Colloid and Polymer Science

, Volume 289, Issue 5–6, pp 711–720

The collapse transition and the segmental dynamics in concentrated micellar solutions of P(S-b-NIPAM) diblock copolymers

  • Joseph Adelsberger
  • Andreas Meier-Koll
  • Achille M. Bivigou-Koumba
  • Peter Busch
  • Olaf Holderer
  • Thomas Hellweg
  • André Laschewsky
  • Peter Müller-Buschbaum
  • Christine M. Papadakis
Original Contribution


We investigate concentrated solutions of poly(styrene-b-N-isopropyl acrylamide) (P(S-b-NIPAM)) diblock copolymers in deuterated water (D2O). Both structural changes and the changes of the segmental dynamics occurring upon heating through the lower critical solution temperature (LCST) of PNIPAM are studied using small-angle neutron scattering and neutron spin-echo spectroscopy. The collapse of the micellar shell and the cluster formation of collapsed micelles at the LCST as well as an increase of the segmental diffusion coefficient after crossing the LCST are detected. Comparing to our recent results on a triblock copolymer P(S-b-NIPAM-b-S) [25], we observe that the collapse transition of P(S-b-NIPAM) is more complex and that the PNIPAM segmental dynamics are faster than in P(S-b-NIPAM-b-S).


Block copolymers Responsive polymers Small-angle neutron scattering Neutron spin-echo spectroscopy 


