화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.17, No.6, 365-377, June, 2009
Export Citation
New Characterization Methods for Block Copolymers and their Phase Behaviors
Hae-Woong Park, Jueun Jung, and Taihyun Chang†
  • Department of Chemistry and Graduate Institute of Advanced Materials Science, Pohang University of Science and Technology, Pohang 790-784, Korea
E-mail:
In this feature article, we briefly review the new methods we have utilized recently in the investigation of morphology and phase behavior of block copolymers. We first describe the chromatographic fractionation method to purify block copolymers from their side products of mainly homopolymers or block copolymer precursors inadvertently terminated upon addition of the next monomer in the sequential anionic polymerization. The chromatographic method is extended to the fractionation of the individual block of diblock copolymers which can yield the diblock copolymer fractions of different composition and molecular weight, which also have narrower distributions in both molecular weight and composition. A more detailed phase diagram could be constructed from the set of block copolymer fractions without the need of acquiring many block copolymers each prepared by anionic polymerization. The fractions with narrow distribution in both molecular weight and composition exhibit better long-range ordering and sharper phase transition. Next, epitaxial relationships between two ordered structures in block copolymer thin film is discussed. We employed the direct visualization method, transmission electron microtomography (TEMT) to scrutinize the grain boundary structure.
Keywords:block copolymer;molecular characterization;chromatography;phase transition;epitaxial grain boundary;transmission electron microtomography.
  1. Park M, Harrison C, Chaikin PM, Register RA, Adamson DH, Science, 276(5317), 1401 (1997)
  2. Hamley IW, The Physics of Block Copolymers, Oxford Univ. Press, New York (1998)
  3. Thurn-Albrecht T, Schotter J, Kastle CA, Emley N, Shibauchi T, Krusin-Elbaum L, Guarini K, Black CT, Tuominen MT, Russell TP, Science, 290, 2126 (2000)
  4. Urbas A, Sharp R, Fink Y, Thomas EL, Xenidou M, Fetters LJ, Adv. Mater., 12(11), 812 (2000)
  5. Black CT, Guarini KW, Milkove KR, Baker SM, Russell TP, Tuominen MT, Appl. Phys. Lett., 79, 409 (2001)
  6. Cheng JY, Ross CA, Chan VZH, Thomas EL, Lammertink RGH, Vancso GJ, Adv. Mater., 13(15), 1174 (2001)
  7. Kim HC, Jia XQ, Stafford CM, Kim DH, McCarthy TJ, Tuominen M, Hawker CJ, Russell TP, Adv. Mater., 13(11), 795 (2001)
  8. Lee W, Cho DY, Chang TY, Hanley KJ, Lodge TP, Macromolecules, 34(7), 2353 (2001)
  9. Park S, Cho D, Im K, Chang T, Uhrig D, Mays JW, Macromolecules, 36(15), 5834 (2003)
