䈱ାภE(t)䈮䉋䉍䋬㕖✢ᒻⶄ⚛⺃㔚} ₸㱑_{n* 䋨䉁䈢䈲ዉ㔚₸}㱟_n*䋩

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(n=1,2,3䊶䊶) (2)

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(n=1,2,3䊶䊶) (3) 䉕᳞䉄䉎䋮ᧄ䉲䉴䊁䊛䈱♖ᐲ䈲䋬࿑_{5ਛ䈮䈍䈔䉎䋬ାภེ䋬䉝} 䊮䊒䋬_{S/NᲧ䈱㜞䈇ାภ♽䈏ᡰ䈋䈩䈇䉎䋮} 䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䊐䉞䊦䊛䈮䈍䈔䉎⺃㔚✭๺⃻⽎䈲䋬ᓥ ᧪ ↰ ኪ╬ 䈏ᛒ 䈦䈩䈐䈢⺃㔚 ✭ ๺ ⃻⽎16-18)䉋䉍䋬ା ภ឵▚䈪 1/100⒟ᐲ䈫䈲䉎䈎䈮ዊ䈘䈒13䋩_{䋬ᓥ᧪䈱㕖✢ᒻ᷹ቯ䈱♖ᐲ䉕} ⿥䈋䈩䈇䈢䋮䈠䈖䈪䋬੹࿁ᚒ䇱䈲䋬᷹ቯ๟ᵄᢙၞ䉕ᄢ᏷䈮೙ 㒢䋨_{25 mHz~10 MHz䋨⚂䋹ᩴ䋩䉕1 kHz~1 MHz(3ᩴ)䋻䉣䉼䊧} 䊮䉝䉟䉥䊉䊙䊷✭๺䈱ሽ࿷䈜䉎▸࿐䈻೙㒢䋩䋬䉁䈢䉝䊮䊒䈫ା ภ ⊒ ↢ེ 䈱䉲䉴䊁䊛᭴ ᚑㇱ ᧚ 䉕ᄢ䈐䈒ᄌ ᦝ 䈚䋬䈘䉌䈮䉼䊠䊷 䊆䊮䉫䉕๟ᵄᢙ․ൻ䈜䉎䈖䈫䈪䋬᷹ቯ♖ᐲ䉕䈅䈕䈢䋮䈭䈍䋬䉝 䊮䊒ಾ䉍ᦧ䈋䈱䉴䉟䉾䉼䊉䉟䉵䈏ᄢ䈐䈇䈖䈫䈎䉌䋬䉝䊮䊒䈲੹࿁ 䈱᷹ቯၞ䈪䉋䉍♖ᐲ䈅䈕䉎䈖䈫䈏䈪䈐䈢㔚⩄䉝䊮䊒䈱䉂䈫䈚䋬 㔚ᵹ䉝䊮䊒䈲ᄖ䈚䈢䋮ᦝ䈮ⓥᭂ䈱䊉䉟䉵ኻ╷䈫䈚䋬᷷ᐲ೙ᓮ ㇱ䋨䊍䊷䉺╬䋩䉕ᄖ䈚䋬ᄖੂାภ䉕೥ᷫ䈚䈢䋨䈠䈱䈢䉄䋬੹࿁䈲 ቶ ᷷ 䈱 䉂 䈱 ᷹ ቯ 䈪 䈅 䉎 䋩 䋮 䈠 䈱 ⚿ ᨐ 䋬 ᓥ ᧪ ⵝ ⟎ 䉋 䉍 䋬 1KHz~1MHZ䈱▸࿐ౝ䈪䈅䉏䈳㕖✢ᒻ⺃㔚♖ᐲ䈲70䌤䌂⒟ ะ਄䈚䈢䋮 3䋮䋮 ⚿  ᨐ ࿑ _{6 䈮ቶ᷷䋨28.5㷄䋩䈮䈍䈔䉎䋬䉦䊥䉡䊛䉟䉥䊮䉕ో䈒฽䉁䈭䈇} 䉣䉼䊧䊮䍃䊜䉺䉪䊥䊦㉄౒㊀ว૕_{E-15MAA 䈫䋬䈠䉏䈡䉏䉦䊥䉡䊛} 䉟䉥䊮䈪_{40mol%(E-15MAA-0.4K)䋬60mol%(E-15MAA-0.6K)䋬} 80mol%(E-15MAA-0.8K)ਛ๺䈚䈢䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䊐䉞䊦 䊛 䈱 ✢ ᒻ ⺃ 㔚 ₸ ⯯ ㇱ㱑_{1” 䈱 䉴 䊕 䉪 䊃 䊦 䉕 䉁 䈫 䉄 䈢 䋮} E-15MAA-0.4K䋬E-15MAA-0.6K䋬E-15MAA-0.8K ో䈩䈱䉦䊥䉡 㪪㪰㪥㪫㪟㪜㪪㪠㪱㪜㪩 㪤㪠㪚㪩㪦㩷㪚㪦㪤㪧㪬㪫㪜㪩 㪮㪘㪭㪜㩷㪤㪜㪤㪦㪩㪰 㪭㪦㪣㪫㪘㪞㪜㩷㪘㪤㪧㪣㪠㪝㪠㪜㪩 㪘㪫㪫㪜㪥㪬㪘㪫㪦㪩 㪪㪘㪤㪧㪣㪜 㪚㪟㪘㪩㪞㪜㩷㪘㪤㪧㪣㪠㪝㪠㪜㪩 㪜㩷㩿㫋㪀 㪛㩷㩿㫋㪀 㪛 㪜㩷㪔㩷㪜㪇㩷㪺㫆㫊㱥㫋

