Crystals and crystallinity in polymers : diffraction analysis of ordered and disordered crystals
- Claudio De Rosa, Dipartimento di Chimica Paolo Corradini, Università di Napoli Federico II, Complesso Monte Sant' Angelo, Napoli, Italy, Finizia Auriemma, Dipartimento di Chimica Paolo Corradini, Università di Napoli Federico II, Complesso Monte Sant' Angelo, Napoli, Italy.
- Hoboken, New Jersey : Wiley, 2014.
- Physical description
- 1 online resource (xiii, 461 pages)
- Includes bibliographical references and index.
- Preface xi 1 Configuration and Conformation of Macromolecules in PolymerCrystals 1 1.1 Crystals of Polymers, 1 1.2 Constitution and Configuration of Crystalline Polymers, 3 1.2.1 Constitution, 3 1.2.2 Configuration, 5 1.2.3 Relative Configurations, 14 1.3 Conformation, 18 1.4 Relationships among Internal Parameters of Macromolecules, 19 1.5 Conformation of Polymer Chains in the Crystalline State, 21 1.5.1 Basic Principles, 21 1.5.2 The Equivalence Principle, 21 18.104.22.168 Symmetry Relations for Cylindrical Coordinates, 29 22.214.171.124 Application of the Equivalence Principle: StereoregularVinyl Polymers, 31 1.5.3 Principle of Minimum Conformational Internal Energy, 33 1.5.4 Relationships between Internal Coordinates andConformational Parameters, 36 1.6 Helical Conformations in Isotactic and SyndiotacticPolymers, 46 1.7 Conformational Energy Calculations, 51 1.7.1 Setting Up Molecular Models: Coordinate Transformations, 52 1.7.2 Calculation of the Conformational Energy for Isotactic andSyndiotactic Polymers, 54 1.8 Helical Conformation and Optical Activity, 66 1.9 Alternating Copolymers, 68 1.10 Polydienes, 73 1.11 Nonhelical Chain Conformations of Isotactic Polymers, 78 References, 81 2 Packing of Macromolecules in Polymer Crystals 88 2.1 General Principles, 88 2.2 The Principle of Density (Entropy)-Driven Phase Formation inPolymers, 92 2.3 Symmetry Breaking, 96 2.4 Impact of Chain Folding on Crystal Structure Symmetry, 103 2.5 Frustrated Polymer Crystal Structures, 107 2.6 Chiral Crystallization of Polymers with Helical ChainConformations, 110 2.7 Packing Effects on the Conformation of Polymer Chains inCrystals: The Case of Aliphatic Polyamides, 113 References, 118 3 Methods in Crystal Structure Determination from X-RayDiffraction 123 3.1 X-Ray Diffraction of Semicrystalline Polymers, 123 3.1.1 Basic Principles, 123 3.1.2 Experimental Techniques for Polymer Crystals, 128 3.2 Fourier Synthesis and the Phase Problem in Crystallography, 134 3.3 X-Ray Fiber Diffraction Analysis, 140 3.3.1 Determination of the Fiber Period and the Bragg Distancesof Diffraction Peaks, 140 3.3.2 Analysis of Nonhelical and Helical Structures, 142 3.3.3 The Structure Factor of a Single Molecule: The ContinuousHelix, 144 3.3.4 CCV Formula for Helical Structures, 147 3.3.5 The Case of Incommensurable Helices, 153 3.3.6 Calculation of Structure Factors of a Single HelicalChain, 162 3.3.7 Calculation of Structure Factors of Crystals of HelicalMolecules Including More Than One Chain per Unit Cell, 163 3.4 Determination of Parameters of the Unit Cell and Indexing ofthe Diffraction Pattern, 165 3.4.1 X-Ray Diffraction Data from Oriented Fibers, 165 3.4.2 X-Ray Diffraction Data from Powder Samples, 170 3.5 Measure of the Integrated Intensities of the Reflections andCorrections for Geometric (Lorentz), Polarization, and AbsorptionFactors, 171 3.6 Calculation of Structure Factors, 174 3.7 Structural Refinement, 