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Abstract
Wormlike micelles are elongated flexible self-assembled structures created from the aggregation of amphiphiles and their resulting dynamic networks have gained attention for a number of uses, particularly in the oil industry.
Written by experts, Wormlike Micelles describes the latest developments in the field providing an authoritative guide on the subject. The book starts with an introductory chapter giving an overview of the area and then looks at the three key topics of new wormlike micelle systems, characterization and applications. New systems covered in the first part include reverse wormlike micelles and stimuli-responsive wormlike micelles. The second part explores cutting-edge techniques that have led to advances in the understanding of their structure and dynamics, including direct imaging techniques and the combination of rheology with small-angle neutron scattering techniques. Finally, the book reviews their use in oil and gas well treatments as well as surfactant drag reducing solutions.
Aimed at postgraduate students and researchers, this text is essential reading for anyone interested in soft matter systems.
Céile A. Dreiss is a Senior Lecturer in the Institute of Pharmaceutical Science, King’s College London, UK. Her research focuses on understanding and exploiting self-assembly in soft matter, spanning colloidal, polymeric and biological systems, by establishing relationships between properties on the macro-scale (bulk behaviour or functionality) and the organization at the nanoscale. She uses neutron and X-ray scattering techniques extensively as well as rheology. Cecile graduated in Chemistry and Chemical Engineering (ENSIC, France). She received her PhD from Imperial College London (Chemical Engineering) in 2003, after which she took up a 2-year postdoc position at the University of Bristol. She then moved back to London and was appointed as a Lecturer in September 2005. Yujun Feng is a Professor at the Polymer Research Institute and State Key Laboratory of Polymer Materials Engineering, Sichuan University. After earning his PhD in applied chemistry from Southwest Petroleum University, China, in 1999, he moved to France to undertake his post-doctoral research at the Laboratoire de Physico-Chimie des Polymeres, CNRS/Universite de Pau, and at the Institut Français du Petrole (IFP), respectively. In 2004, he joined in the Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, and has been serving as a team leader since then. In September 2012, he relocated to Sichuan University where he is focusing stimuli-responsive surfactants and polymers.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | vii | ||
| Preface | v | ||
| Chapter 1 Wormlike Micelles: An Introduction | 1 | ||
| 1.1 Why Do Wormlike Micelles Form? | 1 | ||
| 1.2 Which Surfactants Form Wormlike Micelles? | 3 | ||
| 1.3 Key Structural Parameters | 3 | ||
| 1.4 Linear Rheology of Wormlike Micelles | 4 | ||
| 1.5 Conclusions and Outlook | 6 | ||
| References | 7 | ||
| Chapter 2 Wormlike Micelles: Solutions, Gels, or Both? | 9 | ||
| 2.1 A Brief History of Wormlike Micelles and Their Viscoelasticity | 9 | ||
| 2.2 Comparing Wormlike Micelles and Polymers | 12 | ||
| 2.3 Definition of a Gel | 16 | ||
| 2.4 Wormlike Micelles of Long-tailed Surfactants: Gel-like Behavior | 17 | ||
| 2.5 Why do Certain Wormlike Micelles Form a Gel? | 22 | ||
| 2.6 Can a Gel Be Formed by ‘‘Entanglements\" Alone? | 24 | ||
