1. 1 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

2. 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. 3 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

4. 4 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

5. 5 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

6. 6 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

7. 7 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

8. 8 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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

10. 10 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

11. 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. 12 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies Paul Phillips 1990 Review Tacticity Tacticity governs the helical structure

13. 13 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

14. 14 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

15. 15 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

16. 16 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

17. 17 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

18. 18 Chain Folding and Crystallization

19. 19

20. 20

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

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

23. 23 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

24. 24 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

25. 25

26. 26

27. 27

28. 28 http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

29. 29 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

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

31. 31

32. 32 Why do Chains Fold? http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

33. 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. 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. 35 Why do Chains Fold? or

36. 36 Hoffman-Weeks Plot http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

37. 37 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

38. 38 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

39. 39 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

40. 40 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

41. 41 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

42. 42 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

43. 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. 44 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

45. 45 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

46. 46 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

47. 47 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 2b 0 σl and b 0 σl To the free energy (cost to make a surface)

48. 48 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf First stem:

49. 49 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

50. 50 http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

51. 51 http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

52. 52 http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

53. 53 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

54. 54 http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

55. 55 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

56. 56 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

57. 57 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

58. 58 Hoffman-Lauritzen Secondary Nucleation Theory http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

59. 59 Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

60. 60 Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

61. 61 Spherulites http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

62. 62 Primary Nucleation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

63. 63 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

64. 64 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies http://www.eng.uc.edu/~gbeaucag/Classes/MorphologyofComplexMaterials/Chapter2html/Chapter2.html

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

66. 66 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

67. 67 Semi-Crystalline Polymer Morphologies and their Hierarchical Morphologies

68. 68 Spherulitic Growth Rate

69. 69 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

70. 70 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

71. 71 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

72. 72 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

73. 73 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf

74. 74 Avrami Equation http://scholar.lib.vt.edu/theses/available/etd-051799-162256/unrestricted/polyimide2.pdf