Neutron Spin Echo in Polymer Systems: -/-

32 Pages·2005·0.378 MB·English

by  D. Richter, M. Monkenbusch, A. Arbe, J. Colmenero (auth.)

174
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Neutron Spin Echo in Polymer Systems
By Dieter Richter,Michael Monkenbusch,
Arantxa Arbe,Juan Colmenero
3
Authors
Prof.Dr.Dieter Richter Prof.Dr.Juan Colmenero
[email protected] Unidad Física de Materiales
(CSIC-UPV/EHU)
Dr.Michael Monkenbusch
Apartado 1072
[email protected]
20080 San Sebastián
Institut für Festkörperforschung Spain
Forschungszentrum Jülich and
52425 Jülich
Departamento de Física de Materiales
Germany
(UPV/EHU) and
Dr.Arantxa Arbe Donostia International Physics Center
Apartado 1072
Unidad Física de Materiales
20080 San Sebastián
(CSIC-UPV/EHU)
Spain
Apartado 1072
[email protected]
20080 San Sebastián
Spain
[email protected]
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ISBN 3-540-22862-4Springer Berlin Heidelberg New York
DOI 10.1007/b99835
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Department ofIndustrial Chemistry Physicochimie Curie
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Department ofPolymer Technology Prof.Hans-Henning Kausch
The Royal Institute ofTechnology c/o EPFL,Science de Base (SB-ISIC)
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Welsh School ofPharmacy Prof.S.Kobayashi
CardiffUniversity Department ofMaterials Chemistry
Redwood Building Graduate School ofEngineering
King Edward VII Avenue Kyoto University
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United Kingdom [email protected]
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Prof.Karel Dušek
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Prof.Brigitte Voit
Prof.Ian Manners
Institut für Polymerforschung Dresden
Department ofChemistry Hohe Straße 6
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Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Neutron Scattering and Neutron Spin Echo . . . . . . . . . . . . . 9
2.1 Neutron Scattering Principles . . . . . . . . . . . . . . . . . . . . . 9
2.1.1 Coherent and Incoherent Scattering . . . . . . . . . . . . . . . . . 10
2.1.2 Coherent Scattering and Coarse Graining . . . . . . . . . . . . . . 11
2.1.3 Contrast Variation . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 The Neutron Spin-Echo Method . . . . . . . . . . . . . . . . . . . 12
2.2.1 Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Technical Principles . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.3 Zero Field Spin-Echo Technique . . . . . . . . . . . . . . . . . . . 18
2.2.4 Accessible High Resolution NSE Spectrometers . . . . . . . . . . . 21
2.2.5 Related Methods:Pulsed Field Gradient NMR
and Dynamic Light Scattering . . . . . . . . . . . . . . . . . . . . 21
3 Large Scale Dynamics ofHomopolymers . . . . . . . . . . . . . . 24
3.1 Entropy Driven Dynamics – the Rouse Model . . . . . . . . . . . . 25
3.1.1 Gaussian Chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.1.2 The Rouse Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.1.3 Neutron Spin Echo Results . . . . . . . . . . . . . . . . . . . . . . 31
3.1.4 Rouse Model:Rheological Measurements and NSE . . . . . . . . . 35
3.1.5 Rouse Model:Computer Simulation and NSE . . . . . . . . . . . . 37
3.2 Reptation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2.1 Self-Correlation Function . . . . . . . . . . . . . . . . . . . . . . . 45
3.2.2 Single-Chain Dynamic Structure Factor . . . . . . . . . . . . . . . 45
3.2.3 Neutron Spin Echo Results on Chain Confinement . . . . . . . . . 48
3.2.4 Reptation,NSE and Computer Simulation . . . . . . . . . . . . . . 55
3.2.5 Contour Length Fluctuations . . . . . . . . . . . . . . . . . . . . . 61
4 Local Dynamics and the Glass Transition . . . . . . . . . . . . . . 67
4.1 a-Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.1.1 Structural a-Relaxation:Dynamic Structure Factor . . . . . . . . 72
4.1.2 Self-Atomic Motions ofProtons . . . . . . . . . . . . . . . . . . . 82
4.2 b-Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.2.1 Model for b-Relaxation . . . . . . . . . . . . . . . . . . . . . . . . 99
X Contents
4.3 ab-Merging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.4 Mode Coupling Theory . . . . . . . . . . . . . . . . . . . . . . . . 112
5 Intermediate Length Scales Dynamics . . . . . . . . . . . . . . . . 117
5.1 Chain-Rigidity and Rotational Transitions
as Rouse Limiting Processes . . . . . . . . . . . . . . . . . . . . . 117
5.1.1 Mode Description ofChain Statistics . . . . . . . . . . . . . . . . 118
5.1.2 Effect ofBending Forces . . . . . . . . . . . . . . . . . . . . . . . . 120
5.1.3 Internal Viscosity Effects . . . . . . . . . . . . . . . . . . . . . . . 121
5.1.4 Hydrodynamic Interactions and Internal Viscosity Effects . . . . 123
5.1.5 NSE Results on Chain Specific Effects Limiting
the Rouse Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.1.6 Internal Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
5.1.7 Polymer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
5.1.8 Intrachain Viscosity Analysis ofthe PIB-Data . . . . . . . . . . . . 133
5.2 Collective Motions . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
5.2.1 Application ofMode Coupling Theory . . . . . . . . . . . . . . . . 141
5.3 Self-Motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.4 Scenario for the Intermediate Length Scale Dynamics . . . . . . . 147
5.4.1 Direct Comparison ofthe Correlators . . . . . . . . . . . . . . . . 147
5.4.2 Stressing the Internal Viscosity Approach . . . . . . . . . . . . . . 151
6 The Dynamics ofMore Complex Polymer Systems . . . . . . . . . 153
6.1 Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.1.1 Neutron Scattering and Polymer Blend Dynamics . . . . . . . . . 155
6.1.2 Neutron Spin Echo Results in Polymer Blends . . . . . . . . . . . 156
6.2 Diblock copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.2.1 Dynamic Random Phase Approximation (RPA) . . . . . . . . . . . 163
6.2.2 Static Scattering Function . . . . . . . . . . . . . . . . . . . . . . 165
6.2.3 Dynamic Structure Factor . . . . . . . . . . . . . . . . . . . . . . . 165
6.2.4 Neutron Scattering Results . . . . . . . . . . . . . . . . . . . . . . 167
6.2.5 Static Structure Factor . . . . . . . . . . . . . . . . . . . . . . . . . 167
6.2.6 Collective Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 170
6.2.7 Single Chain Dynamics . . . . . . . . . . . . . . . . . . . . . . . . 173
6.3 Gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
6.4 Micelles,Stars and Dendrimers . . . . . . . . . . . . . . . . . . . . 184
6.4.1 Micelles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.4.2 Stars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.4.3 Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.5 Rubbery Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . 188
6.6 Polymer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
6.6.1 Semidilute Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6.6.2 Theta Solution/Two Length Scales . . . . . . . . . . . . . . . . . . 197
6.6.3 Multicomponent Solutions . . . . . . . . . . . . . . . . . . . . . . 199
6.7 Biological Macromolecules . . . . . . . . . . . . . . . . . . . . . . 200
Contents XI
7 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . 207
8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Abbreviations and Symbols . . . . . . . . . . . . . . . . . . . . . . . . . 219
Author Index Volumes 101–174 . . . . . . . . . . . . . . . . . . . . . . . 223
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243