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1

2 (a) (b) (c) (d) Wunderlich

3 2.5.1

4 = = = (hkl) {hkl} [hkl] <hkl>

5 L tan 2θ = r L nλ = 2dsinθ dhkl ( ) = h k l + + a b c

6 c l=2 l=1 l=0 Polanyi nλ = I sinφ I:

7 B A a 110 B c 110 b b 110 µ a 110 A 10nm

8 c * a b c = * b c a = / V / V V = ab ( c) H hkl s 0 = 2 sinθ = λ 1 d hkl

9 B a A 110 B 110 c 110 b a b 110 A

10 (AFM) (STM)

11 (HDPE Mw=520k) 343K (a) (b) (c) scanning direction 3 µm 3 µm cantilever 2nm

12

13

14 Nakajima 1972 λ = 2d sinθ

15

16 2) 30

17

18 PE : n a =n. b =1.51 n c =1.58( ) n=n c -n a =0.07. a b PE : a=0.493 nm b=0.740 nm c=0.253 nm γ β c a α β b

19 5µm 5µm 2 µm µ µ

20 5µm 5µm 2 µm µ µ

21 µm NSOM AFM

22

23 CH 3 C O H CH 2 O C 2µm 2µm Miles, 1996

24

25 X λ = 2Lsinθ L

26 3)

27

28 4) A C tie

29 C C N N O O H H n Ade, 1996 n r n c 5µm

30 2.5.3 Tm G l Gc G T m = G l = H G f c / S = H f f T m S f H S H DSC G G l

31 T m n 1.5 = n e Tm() l = T (1 σ m ) l hf 6.27 Tm ( l) = 414.2(1 ) l H f =2.79x10 9 ergcm 3 σ e =87.4erg cm -2

32 T m S d T md (diluent) S s T ms

33 2.5.4 A B C H L C33 DSC

34

35 2.5.5 Vρ = Vaρa + Vcρc Vc φc = V ρ ρa φc = ρ ρ X (SAXS) c a d ac 2π q max

36 φ ac =0.85 O ac =0.065nm -1 d a =4.6nm ρ ec -ρ ea =52nm -3 d ac =34nm K( z) = ( ρ (0) ρ ) i( ρ ( z) ρ ) e e e e 1 1 = r 2 4 π qiq ( )cos 2 3 (2 ) q 0 e π = qzdq i φ ac O ac d a ρ ec -ρ ea

37

38 2.6.2 Lauritzen-Hoffman φ = 2νa σ + C νal σ νal f P e p s p σ σ

39 φ p φ p ν φ P ν C = a + a l al f = 2 1/2 1/2 2 σ e ν pσ s p 0 φp l p = C νaσ νa f = s 0 Saddle Point ( ν * a) 1/2 l * p 4σ e = f Cσ s = f

40 Saddle Point f = Hm Tm Sm = H m Tm = S m T c T m T c 0 Hm Tc T f = Hm Tc = Hm(1 ) = Hm( ) Tm Tm Tm * 4σe 4σe Tm lp = = 2C σσ e s 2C Tmσσ e s φ * p = = f Hm T f T H T 2 2 ( ) ( ) ( ) m

41 PE T m0 =418.2K h=2.8x10 9 erg cm -3 Xylene solution σ e =90 erg cm -2 σ s =11.4 erg cm -2 Tc=395.2K l P *=23.4nm Hoffman, Polymer,23,656(1982) b l φ = 2νaσ + 2bl σ νal f s e s s s

42 φs = 2aσ e als f = 0 ν φp l s = 2bσ νa f = 0 s * 2σe 2σe Tm ls = = f H T ν * a 2bσ s f m l * p 2 l s l p 4σ eσsb 4Tmσeσsb φ * s = = f T H φ p m

43 l * s T c 2σ e Tm = H ( T T ) m m c 2σ = Tm(1 ) H l e * m s T c ~T m 2σ T l T 0 e m() = m (1 ) Hml T m0 l

44 2.6.3 c (a) R h G: R= G( t z) vc = πr h= πg ( t z) h dt, dnc A dt R z t w a dnc = Avadt = A dt ρa

45 dt w = π ( ) a 2 2 dnc vc A dt G t z h ρa dw = ρ dv (, t z) c c c wc χc = w wa 1 χc = w ρ w dt ρ dt dχ = A πg ( t z) h = A(1 χ ) πg ( t z) h c c a c c w ρa ρa

46 χ c 0 dχc 1 χ t+ z [ ln(1 χ )] c = ( ) z 2 2 Aπ G t z h 3 t+ z χc 2 ρ c ( t z) c = AπG h 0 ρ a 3 z ρc t ln(1 χc) = AπG h = ρ 3 1 ρ 1 = = c 2 2 K1 AπG h πg I 3 ρa 3 Avrami χ = Kt c a 3 1 exp( 1 ) χ = = Kt 3 1 χc exp( 1 ) a ρcdt ρ a K1t

47 χ a vc n = 1 χc = 1 = exp( K t ) v c v c ln ln 1 = ln K + nln t vc

48 Avrami,n n (sheaf) n>6 Avrami

49 2.6.4 G) φ G = G φ kt F kt * * exp( / )exp( / ) 0 s D φ 4σ eσsb 4Tmσeσsb φ * s = = f T H T φ m

50 Tm G Vogel-Fulcher TA ς exp T T (T v Vogel Tg 30-70K T A K G V ς T + const 1 A log log. T TV

51 Hoffman 1975) T A =750K T V =203K G T A B exp exp 0 T TV Tm T dc ( T) = B T T + 0 m C T m0

52 (Gunther 1994) q

53 C-C CH 2 (M>1M) 126 Strobl 1993)

54 (M>1M) 126 SAXS Strobl 1995)

( ) 2002 1 1 1 1.1....................................... 1 1.1.1................................. 1 1.1.2................................. 1 1.1.3................... 3 1.1.4......................................

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