This volume discusses the application of selected scattering methods, in particular light and neutron scattering, to complex polymeric and colloidal systems. Brown (physical chemistry, U. of Uppsala) and Mortensen (condensed matter physics and chemistry, Riso National Laboratory) present four chapters by a term of international researchers who cover topics including the principles and applications of static multiple scattering; diffusion in polymer solutions; light scattering from ionomers, ternary solutions and semiflexible polymers; the application of light, neutron and x-ray diffraction to microemulsions; critical phenomena in polymer blend solutions; the experimental investigation of thermal composition fluctuations in the equilibrium state; the study of block copolymers; the combination of simultaneous time-resolved small and wide angle x-ray scattering to elucidate structural features; x-ray and neutron reflectometry used to study polymer surfaces, interfaces and thin films; and spin echo spectroscopy for studying polymer dynamics. Annotation c. Book News, Inc., Portland, OR (booknews.com)
The application of selected scattering methods, in particular light and neutron scattering, to complex polymeric and colloidal systems is discussed. Progress in this area of condensed matter is charted and the book provides insight into the theory and practice of the techniques apploed to a number of diverse problems.
Preface xvii Contributors xxi Multiple Scattering of Light: Coherent Backscattering and Transmission 1(74) Ralf Lenke Georg Maret Introduction 2(4) Light Propagation in Single and Multiple Scattering Samples 6(9) The Diffusion Approximation 8(2) Cross-over from Single to Multiple Scattering 10(2) Influence of a Boundary 12(3) Transmission Geometry 15(10) Time-resolved Transmission Experiments 19(2) Frequency-dependent Speckle Correlations 21(3) Diffuse Photon-density Waves 24(1) Coherent Backscattering of Light 25(33) Theory of Coherent Backscattering 28(14) Monte-Carlo Simulations 42(2) Experimental Setup of CB 44(4) Examples of CB-cones 48(10) Transport Mean Free Path l* 58(2) Proof of Equations (57) and (58) 60(2) Monte-Carlo Simulations 62(2) Divergent or Convergent Light Source 64(2) Strongly Inclined Samples and Refraction at the Surface 66(9) Glossary of Symbols 68(1) References 69(6) Thermal-Diffusion Forced Rayleigh Scattering 75(42) Werner Kohler Introduction 76(2) Phenomenological Model 78(5) The Transport Coefficients 78(2) Writing of the Grating 80(1) Detection 81(2) Experimental Aspects 83(5) Setup 83(3) Sample Preparation 86(1) Size of the Effect 86(1) Convection and Flow 87(1) Liquid Mixtures 88(4) Polymer Solutions 92(13) Treatmet of Polydispersity 92(1) Averages of the Transport Coefficients 93(1) Molar Mass Distribution and Averages 94(3) Experimental Determination of the Transport Coefficients 97(5) Broad Molar Mass Distributions 102(3) Semidilute and Concentrated Solutions 105(1) Stochastic TDFRS 105(5) Conclusions 110(7) Acknowledgements 111(1) Glossary of Symbols 111(2) References 113(4) Light Scattering from Ionomer Solutions 117(34) Masanori Hara Introduction 117(3) Ionomer Solutions 117(2) Light Scattering Techniques 119(1) Ionomers in Polar Solvents (Polyelectrolyte Behaviour) 120(20) Introduction 120(1) Static Light Scattering 121(11) Dynamic Light Scattering 132(8) Ionomers in Non-polar Solvents (Aggregation Behaviour) 140(6) Introduction 140(2) Static Light Scattering 142(2) Dynamic Light Scattering 144(2) Conclusions 146(5) Acknowledgements 146(1) Glossary of Symbols 146(2) References 148(3) Light Scattering from Ternary Polymer Solutions 151(46) Claude Cohen Introduction 151(2) Theoretical Background 153(10) Phenomenological Basis 153(2) Thermodynamics and Static Information 155(3) Dynamics and Diffusion Coefficients 158(2) Hydrodynamic Fluctuations and Initial Spinodal Decomposition 160(3) Selected Experimental Results and Discussion 163(28) Thermodynamics and Static Information from SLS 163(8) Dynamic and Static Information from DLS 171(12) The Case of Coils in Solutions with Rodlike Polymers 183(8) Conclusions 191(6) Acknowledgements 191(1) Glossary of Symbols 191(2) References 193(4) Dynamic Scattering from Semiflexible Polymers 197(52) Klaus Kroy Erwin Frey Introduction 198(3) Wormlike Chain Model 201(5) Static Structure Factor 206(2) Critical Comment on Gaussian Models 208(3) Dynamics of Semiflexible Polymers in Solution 