Advanced ESR Methods in Polymer Research

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ISBN: 9780471731894 | 0471731897
Cover: Hardcover
Copyright: 9/18/2006

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A definitive work on ESR and polymer science by today's leading authorities The past twenty years have seen extraordinary advances in electron spin resonance (ESR) techniques, particularly as they apply to polymeric materials. With contributions from over a dozen of the world's top polymer scientists, Advanced ESR Methods in Polymer Research is the first book to bring together all the current trends in this exciting field into one comprehensive reference.Part I establishes the fundamentals of ESR, from experimental techniques to data analysis, and serves as a valuable overview for the beginning ESR student. Part II introduces the broad range of ESR applications to polymeric systems, including living radical polymerization, block copoly-mers, polymer solutions, ion-containing polymers, polymer lattices, membranes in fuel cells, degradation, polymer coatings, dendrimers, and conductive polymers. By exposing readers to the great potential of ESR, the authors hope to encourage more extensive application of these methods.

Preface

About the Editor

Contributors

xiii

PART I ESR FUNDAMENTALS

(98)

Continuous-Wave and Pulsed ESR Methods

(22)

Gunnar Jeschke

Shulamith Schlick

Introduction

(1)

Fundamentals of Electron Spin Resonance Spectroscopy

(12)

Basic Principles

(6)

Anisotropic Hyperfine Interaction and g-Tensor

(2)

Isotropic Hyperfine Analysis

(1)

Environmental Effects on g- and Hyperfine Interaction

(1)

Accessibility to Paramagnetic Quenchers

(2)

Line Shape Analysis for Tumbling Nitroxide Radicals

(1)

Multifrequency and High-Field ESR

(2)

Pulsed ESR Methods

(7)

Acknowledgments

(1)

References

(3)

Double Resonance ESR Methods

(28)

Gunnar Jeschke

Introduction

(1)

Spin--Spin Couplings

(4)

Dipole--Dipole Coupling

(3)

Exchange Coupling

(1)

Fermi Contact Interaction

(1)

Spin Density in p and d Orbitals

(1)

Electron-Electron Double Resonance

(8)

General Considerations

(2)

Experimental Techniques

(2)

Analogy to Form Factor and Structure Factor in Scattering

(3)

Direct Computation of Distance Distributions

(1)

Electron--Nuclear Double Resonance

(5)

General Considerations

(1)

Experimental Techniques

(2)

High-Field ENDOR

(2)

Electron Spin Echo Envelope Modulation

(5)

Principles

(1)

Experimental Techniques

(3)

Data Analysis

(2)

Conclusions

(4)

Acknowledgments

(1)

References

(3)

Calculating Slow-Motion ESR Spectra of Spin-Labeled Polymers

(32)

Keith A. Earle

David E. Budil

Introduction

(1)

Physical Parameters of Nitroxide Labels

(18)

Magnetic Tensors of the Nitroxide

(5)

Diffusion Models

(3)

Orientational Ordering in Spin-Labeled Polymers

(6)

The Microscopic Order-Macroscopic Disorder Model

(1)

Slowly Relaxing Local Structure Model

(3)

Other Stochastic Liouville Calculation Parameters

(6)

Basis Set for the Stochastic Liouville Calculation

(1)

Basis Set Symmetrization

(1)

Basis Set Truncation Parameters

(2)

Guidelines for Selecting Basis Set Truncation Parameters

(2)

Basis Set Pruning

(1)

Nonlinear Least-Squares Analysis

(6)

Acknowledgments

(1)

Appendix: Program Availability

(1)

References

(3)

ESR Imaging

(14)

Shulamith Schlick

Introduction

(2)

ESR Imaging: Hardware, Data Acquisition, and Software

(6)

ESR Spectra in the Presence of Magnetic Field Gradients

(1)

Hardware for ESR Imaging

(2)

Intensity Profiling from ID ESRI

(2)

Line Shape Profiling from 2D Spectral-Spatial ESRI

(1)

ESRI Methods Applied to Polymeric Systems

(6)