  1. 1.
    Heskins M, Guillet JE (1968) J Macromol Sci A2(8):1441Google Scholar
  2. 2.
    Shibayama M, Tanaka T (1992) J Chem Phys 97:6829CrossRefGoogle Scholar
  3. 3.
    Schild HG (1992) Prog Polym Sci 17:163CrossRefGoogle Scholar
  4. 4.
    Arndt KF, Kuckling D, Richter A (2000) Polym Adv Techn 11:496CrossRefGoogle Scholar
  5. 5.
    Nykänen A, Nuopponen M, Laukkanen A, Hirvonen S-P, Rytelä M, Turunen O, Tenhu H, Mezzenga R, Ikkala O, Ruokolainen J (2007) Macromolecules 40:5827CrossRefGoogle Scholar
  6. 6.
    Hoffman AS (1987) J Controlled Release 6:297CrossRefGoogle Scholar
  7. 7.
    Coughlan DC, Quilty FP, Corrigan OI (2004) J Controlled Release 98:97CrossRefGoogle Scholar
  8. 8.
    Schmaljohann D (2006) Adv Drug Delivery Rev 58:1655CrossRefGoogle Scholar
  9. 9.
    Wang W, Metwalli E, Perlich J, Troll K, Papadakis CM, Cubitt R, Müller-Buschbaum P (2009) Macromol Rapid Commun 30:114CrossRefGoogle Scholar
  10. 10.
    Wang W, Metwalli E, Perlich J, Papadakis CM, Cubitt R, Müller-Buschbaum P (2009) Macromolecules 42:9041CrossRefGoogle Scholar
  11. 11.
    Okada Y, Tanaka F (2005) Macromolecules 38:4465CrossRefGoogle Scholar
  12. 12.
    Kujawa P, Watanabe H, Tanaka F, Winnik FM (2005) Eur Phys J E 17:129CrossRefGoogle Scholar
  13. 13.
    Koga T, Tanaka F, Motokawa R, Koizumi S, Winnik FM (2008) Macromolecules 41:9413CrossRefGoogle Scholar
  14. 14.
    Wang W, Troll K, Kaune G, Metwalli E, Ruderer M, Skrabania K, Laschewsky A, Roth SV, Müller-Buschbaum P, Papdakis CM (2008) Macromolecules 41:3209CrossRefGoogle Scholar
  15. 15.
    Nuopponen M, Ojala J, Tenhu H (2004) Polymer 45:3643CrossRefGoogle Scholar
  16. 16.
    Mertoglu M, Garnier S, Laschewsky A, Skrabania K, Storsberg J (2005) Polymer 46:7726CrossRefGoogle Scholar
  17. 17.
    Zhang W, Zhou X, Li H, Fang Y, Zhang G (2005) Macromolecules 38:909CrossRefGoogle Scholar
  18. 18.
    Tang T, Castelletto V, Parras P, Hamley IW, King SM, Roy D, Perrier S, Hoogenboom R, Schubert US (2006) Macromol Chem Phys 207:1718CrossRefGoogle Scholar
  19. 19.
    Zhou X, Ye X, Zhang G (2007) J Phys Chem B 111:5111CrossRefGoogle Scholar
  20. 20.
    Kirkland SE, Hensarling RM, McConaughty SD, Guo Y, Jarret WL, McCormick CL (2008) Biomacromolecules 9:481CrossRefGoogle Scholar
  21. 21.
    Troll K, Kulkarni A, Wang W, Darko C, Bivigou Koumba AM, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2008) Colloid Polym Sci 286:1079 and Erratum (2011)CrossRefGoogle Scholar
  22. 22.
    Bivigou Koumba AM, Kristen J, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2009) Macromol Chem Phys 210:565CrossRefGoogle Scholar
  23. 23.
    Jain A, Kulkarni A, Bivigou Koumba AM, Wang W, Busch P, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Macromol Symp 291–292:221CrossRefGoogle Scholar
  24. 24.
    Bivigou Koumba AM, Görnitz E, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Colloid Polym Sci 288:499CrossRefGoogle Scholar
  25. 25.
    Adelsberger J, Kulkarni A, Jain A, Wang W, Bivigou Koumba AM, Busch P, Pipich V, Holderer O, Hellweg T, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Macromolecules 43:2490CrossRefGoogle Scholar
  26. 26.
    Engels R, Clemens U, Kemmerling G, Nöldgen H, Schelten J (2009) J Nucl Instrum Methods Phys Res Sect A 604:147CrossRefGoogle Scholar
  27. 27.
    Chiklis CK, Grasshoff JM (1979) J Polym Sci: Part A-2 8:1617CrossRefGoogle Scholar
  28. 28.
    Daoud M, Cotton JP (1982) J Physique 43:531Google Scholar
  29. 29.
    Förster S, Wenz E, Lindner P (1996) Phys Rev Letters 77:95CrossRefGoogle Scholar
  30. 30.
    Förster S, Burger C (1998) Macromolecules 31:879CrossRefGoogle Scholar
  31. 31.
    Schulz GV (1939) Z Phys Chem 43:25Google Scholar
  32. 32.
    Hasmy A, Foret M, Pelous J, Jullien R (1993) Phys Rev B 48:9345CrossRefGoogle Scholar
  33. 33.
    Wertheim MS (1963) Phys Rev Letters 10:321CrossRefGoogle Scholar
  34. 34.
    Pedersen JS, Posselt D, Mortensen K (1990) J Appl Cryst 23:321CrossRefGoogle Scholar
  35. 35.
    Monkenbusch M, Schätzler R, Richter D (1997) Nucl Instrum Methods Phys Res A 399:301CrossRefGoogle Scholar
  36. 36.
    Holderer O, Monkenbusch M, Schätzler R, Kleines H, Westerhausen W, Richter D (2008) Meas Sci Technol 19:034022CrossRefGoogle Scholar
  37. 37.
    Percot A, Zhu XX, Lafleur M (2000) J Polym Sci B: Polym Phys 38:907CrossRefGoogle Scholar
  38. 38.
    Carnahan NF, Starling KE (1969) J Chem Phys 51:635CrossRefGoogle Scholar
  39. 39.
    Mezei F (1972) Z Phys 255:146CrossRefGoogle Scholar
  40. 40.
    Kanaya T, Monkenbusch M, Watanabe H, Nagao M, Richter D (2005) J Chem Phys 122:144905CrossRefGoogle Scholar
  41. 41.
    Matsuoka H, Yamamoto Y, Nakano M, Endo H, Yamaoka H, Zorn R, Monkenbusch M, Richter D, Seto H, Kawabata Y, Nagao M (2000) Langmuir 16:9177CrossRefGoogle Scholar
  42. 42.
    Castelletto V, Hamley IW, Yang Z, Haeussler W (2003) J Chem Phys 119:8158CrossRefGoogle Scholar
  43. 43.
    Farago B, Monkenbusch M, Richter D, Huang JS, Fetters LJ, Gast AP (1993) Phys Rev Lett 71:1015CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Joseph Adelsberger
    • 1
  • Andreas Meier-Koll
    • 1
  • Achille M. Bivigou-Koumba
    • 2
  • Peter Busch
    • 3
  • Olaf Holderer
    • 3
  • Thomas Hellweg
    • 4
  • André Laschewsky
    • 2
  • Peter Müller-Buschbaum
    • 1
  • Christine M. Papadakis
    • 1
  1. 1.Lehrstuhl für Funktionelle Materialien/Fachgebiet Physik der weichen MaterieTechnische Universität MünchenGarchingGermany
  2. 2.Institut für ChemieUniversität PotsdamPotsdam-GolmGermany
  3. 3.Jülich Centre for Neutron Science at FRM IIForschungszentrum Jülich GmbHGarchingGermany
  4. 4.Physikalische und Biophysikalische ChemieUniversität BielefeldBielefeldGermany

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