Fig.5 Schematic diagram of experimental system for measuring permittivities.12) 㪄㩿㪚㪟㪉㪄㪚㪟㪉㪀㫅㪄㩿㪚㪟㪉㪄㪚㪀㫄㪄 㪚㪟㪊 㪚㪦㪦㪟 㪄㩿㪚㪟㪉㪄㪚㪟㪉㪀㫇㪄 㪚㪟㪊 㪚㪦㪦㩷㪢㪄㪄 㪂㪂 㪚㪟㪊 㪚㪦㪦㪟 㩿㪚㪟㪉㪄㪚㪀㫈㪄 㩿㪚㪟㪉㪄㪚㪀㫉㪄 䉣䉼䊧䊮䊶䊜䉺䉪䊥䊦㉄౒㊀ว૕ 䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷

Fig.4 Chemical structure of ethylene methacrylic acid copolymer and potassium ionomer.

31 1 2007 4

ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞㧔’ િⴕࠄ㧕 䊛䉝䉟䉥䊉䊙䊷䈮䈍䈇䈩䋬_{10kHz 䈎䉌 100kHz 䈮⺃㔚✭๺䉕␜䈜} 䊏䊷䉪䈏ሽ࿷䈚䈩䈇䉎䋨࿑_{6 ⍫ශㇱಽ䋩䋮䈖䉏䈮ኻ䈚䈩䋬䉦䊥䉡䊛䉟} 䉥䊮䉕ో䈒฽䉁䈭䈇_{E-15MAA 䈪䈲䋬✭๺⃻⽎䉕␜䈜䊏䊷䉪䈏⊒} ⃻䈚䈩䈇䈭䈇䋮䈖䈱᷹ቯ⚿ᨐ䈲䋬⺃㔚✭๺⃻⽎䈱ሽ࿷䈏䋬䉦䊥䉡 䊛䉟䉥䊮䈱ሽ࿷䈮⋥ធ⿠࿃䈚䈩䈇䉎䈖䈫䉕ⵣઃ䈔䈩䈇䉎䋮䉁䈢䋬 䉦䊥䉡䊛䉟䉥䊮Ớᐲ䈏ᷫዋ䈜䉎䈮䈧䉏䈩䋬䊏䊷䉪ᒝᐲ䈏ዊ䈘䈒䈭 䈦䈩䈇䉎䈖䈫䈏䉒䈎䉎䋮䈖䉏䈮ኻ䈚䈩䋬_{3 ᰴ䈱㕖✢ᒻⶄ⚛⺃㔚} 䉴䊕䉪䊃䊦䈪䈅䉎㱑_3*=㱑_{3' - j}㱑_{3"䈲䉋䉍ⶄ㔀䈭ᒻ⁁䉕␜䈚䈢䋮} ࿑_{7 䈮}㱑_{3*䈱᷹ቯ⚿ᨐ䉕␜䈜䋮3 ᰴ䈱㕖✢ᒻⶄ⚛⺃㔚₸ታ} ㇱ㱑3' 䋬 ⯯ ㇱ㱑3" 