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Nonlinear Polymer Rheology: Macroscopic Phenomenology and Molecular Foundation

Nonlinear Polymer Rheology: Macroscopic Phenomenology and Molecular Foundation

Shi-Qing Wang

ISBN: 978-1-119-02905-2

Dec 2017

464 pages

Product not available for purchase


Integrating latest research results and characterization techniques, this book helps readers understand and apply fundamental principles in nonlinear polymer rheology. The author connects the basic theoretical framework with practical polymer processing, which aids practicing scientists and engineers to go beyond the existing knowledge and explore new applications. Although it is not written as a textbook, the content can be used in an upper undergraduate and first year graduate course on polymer rheology.

•    Describes the emerging phenomena and associated conceptual understanding in the field of nonlinear polymer rheology
•    Incorporates details on latest experimental discoveries and provides new methodology for research in polymer rheology
•    Integrates latest research results and new characterization techniques like particle tracking velocimetric method
•    Focuses on the issues concerning the conceptual and phenomenological foundations for polymer rheology
•   Has a companion website for readers to access with videos complementing the content within several chapters





1. Phenomenological description of linear viscoelasticity (LVE)

1.1 Basic modes of deformation                                               

1.2 Linear responses

1.3 Classical rubber elasticity theory

2. Molecular characterization in LVE regime

2.1 Dilute limit                                                                                                                                                                  

2.2 Entangled state

2.3 Molecular-level descriptions of entanglement dynamics                                                                                       

2.4 Temperature dependence3. Experimental Methods

3.1 Shear rheometry

3.2 Extensional rheometry

3.3 Rheo-optical (in situ) methods

3.4 Advanced rheometric methods

4. Characterization of deformation field

4.1 Basic features in simple shear

4.2 Yield stress in Bingham type (yield-stress) fluids

4.3 Cases of homogeneous shear

4.4 Particle tracking velocimetry (PTV)                                                                                                   

4.5 Single molecule imaging velocimetry (SMIV)                                                                                               

4.6 Other visualization methods

5. Improved and other rheometric apparatuses

5.1 Linearly displaced co-cylinder for simple shear

5.2 Cone-partitioned plate for rotational shear

5.3 Other forms of large deformation

5.4 Conclusion


6. Wall slip – Interfacial yielding

6.1 Basic notion of wall slip in steady shear

6.2 Stick-slip transition (in stress-controlled mode

6.3 Wall slip during startup shear - Interfacial yielding                     

6.4 Relationship between slip and bulk shear deformation

6.5 Molecular evidence of disentanglement during wall slip

6.6 Uncertainty in boundary condition

6.7 Conclusion

7. Yielding during startup deformation: from elastic deformation to flow

7.1 Yielding at Wi < 1 and steady shear thinning at Wi > 1

7.2 Stress overshoot in fast startup shear

7.3 Nature of steady shear

7.4 From terminal flow to fast flow under creep: entanglement-disentanglement transition

7.5 Yielding in startup uniaxial extension

7.6 Conclusion

8. Strain hardening in extension

8.1 Conceptual pictures

8.2 Origin of ""strain hardening"" in uniaxial extension

8.3 True strain hardening: non-Gaussian stretching from finite extensibility

8.4 Different responses of entanglement to startup extension and shear

8.5 Conclusion

Appendix 8.A: Conceptual and mathematical account of geometric condensation

9. Shear banding in startup and oscillatory shear: PTV observations

9.1 Shear banding after overshoot in startup shear

9.2 Overcoming wall slip during startup shear

9.3 Shear banding in LAO

10. Strain localization in pressure-driven extrusion, squeezing, and planar extension

10.1 Capillary rheometry in rate-controlled mode

10.2 Instabilities at die entry

10.3 Squeezing deformation

10.4 Planar extension

11. Different modes of structural failure during startup uniaxial extension

11.1 Tensile-like failure (decohesion) at low rates

11.2 Shear yielding and necking-like strain localization at high rates

11.3 Rupture without crosslinking at even higher rates: where is disentanglement?

11.4 Strain localization vs. steady-flow: Sentmanat extensional rheometry vs. Filament stretching rheometry

11.5 Role of long chain branching

Appendix 11.A: Analogy between capillary rheometry and filament stretching rheometry


12. Elastic yielding in stepwise simple shear

12.1 Strain softening after large step strain

12.2 PTV revelation of non-quiescent relaxation: localized elastic yielding

12.3 Quiescent elastic yielding

12.4 Arrested wall slip: elastic yielding at interfaces

12.5 Conclusion

13. Elastic breakup in stepwise uniaxial extension

13.1 Rupture-like failure during relaxation at small magnitude or small rate (WiR < 1)

13.2 Shear-yielding induced failure upon fast large stepwise extension (WiR > 1)

13.3 Nature of the elastic breakup probed by infrared thermal imaging measurements

13.4 Primitive phenomenological explanations

13.5 Stepwise squeeze and planar extension

14. Finite cohesion and the role of chain architecture

14.1 Cohesive strength of an entanglement network

14.2 Enhancing cohesion barrier with long-chain branching to prevent structural breakup


15. Homogeneous entanglement

15.1 What is chain entanglement?

15.2 When, how and why disentanglement occurs

15.3 Criterion for homogeneous shear

15.4 Constitutive non-monotonicity

15.5 Metastable nature of shear banding

16. Molecular networks as the conceptual foundation

16.1 Introduction: the tube model and its predictions

16.2 Essential ingredients in formulation of a new molecular picture

16.3 Overcoming finite cohesion after step deformation: Quiescent or not

16.4 Forced microscopic yielding during startup deformation: stress overshoot

16.5 Interfacial yielding by disentanglement

16.6 Effect of long chain branching

16.7 Decohesion in startup creep: entanglement-disentanglement transition

16.8 Emerging microscopic theory of Sussman and Schweizer

16.9 Further tests to reveal the nature of polymer deformation

16.10 Conclusion

17.  ""Anomalous"" phenomena

17.1 Essence of rheometric measurements: isothermal condition

17.2 Internal energy buildup and non-Gaussian extension

17.3 Breakdown of time-temperature superposition during transient response: shear and extension

17.4 Strain hardening in simple shear of certain polymer solutions

17.5 Lack of universal nonlinear responses: solutions vs. melts

17.6 Emergence of transient glassy responses

18. Difficulties with orthodox paradigams

18.1 Tube model does not to predict key experimental features

18.2 Confusion about local and global deformation

18.3 Molecular network paradigm

19. Strain localization and the fluid mechanics of polymeric liquids

19.1 Relationship between wall slip and banding: a rheological-state diagram

19.2 Modeling of continuum fluid mechanics of entangled polymeric liquids

19.3 Challenges in polymer processing  

20. Conclusions

20.1 Theoretical challenges

20.2 Experimental difficulties