Handbook of Polymer Crystallization

<p>Preface xiii</p>
<p>Contributors xv</p>
<p>1 Experimental Techniques 1<br /> Benjamin S. Hsiao, Feng Zuo, and Yimin Mao, Christoph Schick</p>
<p>1.1 Introduction, 1</p>
<p>1.2 Optical Microscopy, 2</p>
<p>1.2.1 Reflection and Transmission Microscopy, 2</p>
<p>1.2.2 Contrast Modes, 2</p>
<p>1.2.3 Selected Applications, 3</p>
<p>1.3 Electron Microscopy, 5</p>
<p>1.3.1 Imaging Principle, 5</p>
<p>1.3.2 Sample Preparation, 6</p>
<p>1.3.3 Relevant Experimental Techniques, 7</p>
<p>1.3.4 Selected Applications, 8</p>
<p>1.4 Atomic Force Microscopy, 9</p>
<p>1.4.1 Imaging Principle, 9</p>
<p>1.4.2 Scanning Modes, 9</p>
<p>1.4.3 Comparison between AFM and EM, 10</p>
<p>1.4.4 Recent Development: Video AFM, 10</p>
<p>1.4.5 Selected Applications, 10</p>
<p>1.5 Nuclear Magnetic Resonance, 12</p>
<p>1.5.1 Chemical Shift, 13</p>
<p>1.5.2 Relevant Techniques, 13</p>
<p>1.5.3 Recent Development: Multidimensional NMR, 14</p>
<p>1.5.4 Selected Applications, 14</p>
<p>1.6 Scattering Techniques: X–Ray, Light, and Neutron, 15</p>
<p>1.6.1 Wide–Angle X–Ray Diffraction, 15</p>
<p>1.6.2 Small–Angle X–Ray Scattering, 17</p>
<p>1.6.3 Small–Angle Light Scattering, 19</p>
<p>1.6.4 Small–Angle Neutron Scattering, 21</p>
<p>1.7 Differential Scanning Calorimetry, 22</p>
<p>1.7.1 Modes of Operation, 22</p>
<p>1.7.2 Determination of Degree of Crystallinity, 25</p>
<p>1.8 Summary, 25</p>
<p>Acknowledgments, 26</p>
<p>References, 26</p>
<p>2 Crystal Structures of Polymers 31<br /> Claudio De Rosa and Finizia Auriemma</p>
<p>2.1 Constitution and Confi guration of Polymer Chains, 31</p>
<p>2.2 Conformation of Polymer Chains in Crystals and Conformational Polymorphism, 33</p>
<p>2.3 Packing of Macromolecules in Polymer Crystals, 43</p>
<p>2.4 Symmetry Breaking, 49</p>
<p>2.5 Packing Effects on the Conformation of Polymer Chains in the Crystals: The Case of Aliphatic Polyamides, 50</p>
<p>2.6 Defects and Disorder in Polymer Crystals, 55</p>
<p>2.6.1 Substitutional Isomorphism of Different Chains, 56</p>
<p>2.6.2 Substitutional Isomorphism of Different Monomeric Units, 57</p>
<p>2.6.3 Conformational Isomorphism, 58</p>
<p>2.6.4 Disorder in the Stacking of Ordered Layers (Stacking Fault Disorder), 58</p>
<p>2.7 Crystal Habits, 60</p>
<p>2.7.1 Rounded Lateral Habits, 66</p>
<p>Acknowledgments, 67</p>
<p>References, 67</p>
<p>3 Structure of Polycrystalline Aggregates 73<br /> Buckley Crist</p>
<p>3.1 Introduction, 73</p>
<p>3.2 Crystals Grown from Solution, 75</p>
<p>3.2.1 Facetted Monolayer Crystals from Dilute Solution, 75</p>
<p>3.2.2 Dendritic Crystals from Dilute Solution, 81</p>
<p>3.2.3 Growth Spirals in Dilute Solution, 85</p>
<p>3.2.4 Concentrated Solutions, 92</p>
<p>3.3 Crystals and Aggregates Grown from Molten Films, 94</p>
<p>3.3.1 Structures in Thin Films, 94</p>
<p>3.3.2 Structures in Ultrathin Films, 98</p>
<p>3.3.3 Edge–On Lamellae in Molten Films, 102</p>
<p>3.4 Spherulitic Aggregates, 104</p>
<p>3.4.1 Optical Properties of Spherulites, 105</p>
<p>3.4.2 Occurrence of Spherulites, 108</p>
<p>3.4.3 Development of Spherulites, 110</p>
<p>3.4.4 Banded Spherulites and Lamellar Twist, 116</p>
<p>Acknowledgments, 121</p>
