무정형 폴리아릴레이트의 점탄성과 복굴절Ⅰ

황의정; Inoue T; Osaki K

Polymer(Korea), Vol.17, No.3, 249-259, May, 1993

Export Citation

무정형 폴리아릴레이트의 점탄성과 복굴절Ⅰ

Viscoelasticity and Birefringence of Amorphous Polyarylates I

황의정, Inoue T, Osaki K

초록

무정형 폴리아릴레이트에 대해, 고무상 영역에서 유리상 영역에 걸쳐 동적 탄성율, E^* 및 동적스트레인-광탄성 계수, O^*를 측정하여 고찰하였다. 측정은 205℃에서 255℃ 사이의 여러 온도에 대해, 주파수를 1∼130 Hz로 변화시키며 행하였고, 시간-온도 환산칙을 적용하여 E^*, O^*의 마스타 곡선을 합성하였다. 구성한 두 특성치의 주파수 스펙트럼에 대해, 이전에 우리가 제안한 수정 응력-광탄성칙을 적용하여 고찰하였다. 폴리아릴레이트의 동적 탄성율 E^*는 전형적인 무정형 고분자의 특성을 보였으며, 고무 평단 영역의 탄성율, E_N'이 다른 고분자에 비해 매우 큰 11.2MPa을 나타냈다. 동적 스트레인-광탄성 계수 O^*는, 페닐기가 측쇄로 존재하는 고분자들에 비해 매우 억제된 주파수 의존성을 보였다. 또한 측정된 전 영역에서 양의 값을 보였다. 수정 응력-광탄성칙에 의해 구한 폴리아릴레이트의 응력-광탄성 계수, C_R, C_G는 각각 6.8×10^-9Pa^-1과 2.0×10^-11Pa^-1을 나타냈다. 결정된 광탄성 계수를 이용하여, 측정한 영역에서의 동적 탄성율 E^*를, 성분 탄성율 E_R^*, E_G^*로 분리하여, 각탄성율의 발생기구에 대해 고찰하였다. 또한 마스타 곡선 합성시 사용한 각 특성치의 환산이동인자의 온도 의존성에 대해서도 고찰하였다.

The complex Young's modulus, E^*, and the complex strain-optical coefficient, O^*, of a conventional amorphous polyarylate were studied around the glassy-to-rubber transition zone. Measurement were performed over the frequency range of 1 to 130 Hz at various temperature between 205℃ and 255℃ and the master cures were constructed with the time-temperature superposition principle. The E^* of polyarylate showed typical relaxation behavior of amorphous polymers. The rubbery plateau modulus, E_N'=11.2MPa, was higher than the value of common amorphous polymers. The O^* of polyarylate was positive over the whole reduced frequency range. A modified stress-optical rule(M-SOR) proposed previously was applied; by comparing E^* with O^*, the E^* could be separated into two component functions, E_R^* and E_G^* and they allowed the consideration of relaxation mechanism responsible for the complex modulus. The stress-optical coefficients, C_R and C_G, corresponding to E_R^* and E_G^* were 6.8×10^-9 Pa^-1 and 2.0×10^-11Pa^-1, respectively. The temperature dependence of the shift factors used in constructing master curves of E^*, O^*, E_R^* and E_G^* was discussed.

[References]

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Okamoto H, Hwang EJ, Inoue T, Osaki K, Nihon Rheoloji Gakkaishi, accepted in press
Hwang EJ, Inoue T, Osaki K, Polymer, accepted in press
Hwang EJ, Inoue T, Osaki K, Polym. Eng. Sci., accepted in press
Kuske A, Rovertson G, "Photoelastic Stress Analysis," John Wiley Chichester (1977)
Wust CJ, Bouge DC, J. Appl. Polym. Sci., 28, 1931 (1983)
Priss Ls, Vishnyakovm II, Pavlova IP, Int. J. Polym. Mater., 8, 85 (1980)
Alegria A, Macho E, Colmenero J, Macromolecules, 24, 5196 (1991)
Cavaille JY, Etienne S, Perez J, Monnerie L, Johari GP, Polymer, 27, 549 (1986)
Wimberger-Friedl R, Rheol. Acta, 30, 329 (1991)
In Preparation to be published
Stein RS, "Newer Method of Polymer Characterization," Interscience, New York (1964)