  10. Park S, Park I, Chang T, Ryu CY, J. Am. Chem. Soc., 126(29), 8906 (2004)
  11. Chung BH, Park S, Chang TY, Macromolecules, 38(14), 6122 (2005)
  12. Lee B, Park I, Yoon J, Park S, Kim J, Kim KW, Chang T, Ree M, Macromolecules, 38(10), 4311 (2005)
  13. Park I, Lee B, Ryu J, Im K, Yoon J, Ree M, Chang T, Macromolecules, 38(25), 10532 (2005)
  14. Choi C, Jang MK, Nah JW, Macromol. Res., 15(7), 623 (2007)
  15. Dayananda K, Kim MS, Kim BS, Lee DS, Macromol. Res., 15(4), 385 (2007)
  16. Hwang SJ, Kim MS, Han JK, Lee DS, Kim BS, Choi EK, Park HJ, Kim JS, Macromol. Res., 15(5), 437 (2007)
  17. Im K, Park HW, Kim Y, Chung B, Ree M, Chang T, Anal. Chem., 79, 1067 (2007)
  18. Kim GP, Jung YS, Yoon SB, Kim DW, Baeck SH, Macromol. Res., 15(7), 693 (2007)
  19. Kim SY, Cho SH, Lee YM, Chu LY, Macromol. Res., 15(7), 646 (2007)
  20. Lee HS, Roy A, Badami AS, McGrath JE, Macromol. Res., 15(2), 160 (2007)
  21. Lee YK, Hong SM, Kim JS, Im JH, Min HS, Subramanyam E, Huh KM, Park SW, Macromol. Res., 15(4), 330 (2007)
  22. Jun YJ, Park KM, Joung YK, Park KD, Lee SJ, Macromol. Res., 16(8), 704 (2008)
  23. Kim BJ, Oh DK, Chang JY, Macromol. Res., 16(2), 103 (2008)
  24. Kim JK, Lee JI, Lee DH, Macromol. Res., 16(4), 267 (2008)
  25. Lee DH, Kang YS, Kim JH, Kang SW, Macromol. Res., 16(8), 676 (2008)
  26. Lee DK, Park JT, Choi JK, Roh DK, Lee JH, Shul YG, Kim JH, Macromol. Res., 16(6), 549 (2008)
  27. Min Y, Lee S, Park JK, Cho KY, Sung SJ, Macromol. Res., 16(3), 231 (2008)
  28. Park E, Ryu DY, Kim JK, Ree M, Chang T, Polymer, 49, 2170 (2008)
  29. Park HW, Jung J, Chang T, Matsunaga K, Jinnai H, J. Am. Chem. Soc., 131, 46 (2009)
  30. Bates FS, Science, 251, 898 (1991)
  31. Bates FS, Schulz MF, Khandpur AK, Foerster S, Rosedale JH, Almdal K, Mortensen K, Faraday Discuss., 98, 7 (1994)
  32. Li C, Li GH, Moon HC, Lee DH, Kim JK, Cho J, Macromol. Res., 15(7), 656 (2007)
  33. Park C, Rhue M, Im M, Kim C, Macromol. Res., 15(7), 688 (2007)
  34. Park C, Rhue M, Lim J, Kim C, Macromol. Res., 15(1), 39 (2007)
  35. Bang J, Lodge TP, Macromol. Res., 16(1), 51 (2008)
  36. Kim DH, Ko YS, Kwon YK, Macromol. Res., 16(1), 62 (2008)
  37. Forster S, Antonietti M, Adv. Mater., 10(3), 195 (1998)
  38. Khandpur AK, Forster S, Bates FS, Hamley IW, Ryan AJ, Bras W, Almdal K, Mortensen K, Macromolecules, 28(26), 8796 (1995)
  39. Leibler L, Marcromolecules, 13, 1602 (1980)
  40. Matsen MW, Bates FS, Macromolecules, 29(4), 1091 (1996)
  41. Almdal K, Rosedale JH, Bates FS, Wignall GD, Fredrickson GH, Phys. Rev. Lett., 65, 1112 (1990)
  42. Koppi KA, Tirrell M, Bates FS, Phys. Rev. Lett., 70, 1449 (1993)
  43. Hamley IW, Koppi KA, Rosedale JH, Bates FS, Almdal K, Mortensen K, Macromolecules, 26, 5959 (1993)