180 3.8 Form of Diffraction Pattern and Broadening due to the LaueFunction, 181 References, 183 4 Defects and Disorder in Polymer Crystals 185 4.1 Classification of Different Types of Structural Disorder, 185 4.2 Crystals with Partial Three-Dimensional Order (Class A):Disorder with Three-Dimensional Periodicity Maintained for OnlySome Characterizing Points of the Structure, 191 4.2.1 Substitutional Isomorphism of Different Chains, 192 126.96.36.199 Disorder in the Positioning of Right- and Left-HandedHelical Chains, 192 188.8.131.52 Disorder in the Positioning of Up and Down Chains, 195 184.108.40.206 Disorder in the Orientation of Chains around the ChainAxis, 197 4.2.2 Substitutional Isomorphism of Different Monomeric Units, 200 4.2.3 Conformational Isomorphism, 202 4.2.4 Disorder in the Stacking of Ordered Layers of Chains(Stacking Fault Disorder), 204 220.127.116.11 Stacking Faults in Form I and Form II of sPP, 204 18.104.22.168 Stacking Faults in - and -Forms of iPP, 206 22.214.171.124 Stacking Faults in the -Form of sPS, 209 4.2.5 Conformational Kink-Band Disorder, 211 126.96.36.199 Conformational Kink-Band Disorder in PVDF, 212 188.8.131.52 Conformational Kink-Band Disorder in PE, 215 184.108.40.206 Conformational Kink-Band Disorder in sPP, 216 220.127.116.11 The Role of Kink-Band Disorder in the CooperativeCrystal Crystal Polymorphic Transitions, 218 4.3 Solid Mesophases, 219 4.3.1 LCs in Small Molecules and Polymers, 222 4.3.2 Solid Mesophases in Polymers, 227 4.3.3 Solid Mesophases of Class B: Crystals withThree-Dimensional Long-Range Order of Not-Point-Centered Features, 229 18.104.22.168 Solid Mesophase in 1,4-trans-Poly(1,3-butadiene)(trans-PBD), 230 22.214.171.124 Poly( -caprolactame) (Nylon 6), 232 126.96.36.199 Poly(acrylonitrile) (PAN), 235 188.8.131.52 Ethylene Propylene Random Copolymers, 239 184.108.40.206 Pseudohexagonal Form of PE at High Pressure andTemperature, 243 220.127.116.11 Poly(tetrafl uoroethylene) (PTFE), 245 18.104.22.168 Random Copolymers of Tetrafl uoroethylene withFluorinated Comonomers, 251 22.214.171.124 Alternating Ethylene Tetrafl uoroethylene (ETFE)Copolymers, 255 126.96.36.199 Alternating Ethylene-Norbornene Copolymers (ENCs), 264 188.8.131.52 Comblike Polymers, 271 4.3.4 Solid Mesophases of Class C: Crystals with Long-RangePositional Order in Only One or Two Dimensions, 271 184.108.40.206 Poly(ethylene terephthalate) (PET), 272 220.127.116.11 Isotactic Polypropylene (iPP), 275 18.104.22.168 Copolymers of iPP with Branched Comonomers, 276 22.214.171.124 Syndiotactic Polypropylene (sPP), 279 126.96.36.199 Copolymers of sPP, 284 188.8.131.52 Syndiotactic Polystyrene (sPS) and Methyl-SubstitutedPolystyrenes, 286 References, 287 5 Methods of Analysis of Diffuse Scattering from DisorderedStructures of Polymers 296 5.1 Structural Disorder and Diffuse Scattering, 296 5.2 Methods of Diffraction Analysis from Disordered Crystals, 298 5.3 Long-Range Order in Disordered Lattices of Class A, 300 5.4 SRO in Disordered Crystals of Class A, 302 5.5 Short-Range Order in Disordered Crystals withSubstitution-Type Disorder, 305 5.6 Short-Range versus Long-Range Order in Disordered Crystalsof Classes B and C (Solid Mesophases), 309 5.7 Disordered Models with Perturbations Occurring overContinuous Ranges, 311 5.8 Basic Formulas for the Calculation of X-Ray DiffractionIntensity from Disordered Model Structures of Polymers, 316 5.8.1 Brief Overview of Basic Formalism