<p>References, 121</p>
<p>4 Polymer Nucleation 125<br /> Kiyoka N. Okada and Masamichi Hikosaka</p>
<p>4.1 Introduction, 126</p>
<p>4.2 Classical Nucleation Theory, 126</p>
<p>4.2.1 Nucleation Rate (I), 126</p>
<p>4.2.2 Free Energy for Formation of a Nucleus G(N), 127</p>
<p>4.2.3 Free Energy for Formation of a Critical Nucleus ( G∗), 127</p>
<p>4.2.4 Shape of a Nucleus Is Related to Kinetic Parameters, 128</p>
<p>4.2.5 Diffusion, 128</p>
<p>4.3 Direct Observation of Nano–Nucleation by Synchrotron Radiation, 128</p>
<p>4.3.1 Introduction and Experimental Procedure, 128</p>
<p>4.3.2 Observation of Nano–Nucleation by SAXS, 128</p>
<p>4.3.3 Extended Guinier Plot Method and Iteration Method, 129</p>
<p>4.3.4 Kinetic Parameters and Size Distribution of the Nano–Nucleus, 130</p>
<p>4.3.5 Real Image of Nano–Nucleation, 131</p>
<p>4.3.6 Supercooling Dependence of Nano–nucleation, 133</p>
<p>4.3.7 Relationship between Nano–Nucleation and Macro–Crystallization, 133</p>
<p>4.4 Improvement of Nucleation Theory, 135</p>
<p>4.4.1 Introduction, 135</p>
<p>4.4.2 Nucleation Theory Based on Direct Observation of Nucleation, 135</p>
<p>4.4.3 Confirmation of the Theory by Overall Crystallinity, 137</p>
<p>4.5 Homogeneous Nucleation from the Bulk Melt under Elongational Flow, 139</p>
<p>4.5.1 Introduction and Case Study, 139</p>
<p>4.5.2 Formulation of Elongational Strain Rate e, 139</p>
<p>4.5.3 Nano–Oriented Crystals, 140</p>
<p>4.5.4 Evidence of Homogeneous Nucleation, 144</p>
<p>4.5.5 Nano–Nucleation Results in Ultrahigh Performance, 147</p>
<p>4.6 Heterogeneous Nucleation, 148</p>
<p>4.6.1 Introduction, 148</p>
<p>4.6.2 Experimental, 149</p>
<p>4.6.3 Role of Epitaxy in Heterogeneous Nucleation, 150</p>
<p>4.6.4 Acceleration Mechanism of Nucleation of Polymers by Nano–Sizing of Nucleating Agent, 153</p>
<p>4.7 Effect of Entanglement Density on the Nucleation Rate, 156</p>
<p>4.7.1 Introduction and Experimental, 156</p>
<p>4.7.2 Increase of e Leads to a Decrease of I, 157</p>
<p>4.7.3 Change of e with t, 158</p>
<p>4.7.4 Two–Step Entangling Model, 159</p>
<p>4.8 Conclusion, 160</p>
<p>Acknowledgments, 161</p>
<p>References, 161</p>
<p>5 Growth of Polymer Crystals 165<br /> Kohji Tashiro</p>
<p>5.1 Introduction, 165</p>
<p>5.1.1 Complex Behavior of Polymers, 165</p>
<p>5.2 Growth of Polymer Crystals from Solutions, 167</p>
<p>5.2.1 Single Crystals, 167</p>
<p>5.2.2 Crystallization from Solution under Shear, 168</p>
<p>5.2.3 Solution Casting Method, 168</p>
<p>5.3 Growth of Polymer Crystals from Melt, 169</p>
<p>5.3.1 Positive and Negative Spherulites, 169</p>
<p>5.3.2 Spherulite Morphology and Crystalline Modification, 170</p>
<p>5.3.3 Spherulite Patterns of Blend Samples, 172</p>
<p>5.4 Crystallization Mechanism of Polymer, 173</p>
<p>5.4.1 Basic Theory of Crystallization of Polymer, 173</p>
<p>5.4.2 Growth Rate of Spherulites, 177</p>
<p>5.5 Microscopically Viewed Structural Evolution in the Growing Polymer Crystals, 178</p>
<p>5.5.1 Experimental Techniques, 178</p>
<p>5.5.2 Structural Evolution in Isothermal Crystallization, 179</p>
<p>5.5.3 Shear–Induced Crystallization of the Melt, 186</p>
<p>5.6 Crystallization upon Heating from the Glassy State, 189</p>