211(14) Brief Survey of the History 211(2) Introduction of the Equation of Motion 213(4) Linear Mode Analysis 217(3) Entanglement Effects 220(5) Dynamic Structure Factor 225(17) Definitions 225(3) Initial Decay (t < τq) 228(3) Initial Slope from the Smoluchowski Equation 231(3) Stretched Exponential Decay (t > τq) 234(1) Entanglement Effects 235(1) Polydispersity and Clusters 236(3) Applications to Biopolymers 239(3) Conclusions 242(7) Acknowledgements 242(1) Glossary of Symbols 242(2) References 244(5) Microemulsions Studied by Scattering Techniques 249(78) Holger Mays Kell Mortensen Wyn Brown Introduction 250(1) Microemulsions 251(17) Formation of Microemulsions 252(2) Phase Behaviour 254(4) Microstructure 258(9) Experimental Methods 267(1) General Advantage and Disadvantages of Scattering Techniques 267(1) Scattering of Electromagnetic Waves 268(35) The Basic Theory of the Scattering Intensity 269(4) Interference Effects, Interactions and Structure Factor 273(2) Static Light Scattering from Hard Spheres 275(4) Attractive Particle Interactions and Clustering 279(3) Static Light Scattering from Non-spherical Particles 282(2) Static Light Scattering from L3-Phases 284(1) Optical Matching 285(3) Dynamic Light Scattering 288(1) The Technique 288(3) Data Evaluation 291(1) The Concentration Dependence of Dc 292(3) Experimental Studies on Non-attractive Droplet Microemulsions 295(3) Attractive Interactions, Percolating Systems and Phase Transitions 298(2) Microemulsions Containing Networks 300(1) Practical Aspects of Scattering with Microemulsions 301(2) Small Angle Neutron and X-ray Scattering 303(24) Interaction Between Matter and X-ray or Neutrol Radiation 303(2) Contrast Variation 305(2) Indirect Fourier Transformation 307(1) Scattering from Micelles 308(1) Micellar Form Factors 309(1) Inter Micellar Interaction 310(1) Swollen Lamellar Phases 311(2) Bicontinuous Microemulsions 313(2) Acknowledgements 315(1) Glossary of Symbols 315(3) References 318(9) Critical Behaviour in Polymer Blend Solutions 327(44) Takuhei Nose Naoshi Miyashita Introduction 328(4) Critical Behaviour of Fluids 328(2) Critical Behaviour of Polymeric Systems 330(2) Theoretical Backgrounds 332(9) Static Crossover of Critical Behaviour - Mean-field, Ising, and Fishers Renormalized Ising Behaviours 332(1) The Ginzburg Number Gi and Universal Crossover Function 332(1) GiBK (bare) for Polymer Blend Solutions Evaluated with a Blob Model 332(3) Fishers Renormalized Ising Behaviour 335(1) Dynamic Crossover of Critical Behaviour - Diffusive Process and Hydrodynamic Mode-Mode Coupling Process 336(1) Mode-coupling Theory and Dynamic Crossover Number ϵ* 336(3) Concentration Fluctuations in Polymer Blend Solutions and Dynamic-crossover Number ϵ* Evaluated with a Blob Model 339(2) Symmetrical Polymer Blend Solutions 341(13) Static Critical Behaviour - Crossover from the Mean-field to Ising Behaviour 342(1) Static Light Scattering 342(2) Experimental Results and Discussion 344(4) Dynamic Critical Behaviour - Crossover from Diffusive to Hydrodynamic Behaviour 348(1) Dynamic Light Scattering 348(2) Experimental Results and Discussion 350(4) Asymmetrical Polymer Blend Solutions - Molecular-weight Asymmetry and Solvent-quality Asymmetry 354(9) Static Critical Behaviour - Crossover from Ising to Fishers Renormalized Behaviour 356(2) Dynamic Critical Behaviour - Effects of the System-asymmetry on Critical Dynamics 358(5) Conclusions 363(8) Glossary of Symbols 364(3) References 367(4) Thermal Composition Fluctuations in Polymer Blends Studied with Small Angle Neutron Scattering 371(42) Dietmar Schwahn Kell Mortensen Introduction 372(1) Theoretical Background 373(8) Susceptibility 374(1) Crossover Function and Ginzburg Criterion 375(1) Flory-Huggins Theory 375(2) Structure Factor S(Q): RPA; Ornstein-Zernike 377(1) Length Scales in Polymer Blends 377(2) The Effect of Compressibility 379(1) Scattering Contrast in Neutron Scattering 379(2) Thermodynamic Parameters Determined from the Structure Factor 381(9) Structure Factor S(Q) 381(1) Susceptibility in One-Phase Region 381(2) Ginzburg Number 383(2) Flory-Huggins Parameter and Phase Diagram 385(1) Spinodal and Binodal 386(1) Effect of Polydispersity 387(3) Characteristic Lengths in Polymer Blends 390(2) The A, A* Parameters and the Radius of Gyration Rg 390(2) The A Parameter in the Critical Range and the Correlation length 392(1) Structure Factor S(Q) in the Two-phase