䈫 䉅 䋬 䉦䊥䉡䊛䉟䉥䊮Ớᐲ䈏 80mol%䈎䉌 60mol%䈮ਅ䈏䉎䈫䋬✭๺⃻⽎䉕␜䈜䊏䊷䉪ᒝᐲ䈏ᕆỗ䈮ዊ䈘䈒 䈭䈦䈩䈇䉎䋮 ↰ኪ䈲䋬᷹ⷰ䈚䈢㜞ಽሶ䈱✢ᒻ෸䈶㕖✢ᒻ䈱ዉ㔚✭๺䉴 䊕䉪䊃䊦䉕⛔৻⊛䈮ౣ⃻䈜䉎✭๺㑐ᢙ㱟_nrelax12) 䉕䋬ႎ๔䈚䈩䈇䉎䋮䈖䈖䈪䋬✭๺ᒝᐲ㰱㱟_n䋬✭๺ᤨ㑆㱠_n䋬✭ ๺ᤨ 㑆䈱ಽᏓ 䉕⴫䈜ᜰᢙ㱍_n䋬㱎_n䈪䈅䉎䋮࿑_{8䈮(4),(5)ᑼ䉕} ↪䈇䈩䋬_{E-15MAA-0.8K䈱㕖✢ᒻ⺃㔚䉴䊕䉪䊃䊦䈱䇸ᦛ✢䈅䈩} 䈲䉄_{(fitting)䇹䉕䈚䈢⚿ᨐ䉕␜䈜䋮䈖䈖䈪䋬}D3 = 2.98,E3 = 0.88, W3 = 5.03x10-6_{s, 'V3 = 2.12x10}-19_SmV-2_{ߢ޽ࠆ㧚ߎߎߢᓧߚ} 'V3ߩ୯ߪ㧘ࠗࠝࡦ߇㜞ಽሶਛࠍ⥄↱ߦേߌࠆࠗࠝࡦዉ㔚ᕈ 㜞ಽሶߩ୯㧘଀߃߫㧘ࡐ࡝ࠛ࠴࡟ࡦࠝࠠࠪ࠼♽㜞ಽሶߩ'V3 = 8.01x10-17_SmV-2ߣᲧߴ㕖Ᏹߦዊߐ޿16)㧚߹ߚ㧘㔚⩄߇Ყ セ⊛᧤❈ߐࠇߡ޿ࠆ㜞ಽሶߢᓧࠄࠇߡ޿ࠆ'V3 = 5.18x10-18 ࠃࠅ߽ዊߐ޿17,18)㧚හߜ㔚⩄⒖േ߇߆ߥࠅߎߩࠕࠗࠝࡁࡑ࡯ ߪ᧤❈ࠍฃߌߡ޿ࠆߎߣࠍ␜ໂߔࠆ㧚࿑ਛ䈱䂾䈲㱑3'䋬䃂䈲 㱑3"䈱᷹ቯ୯䉕䋬ታ✢䈲(4),(5)ᑼ䈮ၮ䈨䈒⸘▚⚿ᨐ䉕␜䈜䋮 3ᰴ䈱㕖✢ᒻ⺃㔚䉴䊕䉪䊃䊦䈮䈍䈇䈩䋬࿑䈮␜䈜䉋䈉䈮䋬10 kHzએ਄䈪䈲䋬㱑_3’䈫㱑_{3"䈱䊏䊷䉪䉕฽䉄䋬⦟䈒ౣ⃻䈪䈐䉎䈖䈫} 䈏ಽ䈎䉎䋮䈚䈎䈚䈭䈏䉌䋬_{1 kHz䈎䉌10 kHz䈱▸࿐䈪䈲}㱑_3"䈱 ⸘▚୯䈫᷹ቯ୯䈏ᄢ䈐䈒⇣䈭䈦䈩䈇䉎䋮䈖䉏䈲䋬_{20 kHzㄭற} 䈮䈅䉎✭๺⃻⽎䈮೎䈱⃻⽎䋨࿑_6䈱㱑_{䋱"䈱1 