<p>5.6.1 Cold Crystallization, 189</p>
<p>5.6.2 Solvent–Induced Crystallization of Polymer Glass, 189</p>
<p>5.7 Crystallization Phenomenon Induced by Tensile Force, 191</p>
<p>5.8 Photoinduced Formation and Growth of Polymer Crystals, 191</p>
<p>5.9 Conclusion, 192</p>
<p>References, 193</p>
<p>6 Computer Modeling of Polymer Crystallization 197<br /> Gregory C. Rutledge</p>
<p>6.1 Introduction, 197</p>
<p>6.2 Methods, 198</p>
<p>6.2.1 Molecular Dynamics, 199</p>
<p>6.2.2 Langevin Dynamics, 200</p>
<p>6.2.3 Monte Carlo, 200</p>
<p>6.2.4 Kinetic Monte Carlo, 201</p>
<p>6.3 Single–Chain Behavior in Crystallization, 202</p>
<p>6.3.1 Solid–on–Solid Models, 202</p>
<p>6.3.2 Molecular and Langevin Dynamics, 203</p>
<p>6.4 Crystallization from the Melt, 204</p>
<p>6.4.1 Lattice Monte Carlo Simulations, 205</p>
<p>6.4.2 Molecular Dynamics Using Coarse–Grained Models, 206</p>
<p>6.4.3 Molecular Dynamics Using Atomistic Models, 207</p>
<p>6.5 Crystallization under Deformation or Flow, 208</p>
<p>6.6 Concluding Remarks, 210</p>
<p>References, 211</p>
<p>7 Overall Crystallization Kinetics 215<br /> Ewa Piorkowska and Andrzej Galeski</p>
<p>7.1 Introduction, 215</p>
<p>7.2 Measurements, 216</p>
<p>7.3 Simulation, 217</p>
<p>7.4 Theories: Isothermal and Nonisothermal Crystallization, 218</p>
<p>7.4.1 Introductory Remarks, 218</p>
<p>7.4.2 Extended Volume Approach, 218</p>
<p>7.4.3 Probabilistic Approaches, 220</p>
<p>7.4.4 Isokinetic Model, 223</p>
<p>7.4.5 Rate Equations, 223</p>
<p>7.5 Complex Crystallization Conditions: General Models, 224</p>
<p>7.6 Factors Influencing the Overall Crystallization Kinetics, 224</p>
<p>7.6.1 Crystallization in a Uniform Temperature Field, 224</p>
<p>7.6.2 Crystallization in a Temperature Gradient, 225</p>
<p>7.6.3 Crystallization in a Confi ned Space, 226</p>
<p>7.6.4 Flow–Induced Crystallization, 228</p>
<p>7.7 Analysis of Crystallization Data, 230</p>
<p>7.7.1 Isothermal Crystallization, 230</p>
<p>7.7.2 Nonisothermal Crystallization, 231</p>
<p>7.8 Conclusions, 233</p>
<p>References, 234</p>
<p>8 Epitaxial Crystallization of Polymers: Means and Issues 237<br /> Annette Thierry and Bernard A. Lotz</p>
<p>8.1 Introduction and History, 237</p>
<p>8.2 Means of Investigation of Epitaxial Crystallization, 239</p>
<p>8.2.1 Global Techniques, 239</p>
<p>8.2.2 Thin Film Techniques, 239</p>
<p>8.2.3 Sample Preparation Techniques, 240</p>
<p>8.2.4 Other Samples and Investigation Procedures, 241</p>
<p>8.3 Epitaxial Crystallization of Polymers, 241</p>
<p>8.3.1 General Principles, 241</p>
<p>8.3.2 Epitaxial Crystallization of Linear Polymers, 243</p>
<p>8.3.3 Epitaxy of Helical Polymers, 245</p>
<p>8.3.4 Polymer/Polymer Epitaxy, 250</p>
<p>8.4 Epitaxial Crystallization: Further Issues and Examples, 252</p>
<p>8.4.1 Topographic versus Lattice Matching, 252</p>
<p>8.4.2 Epitaxy of Isotactic Polypropylene on Isotactic Polyvinylcyclohexane, 254</p>
<p>8.4.3 Epitaxy Involving Fold Surfaces of Polymer Crystals, 254</p>
<p>8.5 Epitaxial Crystallization: Some Issues and Applications, 256</p>
<p>8.5.1 Epitaxial Crystallization and the Design of New Nucleating Agents, 256</p>