  44. Forster S, Khandpur AK, Zhao J, Bates FS, Hamley IW, Ryan AJ, Bras W, Macromolecules, 27(23), 6922 (1994)
  45. Hajduk DA, Harper PE, Gruner SM, Honeker CC, Kim G, Thomas EL, Fetters LJ, Macromolecules, 27(15), 4063 (1994)
  46. Sakurai S, Kawada H, Hashimoto T, Fetters LJ, Macromolecules, 26, 5796 (1993)
  47. Hajduk DA, Gruner SM, Rangarajan P, Register RA, Fetters LJ, Honeker C, Albalak RJ, Thomas EL, Macromolecules, 27(2), 490 (1994)
  48. Koppi KA, Tirrell M, Bates FS, Almdal K, Mortensen K, J. Rheol., 38(4), 999 (1994)
  49. Schulz MF, Bates FS, Almdal K, Mortensen K, Phys. Rev. Lett., 73, 86 (1994)
  50. Zhao J, Majumdar B, Schulz MF, Bates FS, Almdal K, Mortensen K, Hajduk DA, Gruner SM, Macromolecules, 29, 1204 (1994)
  51. Laradji M, Shi AC, Noolandi J, Desai RC, Macromolecules, 30(11), 3242 (1997)
  52. Sakamoto N, Hashimoto T, Han CD, Kim D, Vaidya NY, Macromolecules, 30(6), 1621 (1997)
  53. Matsen MW, Phys. Rev. Lett., 80, 4470 (1998)
  54. Hamley IW, Fairclough JPA, Ryan AJ, Macromolecules, 31(17), 5702 (1998)
  55. Floudas G, Ulrich R, Wiesner U, J. Chem. Phys., 110(1), 652 (1999)
  56. Hamley IW, Fairclough JPA, Ryan AJ, Mai SM, Booth C, Phys. Chem. Chem. Phys., 1, 2097 (1999)
  57. Ryu CY, Lodge TP, Macromolecules, 32(21), 7190 (1999)
  58. Kimishima K, Koga T, Hashimoto T, Macromolecules, 33(3), 968 (2000)
  59. Krishnamoorti R, Silva AS, Modi MA, Hammouda B, Macromolecules, 33(10), 3803 (2000)
  60. Matsen MW, J. Chem. Phys., 114(18), 8165 (2001)
  61. Lee HH, Jeong WY, Kim JK, Ihn KJ, Kornfield JA, Wang ZG, Qi SY, Macromolecules, 35(3), 785 (2002)
  62. Wang CY, Lodge TP, Macromolecules, 35(18), 6997 (2002)
  63. Ahn JH, Zin WC, Macromol. Res., 11(3), 152 (2003)
  64. Park S, Kwon K, Cho D, Lee B, Ree M, Chang T, Macromolecules, 36(12), 4662 (2003)
  65. Zhu L, Huang P, Chen WY, Weng X, Cheng SZD, Ge Q, Quirk RP, Senador T, Shaw MT, Thomas EL, Lotz B, Hsiao BS, Yeh FJ, Liu LZ, Macromolecules, 36(9), 3180 (2003)
  66. Honda T, Kawakatsu T, Macromolecules, 39(6), 2340 (2006)
  67. Park HW, Im K, Chung B, Ree M, Chang T, Sawa K, Jinnai H, Macromolecules, 40(7), 2603 (2007)
  68. Bates FS, Koppi KA, Tirrell M, Almdal K, Mortensen K, Macromolecules, 27(20), 5934 (1994)
  69. Szwarc M, Nature, 178, 1168 (1956)
  70. Hsieh HL, Quirk RP, Anionic Polymerization: Principles and Practical Applications, Marcel-Dekker, New York, (1996)
  71. Hasneen A, Kim SJ, Paik HJ, Macromol. Res., 15(6), 541 (2007)
  72. Go DH, Jeon HJ, Kim TH, Kim G, Choi JH, Lee JY, Kim J, Yoo HO, Bae YH, Macromol. Res., 16(7), 659 (2008)
  73. Kim KM, Choi SY, Jeon HJ, Lee JY, Choo DJ, Kim J, Kang YS, Yoo HO, Macromol. Res., 16(2), 169 (2008)
  74. Park SD, Xu W, Chung C, Kwon Y, Macromol. Res., 16(2), 155 (2008)
