용액결정화된 비닐리덴플루오라이드와 트리플루오로에틸렌 공중합체의 강유전 전이에 관한 연구

조재환

Polymer(Korea), Vol.15, No.1, 67-75, February, 1991

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용액결정화된 비닐리덴플루오라이드와 트리플루오로에틸렌 공중합체의 강유전 전이에 관한 연구

Studies of Ferroelectric Transition of Solution-Crystallized Copolymer of Vinylidenefluoride and Trifluoroethylene

조재환

초록

Vinylidenefluoride-trifluoroethylene(VDF-TrFE) 공중합체의 용해도 파라미터가 여러 가지 종류의 액체를 이용한 용해도 실험으로부터 구해졌으며 이들 용매로부터 cast된 VDF-TrFE 공중합체의 Curie 전이 및 용융 거동이 시차열분석에 의하여 고찰되었다. 용해도 실험에 의한 3차원 Hansen space로부터 구해진 VDF-TrFE 공중합체의 용해도 파라미터의 값은 23.4MPa^1/2이었으며 이들의 dispersion, polar 및 hydrogen bonding에 따른 성분들은 각각 17.3, 13.8 및 7.7MPa^1/2로 나타났다. 여러 가지 용매로부터 cast된 시료들의 Curie 온도는 용융 결정화된 시료의 그것에 비하여 높은 값을 가졌으며 또 Curie 전이 엔탈피와 융해열은 좋은 직선관계를 보였다. 시료들의 Curie 온도는 용매의 총 용해도 파라미터의 값에 의존하는 것이 아니라 용해도 파라미터의 polar 성분의 값δp)에 다소 의존함을 보였다. 즉 δp의 값이 클수록 더 높은 Curie 온도를 보였다.

Solubility parameter of vinylidenefluoride-trifluoroethylene(VDF-TrFE) copolymer was determined from the solubility test using 30 liquids and the behaviors of Curie transition and melting were investigated by the differential scanning calorimetrical measurements. The value of solubility parameter of VDF-TrFE copolymer was 23.4MPa^1/2 and dispersion, polar and hydrogen bonding terms of solubility parameter were 17.3, 13.8 and 7.7MPa^1/2, respectively, which was calculated from three dimensional hansen space. Curie temperature of sample cast from various solutions was higher than that of sample crystallized from the melt and heat of Curie transition was nearly linear to the heat of fusion. Curie temperature of smple was not dependent on the total solubility parameter but on the polar term of solubility parameter. That is, the higher the polar term of solubility parameter was, the higher the Curie temperature was.

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[1] Lovinger AJ, Furukawa T, Davis GT, Broadhurst MG, Polymer, 24, 1225 (1983)

[2] Yamada T, Kitayama T, J. Appl. Phys., 52, 6859 (1981)

[3] Yamada T, Ueda T, Kitayama T, J. Appl. Phys., 52, 948 (1981)

[4] BeBrierty VJ, Douglass DC, Furukawa T, Macromolecules, 17, 1136 (1984)

[5] Furukawa T, Ohuchi M, Chiba A, Date M, Macromolecules, 17, 1384 (1984)

[6] Tanaka H, Yukawa H, Nishi T, Macromolecules, 21, 2469 (1988)

[7] Cho JW, Br. Polym. J., to be published

[8] Starkweather HW, Zoller P, Jones GA, J. Polym. Sci. B: Polym. Phys., 22, 1431 (1984)

[9] Moggi G, Bonardelli P, J. Polym. Sci. B: Polym. Phys., 22, 357 (1984)

[10] Centore R, DeRosa C, Guerra G, Petraccone V, Corradini P, Villani V, Eur. Polym. J., 24, 445 (1988)

[11] Sanchez IC, Eby RK, Macromolecules, 8, 638 (1975)

[12] Sanchez IC, Eby RK, J. Res. Nat'l Bur. Stand. A. Physics Chem., 77A, 353 (1973)

[13] Salazar JM, Calleja FJB, Polym. Bull., 2, 163 (1980)

[14] Davis GT, Eby RK, Martin GM, J. Appl. Phys., 39, 4773 (1968)

[15] DeSalazar JM, Calleja FJ, J. Cryst. Growth, 48, 283 (1979)

[16] Calleja FJB, Ortega JCG, Salazar JM, Polymer, 19, 1094 (1978)

[17] Vonk C, J. Polym. Sci. C: Polym. Lett., 38, 429 (1972)

[18] Calleja FJB, "Morphology of Polymers," pp. 27-46, Walter De Gryter (1986)

[19] Green JS, Farmer BL, Rabolt JF, J. Appl. Phys., 60, 2690 (1986)

[20] Stack GM, Ting RY, J. Polym. Sci. B: Polym. Phys., 26, 55 (1988)

[21] Bottino A, Capannelli G, Munari S, Turturro A, J. Polym. Sci. B: Polym. Phys., 26, 785 (1988)

[22] Patterson DD, J. Paint Technol., 41, 489 (1979)

[23] Ahmad H, Yaseen M, Polym. Eng. Sci., 19, 858 (1979)

[24] Siddiqui SA, Needles HL, Text. Res. J., 50, 570 (1982)