in X-Ray Modeling, 316 5.8.2 Effect of Longitudinal Translational Disorder andRotational Displacements of Chains about Their Axes: ExplicitFormulas, 319 5.8.3 Substitutional and Translational Disorder in OneDimension, 321 5.9 Examples of Calculation of Average Diffracted Intensity ofStructures Disordered in One Dimension, 328 5.9.1 Substitution-Type Disorder, 328 5.9.2 Translation-Type Disorder, 331 5.9.3 Stacking Fault Disorder in the -Form of sPS, 333 5.10 Line and Surface Integration Method of DiffractionIntensity for Fibers and Powders of Polycrystalline Samples, 337 References, 338 6 Crystal Habits 341 6.1 Basic Remarks, 341 6.2 Rounded Lateral Habits, 347 6.3 Chain Folding, Molecular Orientation, and Sectorization, 349 6.3.1 Chain Tilting, 349 6.3.2 Sectorization, 350 6.3.3 Nonplanar Lamellae, 352 6.4 Twinning and Secondary Nucleation Theory, 355 6.5 Homoepitaxy, Morphology, Stem Orientation, and Polymorphism, 359 References, 367 7 Influence of Crystal Defects and Structural Disorder on thePhysical and Mechanical Properties of Polymeric Materials369 7.1 Introduction, 369 7.2 Stress-Induced Phase Transformations during Deformation, 371 7.3 Isotactic Polypropylene (iPP), 373 7.3.1 Influence of Stereo- and Regiodefects on theCrystallization Behavior of iPP, 374 7.3.2 Influence of Stereo- and Regiodefects on the MechanicalProperties of iPP, 378 7.3.3 Stress-Induced Phase Transformations of iPP during TensileDeformation, 382 7.3.4 Elastic Properties and Phase Transformations inStereodefective iPP, 388 7.3.5 Influence of Constitutional Defects on the CrystallizationBehavior of iPP, 390 7.3.6 Influence of Constitutional Defects on the PhysicalProperties of iPP, 397 7.3.7 Influence of Conditions of Crystallization on the PhysicalProperties of iPP: The Mesomorphic Form, 406 184.108.40.206 Morphology of the Solid Mesophase of iPP, 407 220.127.116.11 Mechanical Properties of the Solid Mesophase of iPP, 412 18.104.22.168 Mechanical Properties of the -Form and SolidMesophase in Metallocene iPPs, 417 7.4 Syndiotactic Polypropylene (sPP), 422 7.4.1 Influence of Stereodefects on the Crystallization Behaviorof sPP, 424 7.4.2 Influence of Stereodefects on the Crystallization of theMesomorphic Form of sPP, 427 7.4.3 Influence of Stereodefects on the Crystallization oftrans-Planar and Helical Forms of sPP in Oriented Fibers:Stress-Induced Phase Transformations during Deformation, 428 7.4.4 Influence of Constitutional Defects on the CrystallizationBehavior of sPP, 431 7.4.5 Physical and Mechanical Properties of sPP, 434 22.214.171.124 Influence of Stereodefects on the Mechanical Propertiesof sPP, 434 126.96.36.199 Mechanical Properties of the Solid Mesophase of sPP, 440 References, 442 Index 449.
- (source: Nielsen Book Data)
- Publisher's Summary
- Polymeric crystals are more complex in nature than other materials' crystal structures due to significant structural disorder present. In fact, they actually exist in a semicrystalline state where the crystals are embedded in an amorphous phase to create a highly interconnected network. Presenting an in-depth and current overview of polymer crystals, Crystals and Crystallinity in Polymers provides researchers, engineers, and graduate students with guidelines to help select the proper crystallization method, evaluate polymer crystallization data, determine which methods to utilize for particular cases, and understand the different analytical techniques utilized.
