Documente Academic
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Polymers
Sergey Vyazovkin
Bulk kinetics
Polymers are materials
Processes of interest:
810
degradation/decomposition 420
FTIR and polymer and
degradation/decomposition 540
mi mT
mi m f
( Heat flow)dT
Tif
( Heat flow)dT
Heat flow
Mass
mT
Ti
mf
T
Ti
Tf
step
Nonisothermal conditions preferred over
isothermal
Single heating rate data analysis preferred
over multiple heating programs
d
k (T ) f ( )
dt
k(T) rate constant
f() reaction model
k (T ) A exp
RT
Svante Arrhenius
1859-1927
d
E
A exp
f ( )
dt
RT
Kinetic triplet:
E activation energy
A preexponential factor
f() reaction model, f()= (1-)n
Henry Eyring
1901 - 1981
E activation energy
Henry Eyring
1901 - 1981
Multiple reactions
d
k1 f1 ( ) k 2 f 2 ( )
dt
d ln(d / dt )
E R
dT
E1 k1 f 1( )E2 k 2 f 2 ( )
k1 f 1( ) k 2 f 2 ( )
200
180
160
140
120
100
350
300
250
200
1501.0
0.8
0.6
0.0
0.2
0.4
Diffusion
1
1
1
kef k R k D
ED k R ER k D
kR kD
ln k
d ln kef
Eef R
1
dT
ED
ER
-1
Condensed phase
Reactions occur in the
mi
mT
Mass
mf
T
mi mT
mi m f
g j ( )
ln
ln
2
Aj R
2
R
T
E
j
j
Ej
RT
Compensation effect
lnA
lnA = aE + b
30
T.B. Brill et al
J. Phys. Chem.
1994, 98, 12242
solid
melt
gas
25
-1
log(A/ s )
20
15
10
5
0
50
100
150
200
E / kJ mol
-1
250
300
Reaction Model
Power law
Power law
Power law
Power law
One dimentional diffusion
Mampel (first order)
Avrami-Erofeev
Avrami-Erofeev
Avrami-Erofeev
Three dimentional diffusion
Contracting sphere
Contracting cylinder
f()
3/4
4
2/3
3
1/2
2
-1/2
(2/3)
-1
(1/2)
1-
3/4
4(1 - )[-ln(1 - )]
2/3
3(1 - )[-ln(1 - )]
1/2
2(1 - )[-ln(1 - )]
2/3
1/3 -1
2(1 - ) (1 - (1 - ) )
2/3
3(1 - )
1/2
2(1 - )
Best
fits
Conversion
Conversion
Temperature
t0
Time
g ( )
E
A exp
RT0
HMX: Predictions
4
5
0.8
0.6
g ( )
t0
E
A exp
RT0
1.0
0.4
Experimental data
o
T=235 C
0.2
0.0
0
100
200
t / min
300
E / kJ mol-1
Step 2
Experiment
Reference
Step 3
vacuum
130 176
Isothermal manometry
1, 2
vacuum
138
Isothermal TGA
vacuum
242
Isothermal TGA
vacuum
117
Isothermal manometry
N2
150 250
Nonisothermal TGA
N2
210
Nonisothermal TGA
N2
154
133
Nonisothermal TGA
11
210
Nonisothermal TGA
12
N2
213-230
N2
31
224
Isothermal TGA
12
N2
233
104
Isothermal heating
13
N2
113
Nonisothermal TGA
15
130 180
Nonisothermal TGA
16
Thermal degradation of PP
Atmosphere
E / kJ mol-1
Method
Ref
N2
244
Nonisothermal TGA
10
N2
216
isothermal TGA
11
N2
214
Nonisothermal TGA
18
N2
160
Nonisothermal TGA
22
N2
115 200
Nonisothermal TGA
19
N2
130 200
Nonisothermal TGA
23
N2
230
Factor-jump TGA
19
Vacuum
257
Factor-jump TGA
19
Ar
98, 328
Nonisothermal TGA
