Kinetic Data for

Polymers
Sergey Vyazovkin

Bulk kinetics
Polymers are materials
Processes of interest:

Thermal and oxidative degradation

Molding (thermoplastics)
Reactive injection molding (thermosets)
Fire resistance
Methods:
DSC (heat release kinetics)
TGA (mass loss kinetics)

Importance of TGA and DSC

ISI Web of Science :
DSC and polymer - 3,900
TGA and polymer 1,200
FTIR and polymer 2,900

Application to particular processes

DSC and crystallization and kinetics 820
Microscopy and crystallization and kinetics

810

DSC and curing/cure and kinetics - 760

FTIR and curing/cure and kinetics - 247
TGA and polymer and

degradation/decomposition 420
FTIR and polymer and
degradation/decomposition 540

Kinetics by TGA and DSC

mi

mi mT

mi m f

( Heat flow)dT

Tif

( Heat flow)dT

Heat flow

Mass

mT

Ti

mf
T

Ti

Tf

Typical kinetic approach

Single-step treatment preferred over multiple-

step
Nonisothermal conditions preferred over
isothermal
Single heating rate data analysis preferred
over multiple heating programs

Single step rate equation

d
k (T ) f ( )
dt
k(T) rate constant
f() reaction model

Arrhenius equation (1889)

E

k (T ) A exp

RT

Svante Arrhenius
1859-1927

Single step rate equation

d
E
A exp
f ( )
dt
RT
Kinetic triplet:
E activation energy
A preexponential factor
f() reaction model, f()= (1-)n

Transition state theory

NA
I
G
I
OR

Henry Eyring
1901 - 1981

E activation energy

Transition state theory

Henry Eyring
1901 - 1981

1. no medium (gas phase)

2. single-step reaction

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

solid or liquid medium

Medium affects the
temperature
dependence of the rate
Experimental E involves
physical properties of
the medium

mf
T

mi mT
mi m f

Single heating rate data analysis

g j ( )
ln
ln
2

Aj R

2
R
T

E
j
j

Ej

RT

Coats-Redfern method (1964): ~2000 citations!

TGA or DSC at 1 heating rate
vs T data fit to different g() models

Compensation effect

lnA

lnA = aE + b

Large uncertainty in E and lnA!

Compensation effect, lnA=aE+b

Decomposition of HMX

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

Solid state reaction models

No.
1
2
3
4
5
6
7
8
9
10
11
12

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 - )

HMX: Kinetic triplets by CoatsRedfern method

Best
fits

Conversion

Practical purpose: predictions

A, E, g( )

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

Thermal degradation of PMMA

Atmosphere
Step 1

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

ICTAC Kinetics Project

ICTAC Kinetics Project

Thermochim. Acta 355(2000)125
Single heating rate methods should be

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

Uses multiple heating rates

Yields a model-free estimate E

Conversion

Activation energy

Isoconversional method

Temperature

E varies with multi-step process

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

Epoxy-amine cure: Variation of

E with
70

Decrease in E

-1

Diffusion
control

E / kJ mol

suggests a shift from

kinetic to diffusion
control that usually
associated with
vitrification.

60

50

40
0.2

0.4

0.6

0.8

1.0

TTT cure diagram

In the glassy
state
molecular
motion is
largely
reduced

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

Epoxy-amine cure: Variation of

E with
Decrease in E is

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

Melt crystallization kinetics

E / kJ mol

-1

Cooled from 290 to 25C

= -3, -4, -6, -8, -12C/min

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 -

Temperature dependence of growth

rate

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

I: Kg=3.2 105 K2 , U*=4300 J/mol

II: Kg=1.9 105 K2 , U*=2300 J/mol

-1

E / kJ mol

nb eTm
Kg
h f k B

0
-50
-100
-150
-200
-250

Macromol. Rapid Commun.

2004, 25, 733

-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

Assuming that kinetic triplet (E, A, reaction

model) at a given does not change when

changing T

t , 0

E
exp
RT0

Conversion

Temperature

E
dt

RT (t )

exp

Time

Activation energy

Conversion

Model-free predictions

Conversion

Model-free predictions, HMX

1.0
0.8

4
5

Model-free

Best-fit models

0.6
0.4
0.2

HMX experimental data

o
T=235 C

0.0
0

100

200
t / min

300

Conversion

Model-free predictions, shelf-life

Temperature

Model-free predictions, shelf-life

Predicted decomposition of Aspirin
1600

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

Model-based methods that use multiple heating

programs are being developed

By far less common than model-free methods

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

Model-based and model-free methods are interrelated

via E dependence

Conclusions
E dependence can generally be interpreted as a

function of the activation energies of individual steps

E is useful in exploring reaction mechanisms
The model-free approach requires only E for kinetic

predictions
E dependence provides a link to model-based methods
Model-free approach can serve as a uniform framework

for creating a database of bulk polymer (and solid-state)

kinetics of thermal reactions

The 16 questions (polymers and

solid-state)
3) nonisothermal data important
4) include overall or both (overall and elementary)

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

The 16 questions (polymers and

solid-state)
11) long term success via agreements w/journals
13) critical assessment is important

ThermoML

ThermoML @ J. Chem. Eng. Data

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and storage of thermophysical property data

Authors download and use the GDC software to
capture the experimental property data that has been
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The output of the GDC Software converted into
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Upon release of the manuscript the ThermoML files
are posted on the public-domain TRC Web site

KineticML @ Thermochim. Acta?