Michael Hess

Department of Physical Chemistry

University Duisburg-Essen
Campus Duisburg
47048 Duisburg, Germany
e-mail: hi259he@uni-duisburg.de
 Principle scheme of a thermogravimetric system

Balance
Optional
to
analyzer: Zero control
IR
GC-MS
etc. oven
Conroller
Analyzer
Data output

Mass
Thermo Carrier gas: N2, air, O2, … compensation
couple
TGA-systems can be combined with:

IR-spectrometry
GC-MS
Product identification
gas phase absorption
thinlayer chromatography
DSC
Enthalpy, phase transitions
DTA

Sample mass  1-20 mg

Sensitivity  10-3 mg
 Processes of interest in polymer science:

In general: m = f(T)dm/dt or m = f(t)T

thermal activated degradation (depolymerization)

thermo-oxidative degradation

Thermal stability i. e. upper limit of use under short-term heat-exposure

Determination of reaction-kinetical data such as:
reaction rate r,
apparent reaction energy Ea
apparent pre-exponential factor A (collision factor)
formal (apparent) reaction order n
rate constant k
 thermal activated degradation (depolymerization)

inert atmosphere, e. g. N2

e. g.: thermal depolymerization of poly(-methyl styrene):

n
dm  
  k   m(t ) dm  with n = 1 in this case
dt  dT 

extend of reaction

This reaction is (during a large part of the reaction) a simple “un-zipping”

of the polymer chain from its end, monomer after monomer.

In polystyrene the depolymerization occurs randomly along the chain

 thermo-oxidative degradation

More complex kinetics which is in particular influenced by

the diffusion process of O2 to the reaction site (char formation),
the activities of flame retardants and inhibitors etc.
 In many cases

•there are complex kinetics

•there is influence of diffusion rates of reactants and products

•there are solid-state reactions

• there are incomplete polymerizations or crosslink reaktions (in thermosets)

•apparent reaction orders different from n = 1 can be observed

 AA + BB+… mM + LL +…

reactants i  0 products i  0

ni = ni0+ i r•= d/dt= - i-1dni/dt [mol s-1]

(rX•= dX/dt= - i-1dci/dt [mol L-1 s-1])

i= stoichiometric coefficient

ni = amount of substance
ni0 = amount of substance at =0 (initial amount of substance)
= extend of reaction
ci=(molar) concentration
X= conversion
r=rate of reaction
isothermal experiments: w = f(t)T isothermal experiments are straight forward
but they are experimentally difficult

dynamic experiments: w = f (T)dT/dt = f (t)

dT

dt
The mass loss at any time is given by:
w = w0-w w = sample mass
w0 = initial sample mass
so that the conversion C is given by: t = time
T = temperature
C = w/w0 = (w0-w)/w0  = heating rate
C = conversion
(1-C) = w/w0 (mass-loss fraction)
rcA (A)
rcB(B
) r= kn cA (A)  cB(B)  …
.
kn = f(T, p, catalyst, solvent,…)
.
. i z

n

ia
i

kn= rate constant

(A), (B) … = partial formal order of component A,
component B,…
n = formal (total) order of reaction
 In case of a pyrolytic reaction frequently the form:

dw

 k n w0  w
n

 
dt
dw Ea 1
 Aexp   w0  w  n
dt RT
 
 

log 
 dT  dw  

    log A 
dt  dt 
Ea 1
2.302R T
 n log w0  w  
   
  r 
can be used:
 Ozawa method

1-C lg  slope m = -0.457 Ea/R

1
1
2
3
2

3

T [K] 1T [K-1]
 Arrhenius’ law:

 
 Ea Ea 1
kn  A
  e RT
 ln k n  ln A  
preexponential factor effectivit y factor R T
collision factor

Ea = (apparent) activation energy [kJ/mol]

In thermogravimetric experiments:

rC •= dC/dt= - dm/dt [mg s-1]

C = conversion
 example of a complex depolymerization

8,000

7,000

6,000
sample mass [mg]

5,000

4,000 nitrogen

3,000

2,000

1,000 Residual material

0,000
0,0 100,0 200,0 300,0 400,0 500,0 600,0 700,0 800,0 900,0
temperature [°C]

Process I

Process II Process IV
Process III
Some examples of pyrolytic reactions

(random) bond scission

volatile products
disproportionation

radical transfer (chain transfer)

volatile products