  75. You JH, Choi SW, Kim JH, Kwak YT, Macromol. Res., 16(7), 609 (2008)
  76. Yau WW, Kirkland JJ, Bly DD, Modern Size-Exclusion Liquid Chromatography, Practice of Gel Permeation and Gel Filtration Chromatograph, John Wiley & Sons, New York (1979)
  77. Mori S, Barth HG, Size Exclusion Chromatography, Springer-Verlag, New York (1999)
  78. Cho H, Park S, Ree M, Chang T, Jung JC, Zin WC, Macromol. Res., 14(3), 383 (2006)
  79. Lee HC, Chang TY, Polymer, 37(25), 5747 (1996)
  80. Lee HC, Lee W, Chang T, Korea Polym. J., 4(2), 160 (1996)
  81. Chang T, Lee HC, Lee W, Park S, Ko C, Macromol. Chem. Phys., 200, 2188 (1999)
  82. Chang T, Adv. Polym. Sci., 163, 1 (2003)
  83. Chang T, J. Polym. Sci. B: Polym. Phys., 43(13), 1591 (2005)
  84. Ryu J, Chang T, Anal. Chem., 77, 6347 (2005)
  85. Lee W, Lee H, Cha J, Chang T, Hanley KJ, Lodge TP, Macromolecules, 33(14), 5111 (2000)
  86. Flory PJ, J. Am. Chem. Soc., 62, 1561 (1940)
  87. Jinnai H, Nishikawa Y, Ikehara T, Nishi T, NMR - 3D Analysis - Photopolymerization, 170, 115 (2004)
  88. Dohi H, Kimura H, Kotani M, Kaneko T, Kitaoka T, Nishi T, Jinnai H, Polym. J., 39, 749 (2007)
  89. Mareau VH, Akasaka S, Osaka T, Hasegawa H, Macromolecules, 40(25), 9032 (2007)
  90. Im K, Park HW, Kim Y, Chang T, Macromol. Res., 16(6), 544 (2008)
  91. Lee HC, Chang TH, Macromolecules, 29(22), 7294 (1996)
  92. Lee W, Cho D, Chun BO, Chang T, Ree M, J. Chromatogr. A, 910, 51 (2001)
  93. Park S, Cho D, Ryu J, Kwon K, Lee W, Chang T, Macromolecules, 35(15), 5974 (2002)
  94. Glockner G, Gradient HPLC of Copolymers and Chromatographic Cross-Fractionation, Springer -Verlag, Berlin (1992)
  95. Pasch H, Trathnigg B, HPLC of Polymers, Springer-Verlag, Berlin (1997)
  96. Berek D, Prog. Polym. Sci., 25, 873 (2000)
  97. Im K, Park HW, Lee S, Chang T, J. Chromatogr. A, 1216, 4606 (2009)
  98. Ahn JH, Zin WC, Macromolecules, 33(2), 641 (2000)
  99. Rosedale JH, Bates FS, Macromolecules, 23, 2329 (1990)
  100. Almdal K, Koppi KA, Bates FS, Mortensen K, Macromolecules, 25, 1743 (1992)
  101. Balsara NP, Perahia D, Safinya CR, Tirrell M, Lodge TP, Macromolecules, 25, 3896 (1992)
  102. Kim JK, Lee HH, Lee KB, Polym. Mater. Sci. Eng., 79, 330 (1998)
  103. Lee SH, Char K, Polym. Mater. Sci. Eng., 79, 314 (1998)
  104. Lodge TP, Pudil B, Hanley KJ, Macromolecules, 35(12), 4707 (2002)
  105. Kiessig H, Ann. Phys., 10, 769 (1931)
  106. Parratt LG, Phys. Rev., 95, 359 (1954)
  107. Russell TP, Mater. Sci. Rep., 5, 171 (1990)
  108. Yoon J, Kim KW, Kim J, Heo K, Jin KS, Jin S, Shin TJ, Lee B, Rho Y, Ahn B, Ree M, Macromol. Res., 16(7), 575 (2008)
  109. Rancon Y, Charvolin J, J. Phys. Chem., 92, 2646 (1988)
  110. Clerc M, Levelut AM, Sadoc JF, J. Phys. II, 1, 1263 (1991)