Motivation of Our Studies

(1)

Acknowledgments

(1)

References

(2)

PART II ESR APPLICATIONS

(240)

ESR Study of Radicals in Conventional Radical Polymerization Using Radical Precursors Prepared by Atom Transfer Radical Polymerization

101

(32)

Atsushi Kajiwara

Krzysztof Matyjaszewski

Introduction

102

(3)

Chain Length Dependence

105

(4)

ESR Spectra of Propagating Radicals Formed in the Polymerization of tert-Butyl Methacrylate

105

(1)

ESR Spectra of Model Radicals with Controlled Chain Lengths

106

(3)

Chain-Transfer Reactions

109

(10)

ESR Spectra Observed in Polymerization of tert-Butyl Acrylate

109

(2)

ESR Study of Model tert-Butyl Acrylate Radicals with Controlled Chain Lengths

111

(5)

Polymeric Radicals and Chain-Length Dependent Changes in ESR Spectra

116

(3)

Penultimate Unit Effect

119

(10)

Monomeric Model Radicals

120

(2)

Dimeric Model Radicals

122

(2)

Dimeric Radicals and the Penultimate Unit Effect

124

(4)

Activation Rate Constants for Monomeric and Dimeric Alkyl Bromides and ESR Spectra

128

(1)

Conclusions

129

(4)

Acknowledgments

129

(1)

References

129

(4)

Local Dynamics of Polymers in Solution by Spin-Label ESR

133

(32)

Jan Pilar

Introduction

134

(1)

Local Dynamics in Polymers by NMR and Fluorescence Techniques

134

(2)

Segmental Mobility of Polymers

134

(1)

NMR and Fluorescence Studies

135

(1)

Effect of Nitroxide Rotational Dynamics on ESR Line Shapes

136

(4)

Basic Principles

136

(2)

Fast-Motional Spectra

138

(1)

Slow-Motional Spectra and Ordering

139

(1)

ESR Studies of Segmental Dynamics of Polymers in Solution

140

(22)

Dynamics of Nitroxide Spin Labels Attached to Polymer Chain in Dilute Solution

140

(2)

Segmental Mobility of Poly(methyl methacrylate)

142

(1)

Segmental Mobility of Poly(methacrylic acid) and Poly(acrylic acid)

142

(5)

Segmental Mobility of Polystyrene

147

(8)

Segmental Mobility of Poly(2-hydroxyethyl methacrylate)

155

(6)

Comparison with Other Techniques

161

(1)

Conclusions

162

(3)

Acknowledgments

162

(1)

References

162

(3)

Site-Specific Information on Macromolecular Materials by Combining CW and Pulsed ESR on Spin Probes

165

(32)

Gunnar Jeschke

Introduction

166

(1)

Strategies for Spin Labeling and Probing

167

(4)

When to Label and When to Probe

167

(1)

Spin Labeling

168

(1)

Spin Probing

168

(1)

Hydrophobic Probes

169

(1)

Hydrogen-Bonding Probes

169

(1)

Ionic Probes

169

(1)

Amphiphilic Probes

170

(1)

Macromolecules in Solution

171

(11)

Choice of Solvent and Temperature

171

(1)

Frozen Solutions

172

(1)

Polyelectrolyte--Counterion Interactions

173

(5)

Coconformation and Motional Modes in [2] Catenanes

178

(4)

Materials with Mesoscopic Structure: Interfaces and Nanostructure

182

(10)

Polymer Latices

182

(5)

Ionomers

187

(5)

Conclusions

192

(5)

Acknowledgements

193

(1)

Reference

193

(4)

ESR Methods for Assessing the Stability of Polymer Membranes Used in Fuel Cells

197

(32)

Emil Roduner

Shulamith Schlick

Introduction and Motivation

198

(3)

Fuel Cell Processes and Their Effects on Membrane Stability

201

(3)

Direct ESR and Spin Trapping as Tools for the Detection of Radical Intermediates

204

(2)

Study of Membrane Stability by ESR

206

(19)

Reaction of Oxygen Radicals with Model Compounds in Solution

206

(4)