<p>8.5.2 Epitaxial Crystallization and the Design of Composite Materials, 257</p>
<p>8.5.3 Conformational and Packing Energy Analysis of Polymer Epitaxy, 258</p>
<p>8.5.4 Epitaxy as a Means to Generate Oriented Opto– or Electroactive Materials, 259</p>
<p>8.6 Conclusions, 260</p>
<p>References, 262</p>
<p>9 Melting 265<br /> Marek Pyda</p>
<p>9.1 Introduction to the Melting of Polymer Crystals, 265</p>
<p>9.2 Parameters of the Melting Process, 267</p>
<p>9.3 Change of Conformation, 268</p>
<p>9.4 Heat of Fusion and Degree of Crystallinity, 270</p>
<p>9.4.1 Heat of Fusion, 270</p>
<p>9.4.2 Degree of Crystallinity, 272</p>
<p>9.5 Equilibrium Melting, 274</p>
<p>9.5.1 The Equilibrium Melting Temperature, 274</p>
<p>9.5.2 The Equilibrium Thermodynamic Functions, 275</p>
<p>9.6 Other Factors Affecting the Melting Process of Polymer Crystals, 277</p>
<p>9.6.1 The Influence of the Polymer s Chemical Structure on the Melting Process, 277</p>
<p>9.6.2 The Effect of Polymer Molar Mass on the Melting Behavior, 277</p>
<p>9.6.3 Influence of Heating Rate on the Melting, 278</p>
<p>9.6.4 Multiple Melting Peaks of Polymers, 279</p>
<p>9.6.5 Influence of Pressure on the Melting Process, 281</p>
<p>9.6.6 The Melting Process by Other Methods, 281</p>
<p>9.6.7 Diluents Effect: The Influence of Small Diluents on the Melting Process, 282</p>
<p>9.7 Irreversible and Reversible Melting, 282</p>
<p>9.8 Conclusions, 284</p>
<p>References, 285</p>
<p>10 Crystallization of Polymer Blends 287<br /> Mariano Pracella</p>
<p>10.1 General Introduction, 287</p>
<p>10.2 Thermodynamics of Polymer Blends, 288</p>
<p>10.2.1 General Principles, 288</p>
<p>10.3 Miscible Polymer Blends, 290</p>
<p>10.3.1 Introduction, 290</p>
<p>10.3.2 Phase Morphology, 291</p>
<p>10.3.3 Crystal Growth Rate, 292</p>
<p>10.3.4 Overall Crystallization Kinetics, 294</p>
<p>10.3.5 Melting Behavior, 295</p>
<p>10.3.6 Blends with Partial Miscibility, 296</p>
<p>10.3.7 Crystallization Behavior of Amorphous/Crystalline Blends, 297</p>
<p>10.3.8 Crystallization Behavior of Crystalline/Crystalline Blends, 298</p>
<p>10.4 Immiscible Polymer Blends, 303</p>
<p>10.4.1 Introduction, 303</p>
<p>10.4.2 Morphology and Crystal Nucleation, 303</p>
<p>10.4.3 Crystal Growth Rate, 304</p>
<p>10.4.4 Crystallization Behavior of Immiscible Blends, 305</p>
<p>10.5 Compatibilized Polymer Blends, 307</p>
<p>10.5.1 Compatibilization Methods, 307</p>
<p>10.5.2 Morphology and Phase Interactions, 308</p>
<p>10.5.3 Crystallization Behavior of Compatibilized Blends, 311</p>
<p>10.6 Polymer Blends with Liquid–Crystalline Components, 314</p>
<p>10.6.1 Introduction, 314</p>
<p>10.6.2 Mesomorphism and Phase Transition Behavior of Liquid Crystals and Liquid Crystal Polymers, 314</p>
<p>10.6.3 Crystallization Behavior of Polymer/LC Blends, 316</p>
<p>10.6.4 Crystallization Behavior of Polymer/LCP Blends, 317</p>
<p>10.7 Concluding Remarks, 320</p>
<p>Abbreviations, 321</p>
<p>References, 322</p>
<p>11 Crystallization in Copolymers 327<br /> Sheng Li and Richard A. Register</p>
<p>11.1 Introduction, 327</p>
<p>11.2 Crystallization in Statistical Copolymers, 328</p>
<p>11.2.1 Flory s Model, 328</p>
<p>11.2.2 Solid–State Morphology, 330</p>