| 2.7 Conclusions | 26 | ||
| References | 26 | ||
| Chapter 3 Reverse Wormlike Micelles: A Special Focus on Nuclear Magnetic Resonance Investigations | 31 | ||
| 3.1 Introduction | 31 | ||
| 3.2 Wormlike Micelles and Microemulsions: Basic Background | 33 | ||
| 3.3 Microstructure and Dynamics from NMR Techniques | 36 | ||
| 3.3.1 Probing Molecular Motion with PFG-NMR | 36 | ||
| 3.3.2 Rheo-NMR | 41 | ||
| 3.4 General Properties of Lecithin Reverse Wormlike Micelles | 44 | ||
| 3.5 Lecithin Reverse Wormlike Micelles in Cyclohexane: Disconnected Worms | 45 | ||
| 3.6 Lecithin Wormlike Micelles in Isooctane: Living Networks | 51 | ||
| 3.7 Disconnected vs. Connected Reverse Wormlike Micelles: Rheology | 55 | ||
| 3.8 Conclusions | 58 | ||
| Acknowledgments | 59 | ||
| References | 59 | ||
| Chapter 4 Unusual Surfactants | 63 | ||
| 4.1 Introduction | 63 | ||
| 4.2 Biological Building Blocks | 64 | ||
| 4.2.1 Amphiphilic Peptides | 64 | ||
| 4.2.2 Nucleolipids | 72 | ||
| 4.2.3 Lipopolysaccharides | 74 | ||
| 4.2.4 Saponins | 74 | ||
| 4.3 Gemini Surfactants | 76 | ||
| 4.3.1 Synergy in Mixtures | 79 | ||
| 4.3.2 Pseudo-gemini | 81 | ||
| 4.3.3 Trimeric Surfactants | 83 | ||
| 4.4 Ionic Liquids | 85 | ||
| 4.4.1 Ionic Liquids as a Solvent | 85 | ||
| 4.4.2 Ionic Liquids as a Surfactant | 86 | ||
| 4.5 Fluorosurfactants | 89 | ||
| 4.6 Surfactants with Ultra-long Alkyl Chain (C22) | 90 | ||
| 4.7 Conclusion and Outlook | 93 | ||
| References | 94 | ||
| Chapter 5 Self-assembled Networks Formed by Wormlike Micelles and Nanoparticles | 103 | ||
| 5.1 Introduction | 103 | ||
| 5.2 Interaction of Wormlike Micelles with Nanoparticles | 104 | ||
| 5.3 Phase Behavior | 106 | ||
| 5.4 Structure | 108 | ||
| 5.5 Tuning Rheology with Nanoparticles | 109 | ||
| 5.5.1 Dilute Solutions | 109 | ||
| 5.5.2 Semi-dilute Solutions | 109 | ||
| 5.6 Imparting New Functional Properties by Nanoparticles | 115 | ||
| 5.6.1 Magnetic Properties | 115 | ||
| 5.6.2 Plasmonic Properties | 116 | ||
| 5.7 Conclusions and Perspectives | 118 | ||
| Acknowledgments | 118 | ||
| References | 119 | ||
| Chapter 6 Stimulus-responsive Wormlike Micelles | 121 | ||
| 6.1 Overview and Scope | 121 | ||
| 6.2 Thermoresponsive Wormlike Micelles | 122 | ||
| 6.2.1 Thermo-thickening Non-ionic Wormlike Micelles | 122 | ||
| 6.2.2 Thermo-thickening Cationic Wormlike Micelles | 124 | ||
| 6.2.3 Thermo-thickening Anionic Wormlike Micelles | 126 | ||
| 6.2.4 Thermo-thickening Zwitterionic Wormlike Micelles | 127 | ||
| 6.2.5 Wormlike Micelles with Thermo-induced ‘‘Sol-Gel\" Transition | 128 | ||
| 6.3 pH-responsive Wormlike Micelles | 130 | ||
| 6.3.1 pH-responsive Wormlike Micelles Based on Zwitterionic Surfactants | 130 | ||
| 6.3.2 pH-responsive Wormlike Micelles Formed by ‘‘Cationic Surfactant+Acid\" Pairs | 132 | ||
| 6.3.3 pH-responsive Wormlike Micelles Based on Anionic Surfactants | 134 | ||
| 6.3.4 pH-responsive Wormlike Micelles Based on ‘‘Pseudo\" Non-covalent Bonds | 135 | ||
| 6.4 Redox-responsive Wormlike Micelles | 139 | ||
| 6.5 Photoresponsive Wormlike Micelles | 142 | ||
| 6.5.1 Light-responsive Wormlike Micelles Formed by a Surfactant+a Light Responser | 142 | ||
| 6.5.2 Photoresponsive Wormlike Micelles Formed by Photosensitive Surfactant | 149 | ||
| 6.6 CO2-responsive Wormlike Micelles | 149 | ||
| 6.6.1 CO2-switchable Wormlike Micelles Based on Pseudo-gemini Surfactants | 150 | ||