Radical Species in Nation Membranes Treated in Fenton Media

210

(1)

Oxygen-Centered Radicals

211

(3)

Fluorinated Alkyl Radicals

214

(1)

Membrane-Derived Fluorinated Radicals in UV-Irradiated Nafion and Dow Ionomers: Effect of Counterions and H2O2

215

(2)

Fluorinated Radical Fragments

217

(5)

In Situ ESR Experiments

222

(3)

Conclusions and Prospects

225

(4)

Acknowledgments

226

(1)

References

226

(3)

Spatially Resolved Degradation in Heterophasic Polymers From ID and 2D Spectral--Spatial ESR Imaging Experiments

229

(26)

Shulamith Schlick

Krzysztof Kruezala

ESR Imaging (ESRI) as a Nondestructive Method for Spatially Resolved Degradation Studies

230

(3)

Experimental Details

233

(2)

ESR Spectra of Nitroxides Derived from Hindered Amine Stabilizers in Aged Heterophasic Polymers

235

(3)

1D and 2D Spectral-Spatial ESRI in Aged Heterophasic Polymers

238

(13)

Poly(Acrylonitrile-Butadiene-Styrene) Systems

238

(1)

Thermal Aging of ABS

238

(3)

Photodegradation of ABS

241

(2)

Heterophasic Propylene-Ethylene Copolymers

243

(1)

Thermal Aging of HPEC

243

(1)

Photodegradation of HPEC

244

(4)

Comparison of ESRI and FTIR Methods

248

(2)

Sensitivity of Crystalline Polymers to Microtoming

250

(1)

Conclusions

251

(4)

Acknowledgments

252

(1)

References

252

(3)

ESR Studies of Photooxidation and Stabilization of Polymer Coatings

255

(24)

David R. Bauer

John L. Gerlock

Introduction

256

(2)

Free-Radical Oxidation and Stabilization

258

(2)

Experimental

260

(4)

Nitroxide Concentration by ESR

260

(2)

UV Exposures

262

(1)

Sample Preparation for Nitroxide Decay Experiments

263

(1)

Sample Preparation for Nitroxide Measurement in HALS Stabilized Coatings

264

(1)

Free-Radical Photoinitiation Rates by Nitroxide Decay

264

(8)

Derivation of Nitroxide Radical Decay Kinetics and Free-Radical Photoinitiation Rates

264

(1)

Photoinitiation Rate Measurements on Model Systems and Nonweathered Coatings

265

(4)

Photoinitiation Rate Measurements on Weathered Coatings

269

(3)

Nitroxide Kinetics and HALS Stabilization of Coatings

272

(5)

Conclusions

277

(2)

Acknowledgements

277

(1)

References

277

(2)

Characterization of Dendrimer Structures by ESR Techniques

279

(28)

M. Francesca Ottaviani

Nicholas J. Turro

Introduction

279

(3)

ESR Studies on Dendrimers

282

(20)

Spin Probes

283

(6)

Spin Labeling with Nitroxides

289

(7)

Paramagnetic Metal Ions Added to Dendrimer Solutions

296

(3)

Metallo-Dendrimers

299

(3)

Conclusions

302

(5)

Acknowledgments

303

(1)

References

303

(4)

High-Field ESR Spectroscopy of Conductive Polymers

307

(32)

Victor I. Krinichnyi

Introduction

307

(3)

Magnetic Parameters of Charge Carriers in Conductive Polymers

310

(7)

Relaxation and Dynamics of Charge Carriers in Slightly Doped Conductive Polymers

317

(9)

Charge Transfer in Highly Doped Conductive Polymers

326

(2)

High-Field Saturation Transfer ESR Method in the Study of Conductive Polymers

328

(2)

High-Field Spin Probe-Method in the Study of Conductive Polymers

330

(3)

Concluding Remarks

333

(6)

Acknowledgments

334

(1)

References

334

(5)

Index

339

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Advanced ESR Methods in Polymer Research

Summary

Author Biography

Table of Contents

Supplemental Materials