<p>11.2.3 Mechanical Properties, 334</p>
<p>11.2.4 Crystallization Kinetics, 335</p>
<p>11.2.5 Statistical Copolymers with Two Crystallizable Units, 337</p>
<p>11.2.6 Crystallization Thermodynamics, 337</p>
<p>11.3 Crystallization of Block Copolymers from Homogeneous or Weakly Segregated Melts, 340</p>
<p>11.3.1 Solid–State Morphology, 340</p>
<p>11.3.2 Crystallization–Driven Structure Formation, 342</p>
<p>11.4 Summary, 343</p>
<p>References, 344</p>
<p>12 Crystallization in Nano–Confi ned Polymeric Systems 347<br /> Alejandro J. M&uuml;ller, Maria Luisa Arnal, and Arnaldo T. Lorenzo</p>
<p>12.1 Introduction, 347</p>
<p>12.2 Confined Crystallization in Block Copolymers, 348</p>
<p>12.2.1 Crystallization within Diblock Copolymers that are Strongly Segregated or Miscible and Contain only One Crystallizable Component, 351</p>
<p>12.2.2 Crystallization within Strongly Segregated Double–Crystalline Diblock Copolymers and Triblock Copolymers, 355</p>
<p>12.3 Crystallization of Droplet Dispersions and Polymer Layers, 361</p>
<p>12.4 Polymer Blends, 368</p>
<p>12.4.1 Immiscible Polymer Blends, 368</p>
<p>12.4.2 Melt Miscible Blends, 371</p>
<p>12.5 Modeling of Confi ned Crystallization of Macromolecules, 371</p>
<p>12.6 Conclusions, 372</p>
<p>References, 372</p>
<p>13 Crystallization in Polymer Composites and Nanocomposites 379<br /> Ewa Piorkowska</p>
<p>13.1 Introduction, 379</p>
<p>13.2 Microcomposites with Particulate Fillers, 380</p>
<p>13.3 Fiber–Reinforced Composites, 382</p>
<p>13.4 Modeling of Crystallization in Fiber–Reinforced Composites, 385</p>
<p>13.5 Nanocomposites, 388</p>
<p>13.6 Conclusions, 393</p>
<p>Appendix, 393</p>
<p>References, 394</p>
<p>14 Flow–Induced Crystallization 399<br /> Gerrit W.M. Peters, Luigi Balzano, and Rudi J.A. Steenbakkers</p>
<p>14.1 Introduction, 399</p>
<p>14.2 Shear–Induced Crystallization, 401</p>
<p>14.2.1 Nature of Crystallization Precursors, 405</p>
<p>14.3 Crystallization during Drawing, 407</p>
<p>14.3.1 Spinning, 408</p>
<p>14.3.2 Elongation–Induced Crystallization; Lab Conditions, 409</p>
<p>14.4 Models of Flow–Induced Crystallization, 410</p>
<p>14.4.1 Flow–Enhanced Nucleation, 411</p>
<p>14.4.2 Flow–Induced Shish Formation, 419</p>
<p>14.4.3 Application to Injection Molding, 421</p>
<p>14.5 Concluding Remarks, 426</p>
<p>References, 427</p>
<p>15 Crystallization in Processing Conditions 433<br /> Jean–Marc Haudin</p>
<p>15.1 Introduction, 433</p>
<p>15.2 General Effects of Processing Conditions on Crystallization, 433</p>
<p>15.2.1 Effects of Flow, 433</p>
<p>15.2.2 Effects of Pressure, 435</p>
<p>15.2.3 Effects of Cooling Rate, 436</p>
<p>15.2.4 Effects of a Temperature Gradient, 437</p>
<p>15.2.5 Effects of Surfaces, 439</p>
<p>15.3 Modeling, 440</p>
<p>15.3.1 General Framework, 440</p>
<p>15.3.2 Simplifi ed Expressions, 441</p>
<p>15.3.3 General Systems of Differential Equations, 441</p>
<p>15.4 Crystallization in Some Selected Processes, 442</p>
<p>15.4.1 Cast Film Extrusion, 442</p>
<p>15.4.2 Fiber Spinning, 445</p>
<p>15.4.3 Film Blowing, 448</p>
<p>15.4.4 Injection Molding, 454</p>
<p>15.5 Conclusion, 458</p>
<p>References, 459</p>
<p>Index 463</p>