| 6.6.2 CO2-switchable Wormlike Micelles Based on a Long-chain Fatty Acid+CO2-responser | 154 | ||
| 6.6.3 CO2-switchable Wormlike Micelles Based on a Single Ultra-long-chain Amine | 156 | ||
| 6.7 Multistimulus-responsive Wormlike Micelles | 159 | ||
| 6.8 Conclusions and Outlook | 162 | ||
| Acknowledgments | 162 | ||
| References | 162 | ||
| Chapter 7 Direct-imaging Cryo-transmission Electron Microscopy of Wormlike Micelles | 171 | ||
| 7.1 Fundamental Aspects of Cryo-transmission Electron Microscopy | 171 | ||
| 7.1.1 Thermal Fixation and Vitrification | 171 | ||
| 7.1.2 Preparation of Vitrified Specimens | 172 | ||
| 7.1.3 Direct Imaging and Low Dose | 176 | ||
| 7.2 Seeing Micelles with Direct-imaging Cryo-TEM | 177 | ||
| 7.2.1 Cryo-TEM of Branched Micelles and the Origin of the Viscosity Peak | 177 | ||
| 7.2.2 Highlights from Recent Literature on Cryo-TEM of Wormlike Micelles | 183 | ||
| 7.3 Summary | 188 | ||
| Acknowledgments | 189 | ||
| References | 189 | ||
| Chapter 8 New Insights from Rheo-small-angle Neutron Scattering | 193 | ||
| 8.1 Introduction | 193 | ||
| 8.2 Rheo-SANS Sample Environments | 194 | ||
| 8.2.1 Rheo-SANS in the 1-3 (Flow-Vorticity) Shear Plane | 194 | ||
| 8.2.2 Rheo-SANS in the 2-3 (Gradient-Vorticity) Shear Plane | 196 | ||
| 8.2.3 Flow-SANS in the 1-2 (Flow-Gradient) Shear Plane | 197 | ||
| 8.2.4 Non-standard Flows and Geometries Studied with SANS | 197 | ||
| 8.3 Analysis of Microstructural Rearrangements Using SANS | 198 | ||
| 8.4 Summary of Rheo-SANS Systems and Literature | 200 | ||
| 8.5 Steady Shear, Shear Startup, and Shear Cessation Studied via Rheo-SANS | 201 | ||
| 8.5.1 Dilute Wormlike Micelle Solutions | 201 | ||
| 8.5.2 Semi-dilute Wormlike Micelle Solutions | 206 | ||
| 8.5.3 Concentrated Wormlike Micelle Solutions Near the I-N Transition | 214 | ||
| 8.6 LAOS Rheo-SANS | 219 | ||
| 8.6.1 Wormlike Micelle Solutions: CPyCl, CTAT/SDBS, PB-PEO Block Copolymers | 221 | ||
| 8.6.2 1-3 Plane Rheo-SANS LAOS Measurements | 221 | ||
| 8.6.3 1-2 Plane Shear-cell Examinations of Shear Banding Under LAOS | 223 | ||
| 8.6.4 Summary | 225 | ||
| 8.7 Results from Non-standard Flow Cells | 225 | ||
| 8.8 Outlook | 227 | ||
| Acknowledgments | 228 | ||
| References | 228 | ||
| Chapter 9 Microfluidic Flows and Confinement of Wormlike Micelles | 236 | ||
| 9.1 Introduction | 236 | ||
| 9.2 Shear Flows of Wormlike Micelles in Microfluidics | 239 | ||
| 9.2.1 Background | 239 | ||
| 9.2.2 Interfacial Instabilities and Shear Localizations of Wormlike Micelles | 242 | ||
| 9.2.3 Microfluidic Rheometry of Wormlike Micelles in Rectilinear Channels | 245 | ||
| 9.3 Extensional Flows of Wormlike Micelles in Microfluidics | 247 | ||
| 9.3.1 Background | 247 | ||
| 9.3.2 Microfluidic Stagnation Point Extensional Flows | 248 | ||
| 9.3.3 Contraction and Expansion Flows | 257 | ||
| 9.4 Wormlike Micelles in Complex Mixed Flow Fields | 261 | ||
| 9.4.1 Flow-induced Structures in Mixed Flows | 263 | ||
| 9.5 Outlook and Perspectives | 267 | ||
| References | 269 | ||
| Chapter 10 Progress in Computer Simulations of Wormlike Micellar Fluids | 279 | ||
| 10.1 Introduction | 279 | ||
| 10.2 Unusual Surfactants | 281 | ||
| 10.2.1 Peptide Amphiphiles | 281 | ||
| 10.2.2 Saponins | 285 | ||
| 10.2.3 Gemini and Oligomeric Surfactants | 285 | ||
| 10.3 Mechanical and Flow Properties of Wormlike Micelles | 287 | ||
| 10.4 Reverse Micelles | 289 | ||
| 10.5 Wormlike Micelles and Nanoparticles | 290 | ||
| 10.6 Microfluidic Flows | 292 | ||
