Handbook of Liquid Crystals

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1 Hans Kelker/Rolf Hatz Handbook of Liquid Crystals With a Contribution by Christian Schumann Eigentum der Firma Kort Eichweber Hamburg-Altona Verlag Chemie Weinheim Deerfield Beach, Florida Basel 1980

Contents - a Summary 1 Microscopic Investigations Including Basic Concepts, Phenomenology, and Morphology 1 2 Chemical Constitution 33 3 Theory of the Liquid-Crystalline State 115 4 Behavior in

2 Contents - a Summary 1 Microscopic Investigations Including Basic Concepts, Phenomenology, and Morphology 1 2 Chemical Constitution 33 3 Theory of the Liquid-Crystalline State Behavior in Magnetic and Electric Fields X-Ray and Neutron Scattermg, Positron Annihilation, Mössbauer Investigations, and Cherenkov Radiation Optical Properties ol Optically Inactive Mesophases Optical Properties of Optically Active Mesophases Thermodynamic Properties Liquid Crystals as Solvents in Gas Chromatography and in Chemical Reactions Nuclear Magnetic Resonance and Electron Spin Resonance Studies (by Ch. Schumann) Lyotropic Mesomorphism Liquid Crystals in Living Systems Liquid-Crystalline Order in Polymers : Technical Applications History, Reviews, and Books 627 References 633 Subject Index 899 Legal Note 911

Contents 1 Microscopic Investigations Including Basic Concepts, Phenomenology, and Morphology 1 1.1 Introduction 2 1.2 Polymorphism 5 1.3 Solid Surface Boundary Action 11 1.

3 Contents 1 Microscopic Investigations Including Basic Concepts, Phenomenology, and Morphology Introduction Polymorphism Solid Surface Boundary Action Textures in Nematic Phases Homogeneous Texture Homeotropic Texture Schlieren Texture (Centered Texture) Nematic Droplets Maugum Texture and Nematic-Cholesteric Phases Textures in Smectic Phases Lyotropic Mesophases Selected Mesogens 30 2 Chemical Constitution Structural Features Aromatic and Heteroaromatic Rings Linear Molecules 37

XII Contents 2.2.2 Sheet Molecules (Platelets, Disc-Shaped Molecules) 40 2.2.3 Heteroaromatic Rings 40 2.3 Bridging Groups 41 2.3.1 Azomethines 43 2.3.2 Azo Compounds 44 2.3.3 Azoxy Compounds 45 2.3.4 Biphenyl Compounds 45 2.

4 XII Contents Sheet Molecules (Platelets, Disc-Shaped Molecules) Heteroaromatic Rings Bridging Groups Azomethines Azo Compounds Azoxy Compounds Biphenyl Compounds Terminal Groups and Homologous Series Broadening of Molecules Aromatic Carboxylic Acids Carboxylic Acid Salts and Ammonium Salts Steroids Aliphatic Compounds Inorganic and Miscellaneous Compounds Conclusion Classification of Mesogens Table of Mesogens 69 3 Theory of the Liquid-Crystalline State Introduction The Continuum Theory Explanation of Some Texture Characteristics The Maier-Saupe Theory (Mean-Field Approximations) Hydrodynamics, Equilibrium Theories The de Gennes Theory Pretransition Phenomena Viscosity and Flow Studies Diffusion and Heat Conductivity Ultrasonic Studies Surface and Interface Properties Behavior in Magnetic and Electric Fields Nematic Phases in Magnetic Fields Magnetic Susceptibility Elastic Deformation (Frederiks Deformation) Action of a Rotating Magnetic Field (Tsvetkov Effect) Thermal Effects of a Magnetic Field (Moll-Ornstein Effect) Optical Rotatory Power and Linear Electro-Optical Effect Other Investigations in Magnetic Fields Cotton-Mouton Effect 167

Contents XIII 4.2 Cholesteric Phases in Magnetic Fields 168 4.2.1 Helical Unwinding 168 4.2.2 Periodic Deformations 169 4.2.3 Elastic Deformation 171 4.2.4 Storage Effect 172 4.

