Crystals and Crystallinity in Polymers Diffraction Analysis of Ordered and Disordered Crystals

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  • Format: Hardcover
  • Copyright: 2013-11-04
  • Publisher: Wiley

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Provides the tools needed to master and apply the fundamentals of polymer crystallography

Using core concepts in physics, chemistry, polymer science and engineering, this book sheds new light on the complex field of polymer crystallography, enabling readers to evaluate polymer crystallization data and determine the best methods to use for their investigations. The authors set forth a variety of tested and proven methods for analyzing ordered and disordered structures in polymer crystals, including X-ray diffraction, electron diffraction, and microscopy. In addition to the basics, the book explores several advanced and emerging topics in the field such as symmetry breaking, frustration, and the principle of density-driven phase formation.

Crystals and Crystallinity in Polymers introduces two new concepts in crystallinity and crystals in synthetic polymers. First, crystallinity in polymeric materials is compatible with the absence of true three-dimensional long-range order. Second, the disorder may be described as a structural feature, using the methods of X-ray scattering and electron diffraction analysis.

The book begins by introducing the basic principles and methods for building structural models for the conformation of polymer crystal chains. Next, it covers:

  • Packing of macromolecules in polymer crystals
  • Methods for extracting structural parameters from diffraction data
  • Defects and disorder in polymer crystals
  • Analytical methods for diffuse scattering from disordered polymer structures
  • Crystal habit
  • Influence of crystal defects and structural disorder on the physical and mechanical properties of polymeric materials

Crystals and Crystallinity in Polymers examines all the possible types of structural disorder generally present in polymer crystals and describes the influence of each kind of disorder on X-ray and electron diffraction patterns. Its comprehensive, expert coverage makes it possible for readers to learn and apply the fundamentals of polymer crystallography to solve a broad range of problems.

Author Biography

CLAUDIO DE ROSA, PhD, is Full Professor of Industrial and Macromolecular Chemistry at the University of Napoli. His research examines the relationships between molecular structure and the physical properties of polymers. He also studies polymers that form into nanostructures by self-assembly.

FINIZIA AURIEMMA, PhD, is Associate Professor of Industrial and Macromolecular Chemistry at the University of Napoli. She conducts theoretical and experimental studies of partially ordered macromolecular systems and polymer gels.

Table of Contents

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

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