1 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies.

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Presentation transcript:

1 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

2 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

3 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

4 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

5 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

6 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

7 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

8 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

9 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Paul Phillips 1990 Review

10 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

11 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

12 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Paul Phillips 1990 Review Tacticity Tacticity governs the helical structure

13 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

14 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

15 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

16 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

17 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

18 Chain Folding and Crystallization

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20

21 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies n-alkane boiling and melting points “n” Boiling (top) or Melting (bottom) Point

22 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies “Crystals act like crosslinks in rubber” P. Phillips 1990

23 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

24 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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29 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

30 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Solution Crystallization

31

32 Why do Chains Fold?

33 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,

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

35 Why do Chains Fold? or

36 Hoffman-Weeks Plot

37 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

38 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

39 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

40 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

41 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

42 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

43 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)

44 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

45 Hoffman-Lauritzen Secondary Nucleation Theory

46 Hoffman-Lauritzen Secondary Nucleation Theory

47 Hoffman-Lauritzen Secondary Nucleation Theory Add a first stem, then subsequent stems. First stem and subsequent stems add 2b 0 σl and b 0 σl To the free energy (cost to make a surface)

48 Hoffman-Lauritzen Secondary Nucleation Theory First stem:

49 Hoffman-Lauritzen Secondary Nucleation Theory

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51

52

53 Hoffman-Lauritzen Secondary Nucleation Theory

54

55 Hoffman-Lauritzen Secondary Nucleation Theory

56 Hoffman-Lauritzen Secondary Nucleation Theory

57 Hoffman-Lauritzen Secondary Nucleation Theory

58 Hoffman-Lauritzen Secondary Nucleation Theory

59 Primary Nucleation

60 Primary Nucleation

61 Spherulites

62 Primary Nucleation

63 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

64 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

65 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Non Crystallographic Branching

66 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

67 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

68 Spherulitic Growth Rate

69 Avrami Equation

70 Avrami Equation

71 Avrami Equation

72 Avrami Equation

73 Avrami Equation

74 Avrami Equation