kHzએਅ䈱┙䈤} ਄䈏䉍䈮෻ᤋ䈜䉎㔚ᭂಽᭂ䈭䈬䈱ᓇ㗀䋩䈏㊀⇥䈘䉏䈩䈇䉎䈢 䉄䈫⠨ 䈋䈩䈇䉎䋮䉁䈢䋬_{E-15MAA-0.4K䋬E-15MAA-0.6K䈪䋬䈖} 䈱✭๺䉴䊕䉪䊃䊦䈏ዊ䈘䈒㕖✢ᒻⵝ⟎䈱♖ᐲ䈱㒢⇇䉅䈅䉍䋬䈲䈦 䈐䉍䈞䈝䋬_{(4),(5)ᑼ䈱ᦛ✢䈅䈩䈲䉄䈲䈪䈐䈭䈎䈦䈢䋮} 4. ⠨ ኤ 䉟䉥䊮ᤃേ䈏᭽䇱䈭_{hopping䉺䉟䊒䉕␜䈜႐ว䈮䈧䈇䈩ᓧ䉌} 䉏䉎㔚ᵹ_{I䈲䋬෩ኒ䈮⸘▚䈘䉏䈩䈇䉎}12,19,20䋩䋮․䈮ᦨㄭ䈪䈲ዉ㔚 ᕈ㜞ಽሶ䈱㔚 ⩄ ⒖ േ ᯏ᭴䈮䈧䈇䈩䈲䋬_{dynamic percolation} theory21,22䋩_{䈏ಽሶ㎮䈱䉶䉫䊜䊮䊃ㆇേ䉕ၮ䈮䈚䈢dynamics䉕෻ᤋ} 䈚䈢䊝䊂䊦䈫䈚䈩ᵈ⋡䉕㓸䉄䈩䈍䉍19䋩䋬䊘䊥䉣䉼䊧䊮䉥䉨䉲䊄♽ 㜞ಽሶ䈮䈧䈇䈩䈲㕖✢ᒻᕈ䉕฽䉄䈩⸃ᨆ䈏ᚑഞ䈚䈩䈇䉎12䋩䋮䈢 䈣䈚䋬䈠䈱ᛒ䈇䈲ᾘ㔀䉕ᭂ䉄䉎਄䈮䋬⸃ᨆ䈮䈲⹦⚦䈭᭴ㅧ䈱 ᖱ ႎ 䈏ᔅ ⷐ 䈪䈅䉍䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱䉋䈉䈭䋬ⶄ 㔀 䈭㜞 -1.0x10-9 -0.5 0.0 0.5 1.0 H  H (1 0-20 m 2/ V 2) 6.0 5.5 5.0 4.5 4.0 3.5 3.0 log f (Hz) K(80) K(80) K(60) K(60) K(40) K(40) ٤ǭ3’ of E-15MAA-0.8K ٨ǭ3” of E-15MAA-0.8K غǭ3’ of E-15MAA-0.6K عǭ3” of E-15MAA-0.6K ٌǭ3’ of E-15MAA-0.4K ًǭ3” of E-15MAA-0.4K

