&

(TGA)

: (.. 5216 )

:

2015

,

.

,

.

.

2015

20 .

, (DTA),

(TGA) (EGA).

.

(Honda, 1915),

1930

(Vallet, 1935). ,

.

, H.

J. Flynn (1969)

.

,

,

,

.

.

20 .

,

.

, ,

.

, AcF9-1

Phenolic AcF9-7b Ceiling.

,

.

5 .

1

.

.

2

(TGA) .

.

3

(TGA)

.

.

4

.

.

5

.

.

................................................................................................................................ 3

.................................................................................................................................... 5

1 ............................................................................................................................... 15

........................................................................................................................ 15

1.1 ......................................................................................................................... 15

1.2 ................................................................................... 16

1.3 & ......................................... 20

2 ............................................................................................................................... 23

&

..................................................................................................................................... 23

2.1 ..................................................................................................................... 23

2.2 (TGA) ................................... 23

2.3 ............................................................ 25

2.4 ................. 26

2.5 (MODEL FITTING APPROACH IN ISOTHERMAL AND

NON-ISOTHERMAL KINETICS) ...................................................................................................... 26

2.5.1 .............................................................................................. 28

2.5.2 ........................................................................................ 28

2.5.3 .................................................................................. 29

2.5.4 COATS-REDFERN COATS-REDFERN ITERATIVE .................................... 31

2.6 (MODEL-FREE ISOCONVERSIONAL METHODS) ............. 34

2.7 (RATE-ISOCONVERSIONAL METHODS) ............................................... 35

2.7.1 FRIEDMAN ............................................................................................... 35

2.8 P(Y)-ISOCONVERSIONAL METHODS ................................................... 36

2.8.1 OZAWA-FLYNN-WALL (OFW) ................................................................... 38

2.8.2 KISSINGER-AKAHIRA-SUNOSE (KAS) ........................................................ 38

2.8.3 ....................................................................................... 38

2.8.4 VYAZOVKIN .............................................................................................. 40

2.8.5 NON-PARAMETRIC KINETIC (NPK) ............................................................ 40

2.9 ...... 41

3 ............................................................................................................................... 45

............................................................................................................ 45

3.1 ..................................................................................................................... 45

3.2 ACF9-1 PHENOLIC ....................................................................................................... 48

3.2.1 .................................................................................. 48

3.2.2 ................................................................. 51

COATS-REDFERN COATS-REDFERN ITERATIVE ............................................................. 51

3.2.3 ........................................................................... 57

FRIEDMAN ........................................................................................................ 57

OZAWA FLYNN WALL (OFW) ....................................................................... 60

KISSINGER AKAHIRA SUNOSE (KAS) ........................................................... 63

VYAZOVKIN ...................................................................................................... 66

3.3 ACF9-7B CEILING (BACK SIDE) ...................................................................................... 69

3.3.1 .................................................................................. 69

3.3.2 ................................................................. 73

COATS-REDFERN COATS-REDFERN ITERATIVE ............................................................. 73

3.3.3 ........................................................................... 76

FRIEDMAN ........................................................................................................ 76

OZAWA FLYNN WALL (OFW) ....................................................................... 79

KISSINGER AKAHIRA SUNOSE (KAS) ........................................................... 82

VYAZOVKIN ...................................................................................................... 85

4 ............................................................................................................................... 89

- ............................. 89

4.1 ..................................................................................................................... 89

4.2 ACF9-1 PHENOLIC ....................................................................................................... 91

4.3.1 COATS REDFERN

ITERATIVE ............................................................................................................................. 91

4.3.2 OZAWA FLYNN

WALL 93

4.3.3 VYAZOVKIN AND

LESNIKOVICH ........................................................................................................................ 95

4.3 ACF9-7B CEILING (BACK SIDE) ...................................................................................... 98

4.3.1 COATS REDFERN

ITERATIVE ............................................................................................................................. 98

4.3.2 OZAWA FLYNN

WALL 100

4.3.3 VYAZOVKIN AND

LESNIKOVICH ...................................................................................................................... 102

5 ............................................................................................................................. 105

............................................................................. 105

5.1 ...................................... 105

5.1.1 ACF9-1 PHENOLIC ................................................................................................. 105

5.1.2 , ACF9-7B CEILING (BACK SIDE) ..................................... 109

5.1.3 ................................................ 113

5.2 ......................... 119

5.2.1 ACF9-1 PHENOLIC ................................................................................................. 119

5.2.2 ACF9-7B CEILING (BACK SIDE) ............................................................................... 120

5.3 ......................................................................................................... 121

......................................................................................................................... 124

x

1.