[1] deGennes PG, J. Chem. Phys., 55, 572 (1971)

[2] Ferry JD, "Viscoelastic Properties of Polymers," 3rd ed., John Wiley & Sons, New York (1980)

[3] Doi M, Edwards SF, "The Theory of Polymer Dynamics," Charendon Press, Oxford (1986)

[4] Raju VR, Menezes EV, Marin G, Graessley WW, Macromolecules, 14, 1668 (1984)

[5] Ngai KL, Plazek DJJ, J. Polym. Sci. B: Polym. Phys., 23, 2159 (1985)

[6] Onogi S, Masuda T, Kitagawa K, Macromolecules, 3, 109 (1970)

[7] Robert GE, White EFT, "The Physics of Glassy Polymers," John Wiley and Sons, New York (1973)

[8] Stockmayer WH, Pure Appl. Chem., 15, 539 (1967)

[9] Adachi K, Yoshida H, Fukui F, Kotaka T, Macromolecules, 23, 3138 (1990)

[10] Onogi S, Keedy DA, Stein RS, J. Polym. Sci., 50, 15 (1961)

[11] Read BE, Polymer, 3, 143 (1962)

[12] Read BE, Polym. Eng. Sci., 23, 835 (1983)

[13] Treloar LRG, "The Physics of Rubber Elasticity," 3rd Ed., Clarendon Press, Oxford (1975)

[14] Wales JLS, "The Application of Flow Birefringence to Rheological Studies of Polymer Melts," Delft Univ. Press, Delft, Netherlands (1976)

[15] Janeschitz-Kriegl H, "Polymer Melt Rheology and Flow Birefringence," Springer-Verlag, Berlin (1983)

[16] Osaki K, Kimura S, Kurata M, J. Rheol., 25, 549 (1981)

[17] Osaki K, Takatori E, Ueda M, Kurata M, Kotaka T, Ohnuma H, Macromolecules, 22, 2457 (1989)

[18] Inoue T, Okamoto H, Osaki K, Macromolecules, 24, 5670 (1991)

[19] Inoue T, Okamoto H, Hayashihara H, Osaki K, J. Polym. Sci. B: Polym. Phys., 30, 409 (1992)

[20] Okamoto H, Hayashihara H, Inoue T, Osaki K, Nihon Rheoloji Gakkaishi, 19, 220 (1991)

[21] Inoue T, Hwang EJ, Osaki K, J. Rheol., 36(8), 1737 (1992)

[22] Inoue T, Hwang EJ, Osaki K, Bull. Inst. Chem. Res. Kyoto Univ., 70(2), 162 (1992)

[23] Okamoto H, Hwang EJ, Inoue T, Osaki K, Nihon Rheoloji Gakkaishi, accepted in press

[24] Hwang EJ, Inoue T, Osaki K, Polymer, accepted in press

[25] Hwang EJ, Inoue T, Osaki K, Polym. Eng. Sci., accepted in press

[26] Kuske A, Rovertson G, "Photoelastic Stress Analysis," John Wiley Chichester (1977)

[27] Wust CJ, Bouge DC, J. Appl. Polym. Sci., 28, 1931 (1983)

[28] Priss Ls, Vishnyakovm II, Pavlova IP, Int. J. Polym. Mater., 8, 85 (1980)

[29] Alegria A, Macho E, Colmenero J, Macromolecules, 24, 5196 (1991)

[30] Cavaille JY, Etienne S, Perez J, Monnerie L, Johari GP, Polymer, 27, 549 (1986)

[31] Wimberger-Friedl R, Rheol. Acta, 30, 329 (1991)

[32] In Preparation to be published

[33] Stein RS, "Newer Method of Polymer Characterization," Interscience, New York (1964)