Fig.7 Frequency spectra of the third-order nonlinear permittivities in potassium ionomers.

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(n=1,3) (5) 0.4 0.3 0.2 0.1 0.0 H1 " / H0 100 102 104 106 f (Hz) K+(0) K+(40) K+(60) K+(80)

ψ

ψ

ψ

᷹ቯ᷷ᐲ30͠ 㪜㪄㪈㪌㪤㪘㪘㪄㪇㪅㪏㪢 㪜㪄㪈㪌㪤㪘㪘㪄㪇㪅㪍㪢 㪜㪄㪈㪌㪤㪘㪘㪄㪇㪅㪋㪢 㪫㪼㫄㫇㪅 㪊㪇㷄 㪜㪄㪈㪌㪤㪘㪘

Fig.6 ǭ_1"/ǭ_{0 spectrum of potassium ionomer, exhibiting a} change in potassium ion content.

ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞㧔’ િⴕࠄ㧕 ᰴ᭴ㅧ䉕ᜬ䈧㜞ಽሶ䈱႐ว䈮䈲㔍䈚䈇19)䋮ㅢᏱ䋬᭴ㅧ㕙䈱 ᖱႎ䈏ዋ䈭䈇႐ว䋬⸃ᨆ䈮䈲_{hoppingℂ⺰}20)䉕↪䈇䉎䋮䈖䉏 䈲䋬_{hoppingℂ⺰䈏䋬䉨䊞䊥䉝䊷䈏site㑆䉕hopping䈪⒖േ䈜䉎} 䈫䈉ᒻ䈪ዷ㐿䈘䉏䉎䈢䉄䈮䋬᭴ㅧ䈱ᖱႎ䉕䈜䈼䈩_{site䉇bond䈫} 䈇䈉ᒻ䈪⟎䈐឵䈋ᓧ䉎䈫䈇䈉೑ὐ䈮䉋䉎䋮ᧄႎ๔䈮䈍䈇䈩䉅䋬 hoppingℂ⺰䉕↪䈇䉎䈏䋬䉋䉍৻⥸⊛䈭⸃ᨆ䈫䈜䉎䈢䉄䈮䋬䉟 䉥䊮䈱_{hopping䈏ㄭធsite㑆䈱䉂䈮⸵䈘䉏䉎䈫䈇䈉න⚐䊝䊂䊦} 䈪䈲䈭䈒䋬䉣䊈䊦䉩䊷⊛䈮ૐ䈇૏⟎䈻䉅_{hopping䈏⸵䈘䉏䉎䋬} 䉋 䉍 ৻ ⥸ ⊛ 䈭 䊝 䊂 䊦 _{variable range hopping model} (VRHM)20)_{䉕↪䈇䉎䋮} 䈖䈖䈪ᐔဋ_{hopping〒㔌a䋬ශട㔚⇇E䋬⛘ኻ᷷ᐲT䋬ᭂ㒢⊛} 䈭_{hopping ⏕ ₸ P0}䋬 ⚛ 㔚 ⩄_{e 䋬 䉨 䊞 䊥 䉝 䊷 䈱 ᢙ ኒ ᐲ N 䋬} Boltzmannቯᢙ㱖䋬site㑆䈱ᵴᕈൻ䉣䊈䊦䉩䊷㰱U䈪䈅䉎䋮䈖 䈖䈪䋬_{I䉕ᒻᑼ⊛䈮E䈪ዷ㐿䈜䉎䈫䋬} 䉕ᓧ䉎䋮䈖䈖䈪䋬✢ᒻⶄ⚛⺃㔚䉴䊕䉪䊃䊦䈎䉌䋨_{8䋩ᑼ䉕↪䈇䈩a} 䈱_{fitting䉕⹜䉂䈩䉅䋬ᧂ⍮ቯᢙ䈏ᄙ䈒䋬૗䉌䈎䈱઒ቯ䉕ዉ౉} 䈚䈭䈔䉏䈳ਇน⢻䈪䈅䉎䋮䈫䈖䉐䈏䋬㱟₁䈫㱟₃䈱Ყ䈲ᰴ䈱ᑼ䈪 ⴫䈞䉎12䋩䋮 䈧䉁䉍䋬㱟₁䈫㱟₃䈱୯䈏ታ㛎⊛䈮⹏ଔ䈏䈪䈐䉏䈳䋬䋨_10䋩ᑼ䉕 ↪䈇৻⟵⊛䈮ታ㛎୯䈱䉂䈪䋬ᐔဋ_{hopping〒㔌a䈱୯䉕᳞䉄} 