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Number TA-125

a constant decomposition level are determined. The kinetic

activation energy is then determined from a plot of the loga-

rithm of the heating rate versus the reciprocal of the tempera-

ture of constant decomposition level. This activation energy

may then be used to calculate estimated lifetime at a given

temperature or the maximum operating temperature for a given

estimated lifetime. This TGA approach requires a minimum of

three different heating profiles per material. However, even

with the associated calculations, the total time to evaluate a

material is less than one day. With an automated TGA such

as the TA Instruments Auto TGA 2950, the actual operator

time is even lower with overnight evaluation being possible.

Experimental

The specific experimental conditions used (such as tempera-

ture range and specimen atmosphere) depend upon the mate-

rial being tested. Experimental design and data reduction are

similar for each material, however. In the analysis illustrated

here, a high temperature fluoropolymer wire insulation mate-

rial was examined.

The sample size was 40 - 60 mg. Decomposition profiles were

obtained while heating at 1, 2, 5, 10 and 20

o

C/minute in nitrogen

between 200 and 500

o

C. The profile during the first 25% of

sample weight loss was used for subsequent calculations.

Results

Figure 1 displays the overlaid weight loss curves for the

fluoropolymer at several different heating rates. The first step

in the data analysis process is the choice of level of decompo-

sition. Typically, a value early in the decomposition profile is

desired since the mechanism here is more likely to be that of

the actual product failure. On the other hand, taking the value

too early on the curve may result in the measurement of some

volatilization (e.g. moisture) which is not involved in the failure

mechanism. A value of 5% decomposition level (sometimes

called conversion) is a commonly chosen value. Other

values may be selected to provide correlation with other types

of lifetime testing (6).

Summary

In many polymer applications the ability to predict product

lifetime is valuable because the costs of premature failure in

actual end use can be high. For example, federal regulations

require the estimation of component lifetime in nuclear reac-

tors, while power companies need to know how long insula-

tion in transformers and transmission lines will last. Thermo-

gravimetric Analysis (TGA) provides a method for accelerat-

ing the lifetime testing of polymers so that short term experi-

ments can be used to predict in-use lifetime.

Introduction

Wire insulation is a polymer application where the ability to

rapidly predict long-term product lifetime is valuable. One test

commonly used for estimating wire insulation lifetime is ANSI/

ASTM procedure D-2307. In this procedure, twisted pairs of

insulated wire are oven aged (for up to 50 days) at elevated

temperatures (up to 240

o

C) until voltage breakdown occurs. A

series of such tests, performed at different oven temperatures,

creates a semi-logarithmic plot of lifetime versus the reciprocal

of failure temperature. The method assumes first order kinetics

and uses extrapolation to estimate the long lifetimes encoun-

tered at normal use temperature. The application of first order

kinetics to the estimation of polymer lifetimes is particularly

fortuitious. Many polymers are known to decompose with

first order kinetics. For those that do not, the earliest stages

of decomposition can be approximated well with first order

kinetics. (1,2,3,4,5). This procedure, while useful, is very time

consuming, often taking many months, particularly for highly

stable materials. As more and more stable polymeric electrical

insulation materials are introduced, the time needed for a full

series of tests becomes excessive. It is desirable, if not

necessary, therefore, to find a more practical technique.

Thermogravimetric Analysis (TGA), which monitors weight

changes in a material as temperature changes, offers a viable

alternative to oven aging. In the TGA approach, the material

is heated at several different rates through its decomposition

region. From the resultant thermal curves, the temperatures for

Thermal Analysis Application Brief

Estimation of Polymer Lifetime by TGA Decomposition Kinetics

Using the selected value of conversion, the temperature (in

kelvin) at that conversion level is measured for each thermal

curve. A plot of the logarithm of the heating rate versus the

corresponding reciprocal temperature at constant conversion

is prepared. The plotted data should produce a straight line.

Figure 2 shows a series of such lines created from the four

curves shown in Figure1 by plotting data at different conver-

sion levels. If the particular specimen decomposition mecha-

nism were the same at all conversion levels, the lines would all

have the same slope. This is not the case here. The lines for

the low conversion cases are quite different from those of 5%

and higher conversion. This justifies our selection of 5%

conversion as the best point of constant conversion for the

purposes of this test.

The next step in the process is the calculation of activation

energy (E) from the slope in Figure 2 using the method of Flynn

and Wall(7).

-R d log

E = (1)

b d (1/T)

Where:

E = Activation Energy (J/mol)

R = Gas Constant (8.314 J/mol K)

T = Temperature at Constant Conversion (K)

= Heating Rate (

o

C/min)

b = Constant (0.457)

The value of the derivative term (d log )/[d (1/T)] is the slope

of the line in Figure 2.

The value for the constant b (given in tabular form in reference

7) varies depending upon the value of E/RT. Thus, an iterative

process must be used where E is first estimated, a correspond-

ing value for b is chosen, then a new value for E is calculated.

This process is continued until E no longer changes with

successive iterations. For the given decomposition reaction

for the values of E/RT between 29 and 46, the value for b is

within +1% of 0.457, thus this value is chosen for the first

iteration.