................................................................................................................................ 24

2. ............... 46

3. ......................................... 46

1.

ACF9-1 PHENOLIC ................................................................................................................ 48

2. FRIEDMAN 1 ................................................... 58

3. FRIEDMAN 2 ................................................... 59

4. FRIEDMAN

............................................................................................................................................ 59

5. OFW 1 .......................................................... 61

6. OFW 2 .......................................................... 62

7. OFW .. 62

8. KAS 1 ........................................................... 64

9. KAS 2 ........................................................... 65

10. KAS . 65

11

VYAZOVKIN ........................................................................................................................... 68

12.

ACF9-7B CEILING ................................................................................................................. 70

13. FRIEDMAN 1 ................................................. 77

14. FRIEDMAN 2 ................................................. 78

15.

FRIEDMAN ............................................................................................................................ 78

16. OFW 1 ........................................................ 80

17. OFW 2 ........................................................ 81

18. OFW 81

19. KAS 1 ......................................................... 83

20. KAS 2 ......................................................... 84

21. KAS . 84

22.

VYAZOVKIN ........................................................................................................................... 87

23. - 2 ........ 93

24. 30 .......................................... 96

25. - 2 ...... 101

26. 36 ........................................ 103

27. 1 .............................. 106

28. 2 .............................. 108

29. 1 .............................. 110

30. 2 .............................. 112

31. OFW ITERATIVE

2 ......................................................................................... 112

32.

1 .................................................... 115

33.

2 ........................................................... 117

34. 2

................................................................................................................................ 118

35. - ..................... 119

36. - ............................ 120

1. ................................................................................................. 30

2. TGA ACF9-1 PHENOLIC

0.10 ( 1) ............................................................................................ 49

3. TGA ACF9-1 PHENOLIC

0.05 ( 2) ............................................................................................ 50

4. COATS REDFERN 1 ...................................... 52

5. COATS REDFERN 2 ...................................... 53

6. COATS REDFERN ITERATIVE 1 .......................................... 55

7. COATS REDFERN ITERATIVE 2 .......................................... 56

8. FRIEDMAN 1 ....................................................... 58

9. FRIEDMAN 2 ....................................................... 58

10. OFW 1 ............................................................ 61

11. OFW 2 ............................................................ 61

12. KAS 1 ............................................................. 64

xii

13. KAS 2 ............................................................. 64

14. TGA VYAZOVKIN........................ 66

15. VYAZOVKIN 1.................................................... 67

16. TGA ACF9-7B CEILING

0.10 ( 1) ............................................................................................ 71

17. TGA ACF9-7B CEILING

0.05 ( 2) ............................................................................................ 72

18. COATS REDFERN ITERATIVE 1 ........................................ 74

19. COATS REDFERN ITERATIVE 2 ........................................ 75

20. FRIEDMAN 1 ..................................................... 77

21. FRIEDMAN 2 ..................................................... 77

22. FRIEDMAN 1 ..................................................... 80

23. FRIEDMAN 2 ..................................................... 80

24. FRIEDMAN 1 ..................................................... 83

25. FRIEDMAN 2 ..................................................... 83

26. TGA VYAZOVKIN........................ 85

27. VYAZOVKIN 1.................................................... 86

28. COATS - REDFERN ITERATIVE .............. 92

29. - G() ........... 94

30. VYAZOVKIN AND LESNIKOVICH ..................................... 95

31. - VYAZOVKIN AND

LESNIKOVICH ........................................................................................................................ 97

32. COATS - REDFERN ITERATIVE .............. 99

33. - G() ......... 100

34. VYAZOVKIN AND LESNIKOVICH ................................... 102

35. - VYAZOVKIN AND

LESNIKOVICH ...................................................................................................................... 104

36. 1.................................. 106

37. 2.................................. 107

38. 1.................................. 109

39. 2.................................. 111

40. TGA ACF9-7B CEILING

0.10 1 .................................................... 113

41. 1 ... 114

42. TGA ACF9-7B CEILING

0.10 2 .................................................... 116

43. 2 ... 117

xiv

A: -

E:

E:

f():

k(T):

m:

mf:

ms:

R:

R2:

t:

T:

:

:

-15-

1

1.1

.

,

( /

). TGA

, ,

, , , . ,

( ), ,

- (.., ). ,

, ,

().

. 1915 (Honda, 1915)

.

,

.

. ,

,

.

,

.

1

-16-

..

.

.