5 Contents XIII 4.2 Cholesteric Phases in Magnetic Fields Helical Unwinding Periodic Deformations Elastic Deformation Storage Effect Smectic Phases in Magnetic Fields Nematic Phases in Electric Fields Dielectric Susceptibility; Dielectric Constants Electric Conductivity Elastic Deformation of Ordinary Nematics (Frederiks Deformation) Elastic Deformation of Twisted Nematics (Schadt-Helfrich Mode, TN Devices) Electrohydrodynamic Instabilities Electrochemical Behavior Periodic Deformations, Type Williams Domains Dynamic Scattering Mode (DSM) Theory of Electrohydrodynamic Instabilities Special Observations Fast Turn-off Mode Curvature Electricity (Piezo- or Flexo-electricity) Ferroelectric Effects Phase Transitions in External Fields Kerr Effect Cholesteric Phases in Electric Fields Dielectric Susceptibility; Dielectric Constants Electric Conductivity Electro-Optical Effects Storage Modes Periodic Deformations Helical Unwinding Conical Deformation, Blue Shift Mode Special Observations Smectic Phases in Electric Fields Dielectric Constants Electric Conductivity Electric Deformations X-Ray and Neutron Scattering, Positron Annihilation, Mössbauer Investigations, and Cherenkov Radiation X-Ray Scattering X-Ray Studies of Special Mesophases Nematic Phases Cholesteric Phases Smectic Phases Mesophases of Carboxylic Acid Salts Neutron Scattering 242

XIV Contents 5.4 Positron Annihilation 246 5.5 Mössbauer Investigations 248 5.6 Cherenkov Structure Radiation 249 5.

6 XIV Contents 5.4 Positron Annihilation Mössbauer Investigations Cherenkov Structure Radiation Bibliography of X-Ray Studies on Liquid Crystals Optical Properties of Optically Inactive Mesophases Birefringence Experimental Results Theoretical Considerations Special Refractive Modes Rayleigh Scattering Nematic Liquid Crystals Smectic Liquid Crystals Pretransition Phenomena UV- and Visible Absorption Spectroscopy Fluorescence Spectroscopy IR Spectroscopy Nematic Phases Smectic and Other Mesophases Raman Scattering Nematic Phases Smectic and Other Mesophases Brillouin Scattering Optical Properties of Optically Active Mesophases Selective Reflection and Optical Activity Helical Structures Basic Observations Theory of Light Propagation Influence of Temperature and Pressure Special Observations Behavior of Mixtures UV- and Visible Absorption Spectroscopy Fluorescence Spectroscopy IR Spectroscopy Raman Scattering Birefringence Rayleigh Scattering Brillouin Scattering Nonlinear Optics 334

Contents XV 7.10 Other Optical Observations 335 7.11 Twisted Nematic Phases 335 7.12 Twisted Smectic Phases 336 8 Thermodynamic Properties 339 8.1 Classification of Phase Transitions 340 8.

7 Contents XV 7.10 Other Optical Observations Twisted Nematic Phases Twisted Smectic Phases Thermodynamic Properties Classification of Phase Transitions Theory of Phase Transitions Pretransition Phenomena Calorimetric Measurements Molar Heat Transition Enthalpy and Entropy Kinetics of Phase Transitions, Glassy State Temperature-Dependence of Density High-Pressure Investigations Mixed Systems with Mesophases Mixtures of an Enantiotropic Mesogenic Substance with a Monotropic or Nonmesogenic Substance Mixtures of Two Enantiotropic Mesogenic Substances Liquid Crystals as Solvents in Gas Chromatography and in Chemical Reactions Liquid Crystals in Gas Chromatography Experimental Results First Statement Second Statement Third Statement Summary Models and Theory Theoretical Background The Regular-Solution Concept The Entropie Part of f The Free Energy Concept The Liquid-Crystalline/Isotropic Transition as a Corresponding-State Condition Pretransition Phenomena Chemical Reactions in Anisotropie Liquids Thermotropic Mesophases Polymerization Reactions in Thermotropic Mesophases Lyotropic Mesophases Nuclear Magnetic Resonance and Electron Spin Resonance Studies 425 (by Ch. Schumann) 10.1 Introduction NMR Studies of Mesophases Basic Principles Available Information 428

