Competition between Phase Separation and Crystallization in a PCL/PEG Polymer Blend Captured by Synchronized SAXS, WAXS, and DSC

Wei-Tsung Chuang; U-Ser Jeng; Hwo-Shuenn Sheu; Po-Da Hong

Macromolecular Research, Vol.14, No.1, 45-51, February, 2006

Wei-Tsung Chuang, U-Ser Jeng^†, Hwo-Shuenn Sheu, and Po-Da Hong¹

National Synchrotron Radiation Research Center101 Hsin-Ann Road, Hsinchu Science Park Hsinchu 30076, Taiwan
¹Department of Polymer Engineering, National Taiwan University of Science and Technology, Taipei 10673, Taiwan

E-mail:

We conducted simultaneous, small-angle, X-ray scattering/differential scanning calorimetry (SAXS/DSC) and simultaneous, wide-angle, X-ray scattering (WAXS)/DSC measurements for a polymer blend of poly( ε-caprolactone)/poly(ethylene glycol) (PCL/PEG). The time-dependent SAXS/DSC and WAXS/DSC results, measured while the system was quenched below the melting temperature of PCL from a melting state, revealed the competitive behavior between liquid-liquid phase separation and crystallization in the polymer blend. The time-dependent structural evolution extracted from the SAXS/WAXS/DSC results can be characterized by the following four stages in the PCL crystallization process: the induction (I), nucleation (II), growth (III), and late (IV) stages. The influence of the liquid-liquid phase separation on the crystallization of PCL was also observed by phase-contrast microscope and polarized microscope with 1/4 λ compensator.

Keywords:phase separation;crystallization;polymer blend;poly( ε-caprolactone);poly(ethylene glycol)

[References]

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[Referenced By]

[1] Russel TP, Koberstein JT, J. Polym. Sci. A: Polym. Chem., 23, 1109 (1985)

[2] Bras W, Derbyshire GE, Devine A, Clark SM, Cooker J, Komanschek BE, Ryan AJ, J. Appl. Crystallogr., 28, 26 (1995)

[3] Lexa D, Rev. Sci. Instrum., 70, 2242 (1999)

[4] Kruger KN, Zachmann HG, Macromolecules, 26, 5202 (1993)

[5] Okamoto S, Yamamoto K, Nomura K, Hara S, Akiba I, Sakurai K, Koyama A, Nomura M, Sakurai S, J. Macromol. Sci.-Phys., 43, 279 (2004)

[6] Wutz C, Bark M, Cronauer J, Dohrmann R, Zachmann HG, Rev. Sci. Instrum., 66, 1303 (1995)

[7] Sics I, Nogales A, Ezquerra TA, Denchev Z, Balta-Calleja FJ, Rev. Sci. Instrum., 71, 1733 (2000)

[8] Bryant GK, Gleeson HF, Ryan AJ, Fairclough JPA, Bogg D, Goossens JGP, Bras W, Rev. Sci. Instrum., 69, 2114 (1998)

[9] Naylor S, Bras W, Derbyshire G, Mant GR, Bogg D, Ryan AJ, Nucl. Instrum. Methods., B97, 253 (1995)

[10] Terrill NJ, Fairclough PA, Towns-Andrews E, Komanschek BU, Young RJ, Ryan AJ, Polymer, 39(11), 2381 (1998)

[11] Lopez-Cabarcos E, Hsiao BS, Balta-Calleja FJ, Phys. Rev. E, 54, 989 (1996)

[12] Tashiro K, Kariyo S, Nishimori A, Fujii T, Saragai S, Nakamoto S, Kawaguchi T, Maatsumoto A, Rangsiman O, J. Polym. Sci. B: Polym. Phys., 40(6), 495 (2002)

[13] Imai M, Kaji K, Kanaya T, Phys. Rev. Lett., 71, 4162 (1993)

[14] Olmsted PD, Poon WCK, McLeish TCB, Terrill NJ, Ryan AJ, Phys. Rev. Lett., 81, 373 (1998)

[15] Tanaka H, Nishi T, Phys. Rev. Lett., 55, 1102 (1985)

[16] Inaba N, Sato K, Suzuki S, Hashimoto T, Macromolecules, 19, 1690 (1986)

[17] Inaba N, Yamada T, Suzuki S, Hashimoto T, Macromolecules, 21, 407 (1988)

[18] Kim JK, Kim BK, J. Polym. Sci. B: Polym. Phys., 37(16), 1991 (1999)

[19] Kim JK, Kim BK, Park M, J. Polym. Sci. B: Polym. Phys., 38(5), 707 (2000)

[20] Wang H, Shimizu K, Kim H, Hobbie EK, Wang ZG, Han CC, J. Chem. Phys., 116(16), 7311 (2002)

[21] Keller A, Cheng SZD, Polymer, 39(19), 4461 (1998)

[22] Chuang WT, Shih KS, Hong PD, J. Polym. Res., 12, 197 (2005)

[23] Lai YH, Sun YS, Jeng U, Song YF, Tsang KL, Liang KS, Nucl. Instrum. Methods Phys. Res. Sect. B-Beam Interact. Mater. Atoms, 238, 205 (2005)

[24] Strobl GR, Schneider M, J. Polym. Sci. B: Polym. Phys., 18, 1343 (1980)

[25] Ruland WJ, J. Appl. Crystallogr., 4, 70 (1971)

[26] Debye P, Bueche AM, J. Appl. Phys., 20, 518 (1949)

[27] Deby P, Anderson HR, Brumberger H, J. Appl. Phys., 28, 679 (1957)

[28] Stein RS, Khambatta FB, Warner FP, Russell TP, Escala A, Balizer E, J. Polym. Sci. Polym. Symp., 3, 313 (1978)

[29] Russell TP, Ito H, Wignall GD, Macromolecules, 21, 1703 (1988)

[30] Nojima S, Satoh K, Ashida T, Macromolecules, 24, 942 (1991)

[31] Hu H, Dorset DL, Macromolecules, 23, 4604 (1990)

[32] Wang ZG, Hsiao BS, Sirota EB, Agarwal P, Srinivas S, Macromolecules, 33(3), 978 (2000)

[33] Elsner G, Zachmann HG, Milch JR, Makromol. Chem., 182, 657 (1981)

[34] Hsiao BS, Kenn G, Corwin H, Wu DQ, Chu B, Polymer, 34, 3986 (1993)

[35] Verma R, Marand H, Hsiao B, Macromolecules, 29(24), 7767 (1996)

[36] Hama H, Tashiro K, Polymer, 44(7), 2159 (2003)