䉎䈖䈫䈏น⢻䈮䈭䉎䋮䈖䈖䈪䈲䋬䉦䊥䉡䊛䉟䉥䊮䈪_{80mol%ਛ๺䈚} 䈢䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷_{(E-15MAA-0.8K)䈱ታ㛎䉋䉍ᓧ䈢㜞๟} ᵄ ஥ ෸ 䈶ૐ ๟ ᵄ ஥ 䈱ᭂ 㒢 ୯ 䈱㱟₁䈫㱟₃䉕↪ 䈇䈩_{a䈱⹏ଔ䉕} ⴕ䈇䋬_{a=3nm䈫a=52nm䉕ᓧ䈢䋮} 䈖䉏䉁䈪ዊⷺᢔੂ_{X✢࿁ᨆ䉇䋬㔚ሶ㗼ᓸ㏜ⷰኤ䋬ේሶ㑆} ജ 㗼 ᓸ ㏜ ᴺ 䈮䉋䉍ႎ ๔ 䈘䉏䈩䈇䉎23-26)䉝䉟䉥䊉䊙䊷䈱䉟䉥䊮 ಝ 㓸 ૕ 䉰 䉟 䉵 䈲 ᢙ_{nm 䈪 䈅 䉎 䈖 䈫 䈎 䉌 䋬 ᚒ 䇱 䈱 ᓧ 䈢 ᐔ ဋ} 䉥䊮ಝ㓸૕䈱䉰䉟䉵䋩䈮ኻᔕ䈚䈩䈇䉎䈫⠨䈋䈩䈇䉎䋮䉁䈢䋬৻ ⥸䈮䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱ዉ㔚ᕈ䈲䋬㜞Ớᐲ䈮䉦䊥䉡䊛䉟䉥 䊮䈪ਛ๺䈘䉏䈢႐ว䈮䈱䉂⊒⃻䈜䉎䈖䈫䈏⍮䉌䉏䈩䈇䉎_(଀䈋 䈳䋬_{E-15MAA䊔䊷䉴䈪䈲⚂80mol%ਛ๺એ਄䈪䋬ዉ㔚ᕈ䈏} ᕆỗ䈮⊒⃻䈜䉎₎6)䋮䈘䉌䈮䋬䉦䊥䉡䊛䉇䊅䊃䊥䉡䊛䉝䉟䉥䊉䊙䊷 䈱䉟䉥䊮ಝ㓸૕ᒻᚑ䈲ਛ๺ᐲ_{60%⒟ᐲ䈪ቢᚑ䈚䋬䈠䉏એ਄} 䈱ਛ๺ᐲ䈪䈲䊚䉪䊨⋧ಽ㔌䈏⿠䈖䉎䈖䈫䈏ႎ๔䈘䉏䈩䈇䉎27)䋮 ᚒ䇱䈲䋬䈖䉏䉌䈱ႎ๔䉕〯䉁䈋䋬㜞Ớᐲ䈮䉦䊥䉡䊛䉟䉥䊮䈪ਛ ๺䈘䉏䈢႐ว䈮䈍䈇䈩䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱䉟䉥䊮ಝ㓸ㇱ 䈲䋬ᐔဋ_{hopping〒㔌a=52nm䈮ኻᔕ䈜䉎䋬⺃㔚✭๺⃻⽎䈮} 㑐 ਈ 䈜 䉎 ⊒ ㆐ 䈚 䈢 䋬 䈅 䉎 ⒳ 䈱 䉟 䉥 䊮 䉪 䊤 䉴 䉺 䊷 ᭴ ㅧ_{( એ 㒠} domain䈫⒓䈜䉎)䉕ᒻᚑ䈜䉎䉅䈱䈫⠨䈋䈩䈇䉎䋮 䈭 䈍 䋬 䉦 䊥 䉡 䊛 䉟 䉥 䊮 䈪_{40mol%(E-15MAA-0.4K) 䋬} 60mol%(E-15MAA-0.6K)ਛ๺䈚䈢䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷䈪䈲䋬 3ᰴ 䈱㕖 ✢ ᒻ ⶄ ⚛ 䉴䊕䉪䊃䊦᷹ ቯ 䈏಴ ᧪ 䈩䈇䈭䈇䋮䈖䉏䈲 domain᭴ㅧ䈏ᒻᚑ䈘䉏䈭䈇䈢䉄䈎䋬᷹ቯ♖ᐲ䈱㒢⇇䈎䈲⃻ ࿷䈱䈫䈖䉐䈲ਇ᣿䈪䈅䉎䋮 5䋮䋮 䉁䉁䈫䈫䉄䉄 䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈱㕖✢ᒻⶄ⚛⺃㔚₸䈱᷹ቯ䈏น⢻䈭 ታ㛎䉲䉴䊁䊛䉕᭴▽䈚䋬㕖✢ᒻⶄ⚛⺃㔚₸䈱䉴䊕䉪䊃䊦䉕᷹