(source: Nielsen Book Data)
- Publication date
- Machine generated contents note: Chapter 1 Configuration and Conformation of Macromolecules in Polymer Crystals 1.1 Crystals of polymers 1.2 Constitution and configuration of crystalline polymers 1.3 Conformation 1.4 Relationships among internal parameters of macromolecules 1.5 Conformation of polymer chains in the crystalline state 1.6 Helical conformations in isotactic and syndiotactic polymers 1.7 Conformational energy calculations 1.8 Helical conformation and optical activity 1.9 Alternating copolymers 1.10 Polydienes 1.11 Non helical chain conformations of isotactic polymers References Chapter 1 Chapter 2 Packing of macromolecules in polymer crystals 2.1 General principles 2.2 The principle of density (entropy)-driven phase formation in polymers 2.3 Symmetry breaking 2.4 Impact of chain folding on crystal structure symmetry 2.5 Frustrated Polymer Crystal Structures 2.6 Chiral crystallization of polymers with helical chain conformations 2.7 Packing effects on the conformation of polymer chains in the crystals: the case of aliphatic polyamides References Chapter 2 Chapter 3 3.1 X-ray diffraction of semicrystalline polymers 3.2 Fourier synthesis and the phase problem in crystallography 3.3 X-ray fiber diffraction analysis 3.4 Determination of parameters of the unit cell and indexing of the diffraction pattern 3.5 Measure of the integrated intensities of the reflections and corrections for geometrical (Lorentz), polarization and absorption factors 3.6 Calculation of Structure Factors 3.7 Structural refinement 3.8 Form of diffraction pattern and broadening due to the Laue function References Chapter 3 Chapter 4 Defects and Disorder in Polymer Crystals 4.1 Classification of different types of structural disorder 4.2 Crystals with partial three-dimensional order (Class A)Disorder with three-dimensional periodicity maintained only for some characterizing points of the structure 4.3 Solid mesophases References Chapter 4 Chapter 5 Methods of Analysis of Diffuse Scattering from Disordered Structures of Polymers 5.1 Structural disorder and diffuse scattering 5.2 Methods of diffraction analysis from disordered crystals 5.3 Long Range Order in Disordered Lattices of Class A 5.4 Short Range Order in Disordered Crystals of Class A 5.5 Short Range Order in Disordered Crystals with Substitution type Disorder 5.6 Short Range vs Long Range Order in Disordered Crystals of Class B and C (Solid Mesophases) 5.7 Disordered Models with Perturbations Occurring over Continuous Ranges 5.8 Basic formulas for the calculation of X-ray Diffraction Intensity from Disordered Model Structures of Polymers 5.9 Examples of calculation of average diffracted intensity of structures disordered in one dimension 5.10 Integration method of diffraction intensity for cylindrically and spherical surfaces in the reciprocal space References Chapter 5 Chapter 6 Crystal habit 6.1 Basic remark 6.2 Rounded lateral habits 6.3 Chain folding, molecular orientation and sectorization 6.4 Twinning and secondary nucleation theory 6.5 Homoepitaxy, morphology, stem orientation and polymorphism References Chapter 6 Chapter 7 Influence of Crystal Defects and Structural Disorder on the Physical and Mechanical Properties of Polymeric Materials 7.1 Introduction 7.2 Stress induced phase transformations during deformation 7.3 Isotactic polypropylene 7.4 Syndiotactic Polypropylene References Chapter 7 .
- Available in another form
- Print version: De Rosa, Claudio. Crystals and crystallinity in polymers Hoboken, New Jersey : Wiley, 2013 ( 9780470175767 )
- 9781118690598 (electronic bk.)
- 1118690591 (electronic bk.)
- 9780470175767 (hardback)