Figure 3 gives values for the activation energy and the

corresponding values for E/RT calculated for the five conver-

sion cases shown in Figure 2. Note that all the activation

energy values calculated on the first iteration yield E/RT

values within the expected range. Thus, no additional itera-

tions are required. The activation energy for the 5% conver-

sion case is quite similar to that for the 1 and 2% cases, giving

additional support to the 5% conversion choice.

[ ]

WIRE INSULATION

THERMAL STABILITY

200 250 300 350 400 450 500

80

85

90

95

100

Temperature (C)

W

E

I

G

H

T

L

O

S

S

(

%

)

0.5%

1.0%

2.5%

5%

10%

20%

10C

5C

2.0C

1.0C

size: 60mg

atm.: N

2

Conversion

Figure 1

LOG HEATING RATE vs TEMPERATURE

OF CONSTANT CONVERSION

1.4 1.5 1.6

1

2

5

10

1000/T (k)

H

E

A

T

R

A

T

E

(

C

/

M

I

N

)

460 440 420 400 380 360

WIRE INSULATION TEMPERATURE (C)

20

10

5

2.5 1.0 0.5

Conversion

Figure 2

ACTIVATION ENERGY

(wire insulation decomposition)

Conversion Activation Energy

% E/RT (kJ/mol)

0.5 31 170

1.0 44 245

2.5 44 246

5.0 42 244

10 36 211

20 36 212

Note: b = 0.457 + 0.004 for 29 < E/RT < 46

Figure 3

Toop has postulated a relationship between activation energy

and the estimated lifetime of some wire insulation (8).

E E

In t

f

= + In P (X

f

) (2)

RT

f

R

Where:

t

f

= Estimated Time to Failure (min)

E = Activation Energy (J/mol)

T

f

= Failure Temperature (K)

R = Gas Constant (8.134 J/mol K)

P (X

f

) = A function whose values depend

on E at the failure temperature.

T

c

= Temperature for 5% Loss at (K)

= Heating Rate (

o

C/min)

To calculate the estimated time to failure (t

f

), the value for the

temperature (T

c

) at the constant conversion point is first

selected for a slow heating rate (). This value, along with the

activation energy (E) is used to calculate the quantity E/RT.

This value is then used to select a value for log P(X

f

) from the

numerical integration table given in Toops paper. The numeri-

cal value for P(X

f

) can then be calculated by taking the

antilogarithm. Selection of a value for failure (or operation)

temperature (T

f

) permits the calculation of t

f

from equation 2

above.

Rearrangement of equation 2 yields a form which may be used

to calculate the maximum use temperature (T

f

) for a given

lifetime (t

f

).

E/R

T

f

=

E

In t

f

- In P (X

f

) (3)

R

Equation 2 may be used to create a plot, similar to Figure 4, in

which (the logarithm of) estimated lifetime is plotted versus (the

reciprocal) of the failure temperature. From a plot of this nature,

the dramatic increase in estimated lifetime for a small decrease

in temperature can be more easily visualized.

Kinetic parameters may also be determined by other

thermoanalytical techniques. Differential Scanning Calorim-

etry (DSC) and Pressure DSC may be used to obtain such

parameters for use in the estimation of thermal hazard potential

of chemicals (9).

[ ]

[ ]

ESTIMATED LIFETIME

TEMPERATURE DEPENDENCE

1.5 1.6 1.7 1.8 1.9

1

2

3

4

5

6

1000/T (k)

E

S

T

I

M

A

T

E

D

L

I

F

E

(

h

r

.

)

260 280 300 320 340 360

1 century

1 decade

1 yr.

1 mo.

1 week

1 day

E

S

T

I

M

A

T

E

D

L

I

F

E

Temperature (C)

Figure 4

References

1. ASTM Test Method D-2307

2. IEEE Test Method 101.

3. IEEE Test Method 259.

4. IEEE Test Method 266.

5. IEEE Test Method 323.

6. L. Krizanovsky, et. al., J. Therm. Anal., 13, 571

(1978).

7. J. H. Flynn, et. al., Polym. Lett., B4, 323 (1966).

8. D. J. Toop, IEEE Trans. Elec. Ins., E1-6, 2 (1971).

9. ASTM Test Method E698

TA-125A

TA Instruments S.A.R.L.

Paris, France

Telephone: 33-1-30489460

Fax: 33-1-30489451

TA Instruments, Inc.

109 Lukens Drive

New Castle, DE 19720

Telephone: (302) 427-4000

Fax: (302) 427-4001

For more information or to place an order, contact:

TA Instruments, Ltd.

Leatherhead, England

Telephone: 44-1-372-360363

Fax: 44-1-372-360135

TA Instruments N.V./S.A.

Gent, Belgium

Telephone: 32-9-220-79-89

Fax: 32-9-220-83-21

TA Instruments GmbH

Alzenau, Germany

Telephone: 49-6023-30044

Fax: 49-6023-30823

TA Instruments Japan K.K.

Tokyo, Japan

Telephone: 813-5434-2771

Fax: 813-5434-2770

Internet: http://www.tainst.com

Thermal Analysis & Rheology

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