25
avoided
Use multiple heating rate methods instead
Importance of detecting complex processes
Model-free kinetics
Rate equation
d
E
A exp
f ( )
dt
RT
Log derivative
d ln(d / dt )
d ln k
d ln f ( )
1
1
1
dT
dT
dT
Model-free kinetics
Isoconversional principle
d ln(d / dt )
d ln k
1
1
dT
dT
d ln f ( )
dT
Conversion
Activation energy
Isoconversional method
Temperature
Conversion
Thermal degradation of PP
N2
244
N2
216
N2
214
N2
160
N2
115 200
N2
130 200
N2
230
Vacuum
257
Ar
98, 328
270
240
-1
E / kJ mol-1
E / kJ mol
Atmosphere
210
180
150
0.0
0.2
0.4
0.6
0.8
1.0
Decrease in E
-1
Diffusion
control
E / kJ mol
60
50
40
0.2
0.4
0.6
0.8
1.0
Detecting vitrification by
temperature modulated DSC
AT = 1 C
t = 1 min
o
-1
= 5 C min
30
20
0
2.7
0.4
0.2
2.6
0.0
2
6
t / min
10
-1
-1
0.6
2.8
T/ C
40
0.8
2.9
Cp/ J g K
1.0
50
3.0
Vitrifcation
60
1.2
Heat fow / mW
70
tt
T(t)T0tATsin 2
50
100
o
T/ C
150
2.5
70
actually caused by
vitrification
0.4
0.6
2.60
0.8
1.0
2.56
-1
*
50
40
0.2
-1
2.64
Cp / J g K
60
Vitrifcation
E / kJ mol
-1
2.68
E / kJ mol
-1
260
240
-50
220
-100
200
180
-150
160
-200
140
-250
-300
120
0.0
0.2
0.4
0.6
0.8
1.0
Tm=280oC
50
T/ C
Poly(ethylene terephthalate)
Aldrich, MW ~18,000,
- CO - O - ] n
[ CH2 - CH2 - O - CO -
E >0
E <0
Tmax
Kg
U
exp
G G0 exp
TTf
R(T T )
T Tm T
f 2T/(Tm T)
*
Growth rate
Hoffman-Lauritzen theory:
Tg
Temperature
Tm
Evaluating Kg and U*
Tm2 T 2 TmT
T2
E vs E vs T: E (T ) U
KgR
2
(T T )
(Tm T ) 2 T
*
50
-1
E / kJ mol
nb eTm
Kg
h f k B
0
-50
-100
-150
-200
-250
-300
420 430 440 450 460 470 480 490 500
T/K
Model-free predictions
t
t ,0
E
exp
dt
RT (t )
E
exp
RT0
t , 0
E
exp
RT0
Conversion
Temperature
E
dt
RT (t )
exp
Time
Activation energy
Conversion
Model-free predictions
Conversion
4
5
Model-free
Best-fit models
0.6
0.4
0.2
0.0
0
100
200
t / min
300
Conversion
Temperature
5%
1400
4%
t / day
1200
3%
1000
800
600
2%
400
200
1%
0
20
25
30
35
o
T/ C
40
45
50
Conversion
Model-based methods
d
k1 f1 ( ) k 2 f 2 ( ) ...
dt
Temperature
d
k1 f1 ( ) k 2 f 2 ( )
dt
d ln(d / dt )
E R
dT
E1 k1 f 1( ) E2 k 2 f 2 ( )
k1 f 1( ) k 2 f 2 ( )
Model-free
Activation energy
Model-based
Conversion
via E dependence
Conclusions
E dependence can generally be interpreted as a
predictions
E dependence provides a link to model-based methods
Model-free approach can serve as a uniform framework
reactions
7) complex reactions unavoidable
8) cannot be limited to single dif. Eq.
9) the database should include:
D) solid-state reactions
H) macromolecular reactions
I) polymerization reactions
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