Block Copolymers in Solution Fundamentals and Applications

by Hamley, Ian W.

• ISBN13: 9780470015575
• ISBN10: 0470015578
• Edition: 1st
• Format: Hardcover
• Copyright: 2005-09-02
• Publisher: WILEY

Summary

This unique text discusses the solution self-assembly of block copolymers and covers all aspects from basic physical chemistry to applications in soft nanotechnology. Recent advances have enabled the preparation of new materials with novel self-assembling structures, functionality and responsiveness and there have also been concomitant advances in theory and modelling. The present text covers the principles of self-assembly in both dilute and concentrated solution, for example micellization and mesophase formation, etc., in chapters 2 and 3 respectively. Chapter 4 covers polyelectrolyte block copolymers - these materials are attracting significant attention from researchers and a solid basis for understanding their physical chemistry is emerging, and this is discussed. The next chapter discusses adsorption of block copolymers from solution at liquid and solid interfaces. The concluding chapter presents a discussion of selected applications, focussing on several important new concepts. The book is aimed at researchers in polymer science as well as industrial scientists involved in the polymer and coatings industries. It will also be of interest to scientists working in soft matter self-assembly and self-organizing polymers.

Author Biography

Ian W. Hamley is the author of Block Copolymers in Solution: Fundamentals and Applications, published by Wiley.

Table of Contents

Preface	xi
Introduction	1	(6)
References	5	(2)
Neutral Block Copolymers in Dilute Solution	7	(98)
Introduction	7	(1)
Techniques for Studying Micellization	7	(11)
Cryo-TEM	7	(1)
Differential Scanning Calorimetry	8	(1)
Dynamic Light Scattering	8	(2)
Ellipsometry	10	(1)
Fluorescence Probe Experiments	10	(1)
Nuclear Magnetic Resonance	10	(1)
Rheology	11	(1)
Scanning Probe Microscopy	11	(1)
Small-angle X-ray and Neutron Scattering	12	(2)
Static Light Scattering	14	(2)
Surface Pressure--Area Isotherms	16	(1)
Surface Tensiometry	16	(1)
Viscometry	17	(1)
X-ray and Neutron Reflectivity	17	(1)
Micellization in PEO-based Block Copolymers	18	(2)
Micellization in Styrenic Block Copolymers	20	(1)
Determination of cmc	20	(2)
Thermodynamics of Micellization	22	(11)
Chain Length Dependence of Micellization	25	(2)
Effect of Architecture	27	(5)
Effect of Solvents and Salts on Micellization	32	(1)
Micellization and Micelle Dimensions: Theory and Simulation	33	(14)
Scaling Models	33	(4)
The Brush Model	37	(3)
The Self-consistent Mean Field Theory	40	(3)
The Model of Nagarajan and Ganesh	43	(1)
Computer Simulations	44	(1)
Theory: ABC Triblock Micelles	45	(2)
Micelle Dimensions: Comparison Between Experiment and Theory	47	(4)
Interaction between Micelles	51	(1)
Dynamics of Micellization	52	(4)
Dynamic Modes	56	(4)
Specific Types of Micelles	60	(15)
Micelles from Telechelics	60	(2)
Micelles from ABC Triblocks	62	(4)
Micelles from Rod--Coil Copolymers	66	(2)
Cross-linked Micelles	68	(3)
Janus Micelles	71	(1)
Nonspherical Micelles	71	(3)
Micelles Formed due to Specific Interactions	74	(1)
Micellization in Mixed Solvents	75	(1)
Mixed Micelles	75	(1)
Block Copolymer/Surfactant Complexes	76	(3)
Complex Morphologies	79	(4)
Vesicles	83	(7)
Crystallization in Micelles	90	(15)
References	91	(14)
Concentrated Solutions	105	(68)
Understanding Phase Diagrams	105	(6)
Phase Behaviour of PEO-containing Block Copolymers	111	(6)
Gelation	117	(15)
Rheology	117	(7)
Structure -- Packing of Micelles	124	(2)
Thermodynamics of Gelation and Micellization in Concentrated Solution	126	(1)
Effect of Added Homopolymer, Salt or Surfactant	127	(2)
Influence of Architecture	129	(3)
Order-Disorder Phase Transition	132	(3)
Order-Order Phase Transitions	135	(5)
Structural Aspects	135	(4)
Ordering Kinetics	139	(1)
Domain Spacing Scaling, and Solvent Distribution Profiles	140	(3)
Semidilute Block Copolymer Solution Theory	143	(3)
Theoretical Understanding of Phase Diagrams	146	(3)
Flow Alignment	149	(10)
Lamellar Phase	149	(2)
Hexagonal Phase	151	(1)
Cubic Micellar Phases	152	(7)
Dynamics	159	(14)
Dynamic Modes	159	(1)
Dynamics of Gelation	160	(4)
References	164	(9)
Polyelectrolyte Block Copolymers	173	(42)
Micellization	173	(11)
General Remarks	173	(2)
Micellization in Block Copolymers Containing Anionic Blocks	175	(4)
Micellization in Block Copolymers Containing Cationic Blocks	179	(3)
Micellization of Polyampholyte Block Copolymers	182	(1)
Micellization of Polyelectrolyte-containing ABC triblocks	182	(1)
Micellization of Block Copolymers Containing Grafted Polyelectrolytes	183	(1)
Micellization in Block Copolymers Containing Sulfonated Polyisoprene	183	(1)
Chain Conformation	184	(4)
Theory	188	(7)
Polyion Complexes	195	(3)
Copolymer--Surfactant Complexes	198	(1)
Complexation with other Molecules	199	(1)
Gelation	200	(1)
Hierarchical Order in Peptide Block Copolyelectrolyte Solutions	200	(15)
α Helix Structures	202	(2)
β Sheet Structures	204	(2)
Hydrogels	206	(1)
Polypeptide Block Copolymer-based Complexes	207	(1)
References	208	(7)
Adsorption	215	(26)
Introduction	215	(1)
Adsorption at the Air-Water Interface	215	(7)
Adsorption of Neutral Block Copolymers	215	(6)
Adsorption of Polyelectrolyte Block Copolymers	221	(1)
Adsorption on Solid Substrates	222	(9)
Adsorption of Neutral Block Copolymers	222	(3)
Adsorption of Polyelectrolyte Block Copolymers	225	(1)
Surface Micelles	226	(5)
Surface Forces Experiments	231	(3)
Modelling Adsorption	234	(7)
References	236	(5)
Applications	241	(44)
Surfactancy/Detergency	241	(1)
Solubilization, Emulsification and Stabilization	241	(6)
Solubilization	241	(4)
Emulsification and Stabilization	245	(2)
Drug Delivery	247	(6)
Biodegradable Block Copolymer Micelles	253	(1)
Thermoresponsive Micellar Systems	254	(1)
Metal-containing Copolymer Micelles and Nanoreactors	255	(6)
Vesicles	261	(7)
Separation Media	268	(1)
Templating	268	(6)
Membranes	274	(1)
Other Applications	275	(10)
References	276	(9)
Index	285