Semi-Crystalline Polymer Morphologies and their Hierarchical - - PowerPoint PPT Presentation

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Semi-Crystalline Polymer Morphologies and their Hierarchical - - PowerPoint PPT Presentation

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies 1 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Semi-Crystalline Helical Structure Chain Folding Semi-Crystalline Fibrillar Growth

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Semi-Crystalline Helical Structure Chain Folding Semi-Crystalline Fibrillar Growth Spherulitic, shish-kabob, epitaxial surface nucleation, Crystalline Orientation Lamellar Orientation Macroscopic Orientation

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Paul Phillips 1990 Review

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Paul Phillips 1990 Review Rigid, semi-Rigid, Flexible Polymer Chains On melting the entropy gain is small because the crystallizing units are chemically bound. The random coil state is seen classically as the highest entropy state. For rigid polymers the ground state may be a lower entropy state. Kevlar Polythiophene

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Paul Phillips 1990 Review Tacticity Tacticity governs the helical structure

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Chain Folding and Crystallization

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

n-alkane boiling and melting points “n” Boiling (top) or Melting (bottom) Point

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

“Crystals act like crosslinks in rubber” P . Phillips 1990

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Solution Crystallization

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Why do Chains Fold? http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Why do Chains Fold? For an infinite crystal V/S is very large and we can ignore the surface At the equilibrium melting point ΔG = 0 so: substituting in the first equation,

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Why do Chains Fold? For a lamellar crystal S is 2R2 and V is tR2 At a pseudo-equilibrium point where the crystal has a finite thickness of t and a depressed melting point, T

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Why do Chains Fold?

  • r
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Hoffman-Weeks Plot http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Diffusion of impurities versus growth rate of crystallization front J = -D dc/dx for flux of impurities G = linear growth rate of crystal D/G = δ, the Keith-Padden δ-parameter This determines the coarseness of the spherulite (lateral size)

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf Add a first stem, then subsequent stems. First stem and subsequent stems add 2b0σl and b0σl To the free energy (cost to make a surface)

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf First stem:

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Spherulites http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

Non Crystallographic Branching

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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Spherulitic Growth Rate

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

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Avrami Equation

http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf