Zoelen, Wendy van

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PS-b-P4VP(PDP) comb-shaped supramolecules:nanorods and thin films for nanotemplating

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PS-b-P4VP(PDP) comb-shaped supramolecules
Zoelen, Wendy van
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Zoelen, W. V. (2009). PS-b-P4VP(PDP) comb-shaped supramolecules: nanorods and thin films for
nanotemplating s.n.
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PS-b-P4VP(PDP) Comb-Shaped Supramolecules: 
Nanorods and Thin Films for Nanotemplating 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Wendy van Zoelen 
  
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
PS-b-P4VP(PDP) Comb-Shaped Supramolecules: 
Nanorods and Thin Films for Nanotemplating 
 
Wendy van Zoelen 
 
Ph.D. thesis 
University of Groningen 
The Netherlands 
 
March 2009 
 
Zernike Institute PhD thesis series 2009-03 
ISSN 1570-1530 
ISBN 978-90-367-3735-7 
ISBN electronic 978-90-367-3736-4 
  
  
 
 
RIJKSUNIVERSITEIT GRONINGEN 
 
 
 
 
 
PS-b-P4VP(PDP) Comb-Shaped Supramolecules: 
Nanorods and Thin Films for Nanotemplating 
 
 
 
 
 
Proefschrift 
 
 
ter verkrijging van het doctoraat in de 
Wiskunde en Natuurwetenschappen 
aan de Rijksuniversiteit Groningen 
op gezag van de 
Rector Magnificus, Dr. F. Zwarts, 
in het openbaar te verdedigen op 
vrijdag 13 maart 2009 
om 16.15 uur 
 
 
door 
 
 
Wendy van Zoelen 
 
 
geboren op 1 september 1981 
te Groningen 
  
  
Promotor: Prof. Dr. G. ten Brinke 
 
 
Beoordelingscommissie: Prof. Dr. O. Ikkala 
  Prof. Dr. R. Magerle  
  Prof. Dr. U. Steiner 
 
  
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Aut numquam tentes,  
aut perfice. 
 
Ovidius 
 

 Contents 
Chapter 1: Introduction .................................................................. 11 
1.1 Polymers........................................................................................ 12 
1.2 Block copolymers........................................................................... 13 
1.2.1 Block copolymer thin films ............................................................15 
1.2.2 Templating with thin films ............................................................20 
1.3 Thin films of complex systems ....................................................... 24 
1.3.1 Functional block copolymers.........................................................25 
1.3.2 ABC triblock copolymers ...............................................................27 
1.3.3 Supramolecular systems...............................................................28 
1.4 Thesis overview.............................................................................. 37 
1.5 References ..................................................................................... 39 
Chapter 2: Nanorod Engineering by Reinforcing 
Hexagonally Self-Assembled PS-b-P4VP(DDP) with PPE .................... 47 
2.1 Introduction................................................................................... 48 
2.2 Experimental section ..................................................................... 49 
2.2.1 Materials and sample preparation................................................49 
2.2.2 Instrumental methods...................................................................51 
2.3 Results and discussion .................................................................. 52 
2.3.1 Alumina membranes.....................................................................52 
2.3.2 Nanorod properties .......................................................................53 
2.3.3 Addition of PPE .............................................................................56 
2.4 Conclusion..................................................................................... 58 
2.5 References ..................................................................................... 58 
8   Contents 
  
Chapter 3: Incorporation of PPE in Lamellar Self-
Assembled PS-b-P4VP(PDP) Supramolecules and PS-b-
P4VP Diblock Copolymers ............................................................... 61 
3.1 Introduction................................................................................... 62 
3.2 Experimental section ..................................................................... 64 
3.2.1 Materials and sample preparation................................................64 
3.2.2 Instrumental methods...................................................................65 
3.3 Results and discussion .................................................................. 67 
3.3.1 Thermal analysis ..........................................................................67 
3.3.2 Small Angle X-ray Scattering ........................................................71 
3.4 Conclusion..................................................................................... 76 
3.5 References ..................................................................................... 77 
Chapter 4: Phase Behavior of Solvent Vapor Annealed 
Thin Films of PS-b-P4VP(PDP) Supramolecules ................................ 79 
4.1 Introduction................................................................................... 80 
4.2 Experimental section ..................................................................... 82 
4.2.1 Materials and sample preparation................................................82 
4.2.2 Instrumental methods...................................................................83 
4.3 Results and discussion .................................................................. 85 
4.3.1 Swelling of cylindrical P228(PDP)1.5 ..............................................86 
4.3.2 Swelling of lamellar P5154(PDP)1.0 ...............................................93 
4.4 Conclusion................................................................................... 102 
4.5 Appendix ..................................................................................... 103 
4.6 References ................................................................................... 104 
Chapter 5: Hierarchical Terrace Formation in PS-b-
P4VP(PDP) Supramolecular Thin Films .......................................... 107 
5.1 Introduction................................................................................. 108 
5.2 Experimental section ................................................................... 110 
5.2.1 Materials and sample preparation..............................................110 
5.2.2 Instrumental methods.................................................................111 
5.3 Results and discussion ................................................................ 111 
5.4 Conclusion................................................................................... 121 
Contents  9 
  
5.5 References ................................................................................... 122 
Chapter 6: Nanostructured PS-b-P4VP(PDP) Thin Films 
as Templates for Polypyrrole Synthesis......................................... 125 
6.1 Introduction................................................................................. 126 
6.2 Experimental section ................................................................... 127 
6.2.1 Materials and sample preparation..............................................127 
6.2.2 Instrumental methods.................................................................129 
6.3 Results and discussion ................................................................ 131 
6.4 Conclusion................................................................................... 141 
6.5 References ................................................................................... 142 
Chapter 7: Self-Assembled PS-b-P4VP(PDP) 
Supramolecular Thin Films as a Nano-Template for 
Ferroelectric PbTiO3 ..................................................................... 145 
7.1 Introduction................................................................................. 146 
7.2 Experimental section ................................................................... 148 
7.2.1 Materials and sample preparation..............................................148 
7.2.2 Instrumental methods.................................................................150 
7.3 Results and discussion ................................................................ 151 
7.4 Conclusion................................................................................... 155 
7.5 References ................................................................................... 155 
Summary...................................................................................... 157 
Samenvatting ............................................................................... 163 
List of Publications....................................................................... 169 
Dankwoord ................................................................................... 171 



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