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₍₁₀₎ -1.0x10-9 -0.5 0.0 0.5 1.0 H  H (1 0-20 m 2/ V2 ) 6.0 5.5 5.0 4.5 4.0 3.5 3.0 log f (Hz) K(80) K(80) theory ٤ǭ3’ of E-15MAA-0.8K ٨ǭ₃” of E-15MAA-0.8K 㧙ޓޓޓtheory -1.0x10-9 -0.5 0.0 0.5 1.0 H  H (1 0-20 m 2/ V2 ) 6.0 5.5 5.0 4.5 4.0 3.5 3.0 log f (Hz) K(80) K(80) theory ٤ǭ3’ of E-15MAA-0.8K ٨ǭ₃” of E-15MAA-0.8K 㧙ޓޓޓtheory

Fig.8 Comparison of observed (circles) and fitted (solid lines) frequency spectra of the third-order nonlinear permittivities of E-15MAA-0.8K. 31 1 2007

7 ࠞ࡝࠙ࡓࠕࠗࠝࡁࡑ࡯ߩ㕖✢ᒻ⺃㔚ࠬࡍࠢ࠻࡞㧔’ િⴕࠄ㧕 ቯ䈚䈢䋮᷹ቯ䈚䈢⺃㔚䉴䊕䉪䊃䊦䈲䋬✭๺⃻⽎䉕઻䈇ⶄ㔀䈭 ๟ᵄᢙଐሽᕈ䉕␜䈚䈢䋮䈖䉏䉌䈱䉴䊕䉪䊃䊦䉕⛔৻⊛䈮ౣ⃻ 䈪䈐䉎⚻㛎ᑼ䉕↪䈇䋬᷹ቯ䈚䈢㕖✢ᒻ⺃㔚₸䈱୯䉕૶䈉䈖䈫 䈪䋬ታ㛎୯એᄖ䈱૗䉌䈱઒ቯ䈭䈚䈮㔚⩄⒖േ䈮㑐䉒䉎ၮᧄ ⊛䈭_{hopping〒㔌䉕⹏ଔ䈜䉎䈖䈫䈏䈪䈐䈢䋮} 䈖䉏䉁䈪䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䉕฽䉃䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷 䈪ឭ໒䈘䉏䈩䈇䉎䉟䉥䊮ಝ㓸૕䈱ᄢ䈐䈘䈲ᢙ_{nm䈪䈅䉍䋬䈖䉏} 䈲ᧄ ᬌ ⸛ 䈪⏕ ⹺ 䈘䉏䈢䋬ᐔ ဋ_{hopping〒㔌a=3nm䈏␜䈜㔚} ⩄⒖േ䈱⚛ㆊ⒟_{(Elementary Process)䈮ኻᔕ䈚䈩䈇䉎䈫⠨䈋} 䈩䈇䉎䋮䈖䉏䈮ኻ䈚_{a=52nm䈱᷹ቯ⚿ᨐ䈲䋬E-15MAA-0.8K䈮} 䈍䈔䉎૗䉌䈎䈱㜞ᰴ᭴ㅧ_{(domain)䉕␜䈚䈩䈇䉎䉅䈱䈫⠨䈋䈩䈇䉎䋮} 䈖䉏䉌䈱⚿ᨐ䈲䋬䈖䉏䉁䈪䈮䉣䉼䊧䊮䉝䉟䉥䊉䊙䊷䈮䈍䈇䈩ឭ ໒䈘䉏䈩䈇䉎䋬㜞ᰴ᭴ㅧ䊝䊂䊦1)䉇䋬䉟䉥䊮䉪䊤䉴䉺䊷㗔ၞ䈱 ሽ࿷2)䈫䋬䉦䊥䉡䊛䉝䉟䉥䊉䊙䊷䈮䈍䈔䉎䋬⺃㔚✭๺⃻⽎䈏ኒ ធ䈮㑐ଥ䈚䈩䈇䉎䈖䈫䉕␜䈜䉅䈱䈫⠨䈋䈩䈇䉎䋮੹ᓟ䈲䋬ⶄ⚛ 㕖✢ᒻ⺃㔚䉴䊕䉪䊃䊦䈱᷷ᐲଐሽᕈ䈱᷹ቯ䉕น⢻䈮䈚䋬䉦䊥 䉡䊛䉝䉟䉥䊉䊙䊷ਛ䈱㔚⩄᜼േ䈱⸃᣿䈮䈧䈭䈕䈢䈇䈫⠨䈋䈩 䈇䉎䋮 5. ෳෳ⠨⠨ᢥᢥ₂₂

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