, ,

, ,

.

,

.

.

.

,

,

.

.

1.2

20 .

, (DTA),

(TGA) (EGA).

.

(Honda, 1915),

1930

(Vallet, 1930). ,

.

, H.

-17-

J. Flynn (1969)

.

= ()()

, , ,

() ()

.

.

1920, Tamman et al. (1928), Jander (1927 1928)

Topley & Hume (1928).

,

Johanson Mehl (1939), Avrami (1939), Mampel (1940),

Erofeev (1946) Ginstling & Braunshtein (1950).

. Bruzs (1926)

Arrhenius

() = exp (

)

( - , R

)

. Httig et. al (Httig et. Al, 1932)

,

.

,

.

Arrhenius

Arrhenius .

Arrhenius

. Garn (1972 & 1990),

1

-18-

.

Arrhenius

. Arrhenius

,

,

Boltzman.

, Arrhenius

,

.

,

E A

. ,

. ,

. ,

Arrhenius

,

.

H. J. Flynn (1997)

, . Dollimore (1996)

Harcourt & Esson (1895)

.

,

= /. ,

Vallet (1935), = /

.

= ()()

.

.

, ,

-19-

. ,

, .

1950 .

Arrhenius

.

Kissinger (1957), Doyle (1961), Coats & Redfern (1964),

Friedman (1964), Ozawa (1965) Flynn & Wall (1966).

,

.

,

.

. ,

,

Arrhenius

. , ,

.

1970

Arrhenius

. ,

. (Dollimore et. al, 1969, Johnson & Gallagher,

1972, Gallagher & Johnson, 1973)

, ,

(McCarty et. Al, 1968, Palanisamy et. Al, 1971,

Zsako & Arz, 1974).

.

McCallum & Tanner (1970)

Arrhenius .

. J.

Sestak (1984)

1

-20-

, . ,

Arrhenius,

.

Vyazovkin & Wight (1998) ,

( ) .

Arrhenius

(force-

fitting) .

,

.

1.3 &

Vyazovkin (2000) :

Arrhenius

Arrhenius

, .

,

,

.

..

. T .

.

-21-

,

Vyazovkin

:

Maciejewski (1987 & 1987)

,

`

. ,

.

,

,

,

-23-

2

&

2.1

(TGA).

.

,

.

2.2 (TGA)

,

, ,

.

,

,

( ),

, .

.

, (DTG

curve). () :

=

2

-24-

, =

=

=

,

.

,

.

TGA , ,

,

.

,

:

,

,

, .

(dynamic mode) (Hatakeyama & Quinn, 1999)

1.

-25-

2.3

.

.

- ,

.

, ,

10-20% -

. , ,

.

, (3)

(5) (Vyazovkin et. Al, 2011).

.

. ,

(.. TGA)

(.. DSC) , .

,

,

.

,

, (proper

baseline).

(baseline corrections).

.

(TGA)

. ,

2

-26-

.

.

2.4

.

.

.

. , ,

,

. ,

,

.

Arrhenius .

.

2.5 (Model fitting

approach in isothermal and non-isothermal kinetics)

,

Arrhenius,

().

.

Arrhenius, .

-27-

() = ()

() = ln

ln , = ln [

()]

ln , 1/. , ()

().

, ,

() = . ()

.

() , ()

.

. ()

.

Arrhenius

().

,

(), ().

,

() ,

Arrhenius

, ,

. ,

Arrhenius

.

.

.

2

-28-

.

.

2.5.1

,

.

.

r s2

.

(confidence limits).

,

.

Liqing Donghua

ln () = [ln

+ ln

2+ ln ()] ln

, h(x)

Senum Yang 4

h(x) =x4 + 18x3 + 88x2 + 96x

x4 + 20x3 + 120x2 + 240x + 120

ln () ln

(),

-1 2

.

2.5.2

-29-

.

- . ,

- ,

.

, ,

.

2.5.3

,

.

() .

,

.

,

.

Sestak & Berggren (1971)

() = (1 )[ ln(1 )]

m, n p

. m, n p

,

( 1).