Contents 10.2.3 Experimental Methods 429 10.2.4 Results 431 10.2.5 Table of Thermotropic Mesophases 435 10.2.6 Table of Synthetic Lyophases 445 10.2.7 Table of Biological Lyophases 451 10.

8 Contents Experimental Methods Results Table of Thermotropic Mesophases Table of Synthetic Lyophases Table of Biological Lyophases NMR Studies of Mesophase-Oriented Solutes Basic Principles Available Information Experimental Methods Results Table of Nematic Solvents Table of Solutes ESR Investigations Table of Mesophases Table of Paramagnetic Solutes List of Spin Label Studies in Biological Systems Lyotropic Mesomorphism Introduction Mesophases in Soap Solutions and their Textures X-Ray Analysis Electron Microscopy Composition of Lyotropic Mesophases Binary Systems with Soaps Binary Systems with other Amphiphiles Ternary and Multicomponent Systems Solubilization Other Properties of Lyotropic Mesophases Mesomorphous Solutions of Synthetic Polymers and Copolymers Polymers Copolymers Mesomorphous Solutions of Miscellaneous Types of Substances Technical Importance of Lyotropic Mesophases Foams and "Black Foam Films" Emulsions Suspensions Liquid Crystals in Living Systems Polypeptide Model Substances Cholesteric Pseudomorphosis in Crustacean and Insect Cuticles Binary Aqueous Mesophases of Lipids Monoglycerides Phospholipids 565

Contents XVII 12.4 Classification of Biological Lipids 569 12.5 Phase Characteristics of Lipids in Systems with Three or More Components. 570 12.5.1 Bile Analog Systems 572 12.5.2 Atherosclerotic Lesions 573 12.

9 Contents XVII 12.4 Classification of Biological Lipids Phase Characteristics of Lipids in Systems with Three or More Components Bile Analog Systems Atherosclerotic Lesions Myelin The Liquid-Crystalline State in Biological Membranes Constituents of Membranes Solubilization and Reconstitution Structure and Membrane Models Properties and Membrane Functions Nucleic Acids and Viruses Blood MuscleTissue Other Biological Objects Final Remark Liquid-Crystalline Order in Polymers Introduction Polymers without a Typical Mesogenic Group Polymers with a Typical Mesogenic Group in the Main Chain Polymers with a Typical Mesogenic Group in the Side Chain Directly Attached to the Main Chain Polymers with a Typical Mesogenic Group in the Side Chain and a Flexible Spacer Inserted between the Main Chain and the Rigid Mesogenic Group Technical Applications Embodiments Optical Devices Thermography Medical Applications Nondestructive Testing Electromagnetic Radiation Detectors Sound Wave and Pressure Detectors Electro-Optical Display Devices The DAP Mode The Color-Switching Mode The Schadt-Helfrich Mode The Dynamic Scattering Mode The Cholesteric Storage Mode Liquid-Crystal Cells with Photoconductors Special Electro-Optical Devices 622

XVIII Contents 14.5 Holography and Interferometry 624 14.

10 XVIII Contents 14.5 Holography and Interferometry Miscellaneous Possibilities of Application History, Reviews, and Books History Reviews Books and Monographs Symposia 631 References 633 Subject Index 899 Legal Note 911

LIQUID CRYSTAL DISPERSIONS

.IES ON LIQUID CRYSTALS Volume 1 LIQUID CRYSTAL DISPERSIONS Paul S. Drzaic Raychem Corporation World Scientific Singapore New Jersey London Hong Kong Contents Preface Credits yii ix Introduction 1 The