Regime 392(4) Mixed State during the Early Stage of Spinodal Decomposition 393(2) Decomposed in Domains of Equilibrium Composition 395(1) External Fields 396(7) Pressure 397(4) Shear 401(2) Polymer Blends with Additives of a Good Solvent and a Diblock Copolymer 403(5) Low Molecular Weight Solvents 403(1) Addition of a Diblock Copolymer 404(4) Summary 408(5) Appendix 409(1) Acknowledgements 409(1) Glossary of Symbols 409(1) References 410(3) Block Copolymers Studies with Small Angle Neutron Scattering 413(44) Kell Mortensen Introduction 414(2) Experimental 416(5) Interaction Between Matter and X-ray/Neutron Radiation 417(1) Scattering Amplitude and Intensity 418(2) Auxiliary Instrumentation in Scattering Experiments 420(1) Disordered Block Copolymer Melts 421(10) Concentration Fluctuations in the Mean-field Approximation 423(5) Effect of Polydispersity 428(1) Fluctuation Effects 429(2) Peak Position q*, and Polymer Radius of Gyration, Rg 431(5) N-Scaling of Peak-value q* 433(1) Gaussian Regime 433(1) Weak Segregation 434(1) Strong Segregation 434(1) Direct Measurement of Polymer Size 434(2) Order-Disorder Transition and Microphase Separation 436(8) Leibler Theory 436(1) Micellar Precursor 437(1) Fluctuation Effects on the Order-Disorder Transition 438(2) Order-Disorder Transition Dependence of Pressure 440(2) Order-Disorder Transition Dependence on Shear 442(2) Ordered Phases 444(7) Conformational Asymmetry 446(1) Thermodynamically Stable Ordered Structures 446(4) Epitaxy 450(1) Conclusions 451(6) Acknowledgements 451(1) Glossary of Symbols 451(2) References 453(4) Time-Resolved SAXS/WAXS Experiments 457(38) Wim Bras Introduction 458(4) Instrumentation for SAXS/WAXS Experiments 462(19) X-ray Sources, Detectors and Data-analysis 462(1) Rotating Anode X-ray Generator 462(1) Synchrotron Radiation Beamlines 462(3) Position Sensitive Detectors 465(2) Normalisation 467(1) Data Analysis 467(2) Data Collection Strategy 469(1) Isotropic Scatterers 470(2) Anisotropic Scatterers 472(1) Instrumental Limitations 472(1) Time Resolution 472(5) Accessible Scattering Vector Range 477(1) Sample Environments 478(1) Determining the Limiting Parameters 478(3) Examples 481(9) Examples of Isotropically Scattering Systems 481(1) Isotactic Polypropylene 481(4) Heat Treatment of Cordierite Glass 485(2) Examples of Anisotropically Scattering Systems 487(2) Examples of Combinations with Other Techniques 489(1) Conclusions 490(5) Acknowledgements 490(1) Glossary of Symbols 491(1) References 491(4) Polymer Surfaces, Interfaces and Thin Films Studied by X-ray and Neutron Reflectometry 495(40) Manfred Stamm Introduction 496(11) The Contrast between Components 497(1) The Reflection of X-rays and Neutrons 498(6) Sample Preparation 504(1) Instrumentation 505(1) Advantages and Limitations of the Technique 506(1) Surface Roughness and Structures in Thin Films 507(11) Interface Roughness 507(1) Structure in Thin Films 508(2) Capillary Waves and Correlated Roughness between Different Interfaces 510(3) Dewetting and Demixing in Thin Polymer Films 513(3) Conformation and Dynamics of Polymers at Interfaces 516(2) Interfaces between Incompatible Polymers 518(10) Theoretical Aspects 520(2) Interfaces between Polystyrene (PS)/Polymethylmethacrylate (PMMA) 522(3) PS/poly(styrene-stat-para bromo styrene) (PBrxS) 525(1) Correlation between Interface Width and Adhesion 526(2) Interdiffusion at the Interface between Compatible Polymers 528(2) Initial Stages of Segment Diffusion at the Interface 528(1) Influence of Chain Mobility on Segment Diffusion 529(1) Conclusion 530(5) Acknowledgements 530(1) Glossary of Symbols 531(1) References 531(4) Polymer Dynamics by Neutron Spin Echo Spectroscopy 535(42) Dieter Richter Introduction 535(2) Quasielastic Neutron Scattering 537(7) Principles of the Method 537(3) Neutron Spin Echo Technique 540(1) Neutron Spin Manipulations with Magnetic Fields 540(2) The Spin Echo Spectrometer 542(2) Local Relaxation Processes 544(6) Dynamic Structure Factor 545(2) Results on Polybutadiene 547(3) Entropy Driven Dynamics - The Rouse Regime 550(9) Entropic Forces - The Rouse Model 550(2) Dynamic Structure Factors for the Rouse Model 552(2) Neutron Spin Echo Results at PDMS Melts 554(5) Onset of Entanglements 559(4) Long Chains - Reptation 563(8) Summary 571(6) Glossary of Symbols 572(1) References 573(4) Index 577
Wyn Brown, Kell Mortensen
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