2

-30-

/ () ()

1 Exponential law ln

2 Power law 43/4 1/4

3 Power law 32/3 1/3

4 Power law 21/2 1/2

5 Power law 2/31/2 3/2

6 Avrami-Erofeev

equation 2(1 )[ ln(1 )]1/2 [ ln(1 )]1/2

7 Avrami-Erofeev

equation 3(1 )[ ln(1 )]2/3 [ ln(1 )]1/3

8 Avrami-Erofeev

equation 4(1 )[ ln(1 )]3/4 [ ln(1 )]1/4

9 One-dimensional

diffusion 1/2 2

10 Two-dimensional

diffusion [ ln(1 )]1 [(1 ) ln(1 )] +

11 Three-dimensional

diffusion 3(1 )2/3/[2(1 (1 )1/3)] (1 (1 )1/3)

2

12 First-order 1 ln(1 )

13 Second-order (1 )2 (1 )1 1

14 Third-order (1 )3 [(1 )2 1]/2

15 Contracting area 2(1 )1/2 [1 (1 )1/2]

16 Contracting volume 3(1 )2/3 [1 (1 )1/3]

1.

-31-

,

. ,

,

. ,

m, n p.

,

. Jacobs Tompkins

.

,

, Arrhenius

.

,

, , , , , , .

,

.

.

,

.

,

.

2.5.4 Coats-Redfern Coats-Redfern Iterative

Coats-Redfern

Coats-Redfern Iterative.

2

-32-

() =

()

Arrhenius

= (

a

) ()

,

, = /,

=

(

a

) ()

() =

(

a

)

0

,

(a

)

0

= (

) 2 exp() ()

a/() ()

, .

.

() =

2 exp() ()

Coats Redfern

() = 2

= 1

2

Coats - Redfern

-33-

ln()

2= ln [

a(1

2

a)]

a

,

() 1/, a

. 2

1

, .

Coats Redfern Itrative

() =(3 + 102 + 18)

3 + 122 + 36 + 24

. Coats Redfern Iterative

ln()

()2= ln

a

a

a

a .

Coats-Redfern, Coats-Redfern Iterative

.

,

.

Coats-Redfern , -

.

2

-34-

2.6 (Model-free isoconversional

methods)

(model-free)

(isoconversional principle),

( ln (

)

1)

=

,

.

Arrhenius

.

,

1960.

, .

/

DTA DSC.

TG,

, .

,

.

TG ,

. ,

() =

exp (

) =

(, )

0

.

-35-

. Flynn (1997)

.

,

.

.

,

.

rate-isoconversional.

().

p(y)-isoconversional.

(TGA) .

2.7 (rate-isoconversional methods)

2.7.1 Friedman

Friedman H. Friedman 1964.

. ,

Friedman

. , H. Friedman

.

ln (

)

,= ln (

)

,= ln[()]

,

ln( ) 1

. ,

2

-36-

Friedman ,

,

, . ,

.

2.8 p(y)-isoconversional methods

-

() [()]1

0

= exp (

)

0

.

() = exp (

)

ln , =

+ ln [()

]

,

ln , 1/.

() =

[exp ()

(

exp ()

)

] =

()

= .

() .

,

:

() =exp ()

2(1 +

2!

+

3!

()2+

4!

()3 )

-37-

() =exp ()

(1 + )(1

1

2 + +

2

(2 + )(3 + )

4

(2 + )(3 + )(4 + ) )

() =exp ()

(2 + )(1 +

2

(2 + )

8

(2 + )2+ (4) )

Murray & White (1955)

() =exp ()

2

O Doyle (1961)

log () 0.4567 2.315 () exp (1.0518 5.330)

() exp ( + )

direct p(y)-isoconversional :

ln (

, ) = (

)

B C

.

2

-38-

2.8.1 Ozawa-Flynn-Wall (OFW)

H Flynn-Wall-Ozawa Takeo

Ozawa 1965 Flynn Wall 1966

Ozawa 1975. Doyle

, = 0 = 1.052.

Arrhenius

. Ozawa (1976),

.

,

ln() 1

ln() = ln

() 5.331 1.052

,

1.052

.

.

-

.

2.8.2 Kissinger-Akahira-Sunose (KAS)

Kissinger-Akahira-Sunose,

Murray = 2 = 1.

.

KAS ln (

2 )

1

ln (

,2 ) = ln

()

,

.

2.8.3

-39-

. (Vlaev et. Al, 2008)

, Ozawa

- Flynn - Wall

ln (

()) = ln

()

5.331 1.052

,

Kissinger-Akahira-Sunose

ln (

(),2 ) = ln

()

,

() Senum Yang 4

() =4 + 183 + 882 + 96

4 + 203 + 1202 + 240 + 120

() Liqing Donghua

() =exp () () 2

0.0048exp (1.0516)

= .

:

1. 1

() = 1 () = 1.

.

2. 1 2,

ln[ () ] 1

ln[ ()2 ] 1 .

3. (2) 1