| 10.7 Conclusion | 296 | ||
| Acknowledgments | 297 | ||
| References | 297 | ||
| Chapter 11 New Insights into the Formation of Wormlike Micelles: Kinetics and Thermodynamics | 298 | ||
| 11.1 Introduction | 298 | ||
| 11.2 Wormlike Micelles from a Molecular Point of View | 299 | ||
| 11.3 Thermodynamic Considerations | 310 | ||
| 11.4 Kinetic Considerations | 321 | ||
| 11.5 Conclusions and Perspectives | 325 | ||
| Acknowledgements | 326 | ||
| References | 327 | ||
| Chapter 12 Applications of Wormlike Micelles in the Oilfield Industry | 330 | ||
| 12.1 Introduction | 330 | ||
| 12.2 Viscoelastic Fluids from Wormlike Micelles | 331 | ||
| 12.3 Representative Surfactant Chemistries Used in the Oil Field | 332 | ||
| 12.3.1 Cationic Surfactants | 332 | ||
| 12.3.2 Anionic Surfactants | 333 | ||
| 12.3.3 Zwitterionic Surfactants | 333 | ||
| 12.4 Characteristics and Advantages of Viscoelastic Surfactant Fluids | 334 | ||
| 12.4.1 Operational Simplicity | 334 | ||
| 12.4.2 Ability to Reform After Exposure to High Shear | 335 | ||
| 12.5 Effective Drag Reduction | 335 | ||
| 12.5.1 Particle Suspension and Transport | 336 | ||
| 12.5.2 Clean-up | 337 | ||
| 12.6 Applications in Upstream Operations | 337 | ||
| 12.6.1 Fracturing Fluids | 338 | ||
| 12.6.2 Matrix Acidizing and Acid Fracturing | 339 | ||
| 12.6.3 Wellbore Fill Removal | 343 | ||
| 12.6.4 Sand Control and Gravel Packing | 344 | ||
| 12.7 Incorporation of Nano-additives with Wormlike Micelles | 345 | ||
| 12.8 Conclusions | 348 | ||
| References | 349 | ||
| Chapter 13 Turbulent Drag-reduction Applications of Surfactant Solutions | 353 | ||
| 13.1 Introduction and Background | 353 | ||
| 13.1.1 History | 353 | ||
| 13.1.2 Degradation of High Molecular Weight Polymer Drag-reducing Additives | 354 | ||
| 13.1.3 Surfactant Drag-reducing Additives | 354 | ||
| 13.1.4 Maximum Drag-reduction Asymptotes | 355 | ||
| 13.2 Oilfield Applications | 356 | ||
| 13.2.1 Outline | 356 | ||
| 13.2.2 Significance of Surfactant Drag Reducers in Oilfield Applications | 357 | ||
| 13.2.3 Benefits and Advantages of Surfactant Drag Reducers | 357 | ||
| 13.2.4 Large-scale Measurements and Scale-up Relations | 358 | ||
| 13.2.5 Oilfield Applications-Summary and Conclusions | 362 | ||
| 13.3 Heating and Cooling Systems | 362 | ||
| 13.3.1 Early Field Tests | 362 | ||
| 13.3.2 Applications for Heating and Cooling Systems in Japan | 364 | ||
| 13.3.3 Problems in Practical Use | 370 | ||
| 13.4 Other Possible Applications | 372 | ||
| 13.5 Conclusions | 373 | ||
| References | 373 | ||
| Chapter 14 Process Flow of Wormlike Micelle Solutions in Simple and Complex Geometries | 379 | ||
| 14.1 Introduction | 379 | ||
| 14.2 Experimental Materials, Properties, and Apparatus | 381 | ||
| 14.2.1 Materials | 381 | ||
| 14.2.2 Rheological Properties | 382 | ||
| 14.2.3 Experimental Apparatus for Flow Experiments | 383 | ||
| 14.3 Results for Simple Flows–Comparison of Viscosity Derived from Velocity Profiles to Rotational Viscometry | 387 | ||
| 14.3.1 Velocity Profile Imaging Using NMR | 387 | ||
| 14.3.2 Slip Measurements and Model | 389 | ||
| 14.4 Results for Complex Flows-Models for Flow in Static Mixers | 392 | ||
| 14.4.1 Static Mixer Models | 393 | ||
| 14.4.2 Viscosity Models and Fits to Experimental Data | 394 | ||
| 14.4.3 Comparison of Static Mixer Models to Experimental Data | 395 | ||
| 14.5 Conclusions | 396 | ||
| References | 397 | ||
| Subject Index | 399 |