Time-temperature

superposition
Time-temperature superposition is a tool to
determine the material properties over broad range
of times and temperaturesby shifting data.

Prior viewing: Creep and stress relaxation

Future viewing: Linear viscoelastic superposition
Course Name: Polymeric Materials
Level(UG/PG): PG

Author: Manish Gupta, MTech student, IIT Madras

Mentor: Dr. Abhijit P. Deshpande
 Learning objectives
1
After interacting with this Learning Object, the
learner will be able to:
2
Appreciate the concept of time temperature superposition
principle.
Calculate shift factor.
3 Predict material properties at extremely low and high time
scales.

5
 Definitions and Keywords
1
1. Time-temperature superposition: Time-temperature superposition is a
tool to determine the material properties over broad range of times and
2 temperaturesby shifting data.

2. Shift factor: It is the factor by which data need to be shifted.

3. Storage modulus (G): It describes the elastic or energy storage behavior

3 of the material.

4. Relaxation modulus (E): It is defined as the ratio of stress (a function of

time) to constant strain.

5
 Master Layout
1 This animation consists of three parts:
Part 1: Importance of time-temperature superposition (TTS)
Part 2: Time-temperature superposition in frequency domain
Part 3: Time-temperature superposition in time domain
2 Part 4: Calculation of shift factor
1.1
Temperature = 110o C

Conversion = 70%
A+B C
3 Time of reaction = 2 hrs

4
Temperature Temperature = 110o C
or
Time of reaction = 2 hrs Time of reaction

5
 Slide 1
Part 1: Step 1

1 Importance of time-temperature
superposition
1.1

T = 110o C Conversion = 70%

2 A+ B C Time of reaction = 2 hrs More
than
two
hours

3 A+ B
T = 60o C
C
Conversion = 70%

Time of reaction = ??? Less

than
two
hours
4 T = 150o C Conversion = 70%
A+ B C Time of reaction = ???

5
 Part 1: Step 1 Slide 2

1 Importance of time-temperature
superposition
1.1
Temperature = 110o C

2 A+ B C Conversion = 70%

Time of reaction = 2 hrs

3 If the desired conversion is 80%, then this conversion can be obtained either by

Temperature Temperature = 110o C

or
Time of reaction = 2 hrs Time of reaction
4
Analogously, polymer behavior obtained at a particular
combination of time (or frequency) and temperature, can also
be obtained at some other combinations of time ( or frequency)
and temperature. And, the technique used for this purpose is
known as time-temperature superposition.
5
 Part 1: step 1,2 and 3:
1
Action Description of the action
As shown in 1. Picture should appear one after another
animation as shown in the slides.
2. Maroon call out ( in slide 1) should appear
in sync with the sentence highlighted in
red in audio narration para 3.
2 3. Green call out ( in slide 1) should appear
in sync with the sentence highlighted in
pink in para 3.
4. In slide 2, both yellow and pink item
should appear in sync with sentence
3 5.
highlighted in green in audio narration
para 5.
In slide 2, green box should appear when
narrator is narrating the sentence of para
7 highlighted in blue.
4 hours. Similarly, when reaction is
5 combinations of temperature and
Audio Narration
1. To understand the principle of
time temperature superposition,
let me start with a chemical
reaction as an analogy.
2. Consider a chemical reaction
between A and B which gives C as
a product. Let us assume that this
reaction is taking place at one
hundred and ten degree Celsius
for two hours, and conversion is
3.
seventy percent.
If I ask you to achieve the same
conversion, with the reaction
temperature of sixty degree
Celsius, then naturally you will
have to wait for longer time. Time
require to complete the reaction
will definitely be more than two
carried out at temperature higher
than one hundred and ten degree
Celsius, time of reaction
decreases.
4. It means that the same conversion
can be obtain at different
time of reaction.
5. If the desired conversion is
 Part 1: Step 1

1 Importance of time-temperature
superposition
1.1
What is time-temperature superposition ?
2
Time-temperature superposition is a tool to
determine material properties over broad range

3 of times and temperatures by shifting data.

Material properties should be temperature
dependent such as creep compliance, relaxation
modulus, loss and storage moduli, viscosity etc.
A material to which this technique is applicable
are said to be thermorheologically simple. This
4 terminology was introduced by Schwarzl and
Staverman.

5
 Part 1:

1 Time temperature superposition

T TS
2 G(t,T) vs. t G(at t,To) vs. at t

3 Where,
G is modulus
t is time
T is temperature
4 To is reference temperature
at is horizontal shift factor

5
 Part 1: Step 1

1 Importance of time-temperature
superposition
1.1
What is the importance of time-temperature
2 superposition ?
Any instrument, due to its mechanical limitations
can usually give data over a limited range of time or

3 frequency at a particular temperature, and this is

inadequate to determine viscoelastic properties at
very large time scale or at very low frequency.
Therefore, in order to probe the viscoelastic
properties of the material at extreme time scales,
time temperature superposition principle is needed.
4

5
 Part 1: Step 1

1 Importance of time-temperature superposition

1.1
Assumptions behind time-temperature
2 superposition principle:

1. The material does not undergo any chemical or

physical changes as a result of the temperature

3 change.
2. There is no phase transition as a result of
change in temperature.

4 3. There is no heterogeneity in the sample.

4. Applicable in linear viscoelastic regime only.

5
 Part 1: step 1,2 and 3:

1
Action Description of the action Audio Narration
As shown in 1. Picture should appear one after another 1. Now we can define time
animation as shown in the slides. temperature superposition.
2. Time-temperature superposition is
a tool to determine material
properties over broad range of
2 times and temperatures by
shifting data. Material properties
should be temperature dependent
such as creep compliance,
relaxation modulus, loss and

3 storage moduli, viscosity etc. A

material to which this technique is
applicable are said to be
thermorheologically simple. This
terminology was introduced by
Schwarzl and Staverman.
3. Before going into detail, we ought
to know why we should go for
4 time temperature superposition
and what is the importance of
time temperature superposition ?
4. Time temperature superposition is
needed because any instrument,
due to its mechanical limitations
can usually give data over a
5 limited range of time or frequency
at a particular temperature, and
this is inadequate to determine
 Master Layout
1 This animation consists of three parts:
Part 1: Importance of time-temperature superposition (TTS)
Part 2: Time-temperature superposition in frequency domain
Part 3: Time-temperature superposition in time domain
2 Part 4: Calculation of shift factor
Master curve
110o C
120o C
6 6
130o C

Log G, dyne/cm 2
Log G, dyne/cm2

3 140o C
5 5

150o C

4 4 4 at horizontal shift factor

160o C

170o C
3 3
-3 -2 -1 0 1 -3 -2 -1 0 1
5 Log , Hz Log at + Log , Hz
 Part 2

1 Time-temperature superposition in frequency domain

Frequency sweep of polymer melt Reference temperature is 140o C
110o C
120o C
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5

3 4
150o C

160o C
4

170o C

4 3
-3 -2 -1 0 1
3
-3 -2 -1 0 1

Log , Hz Log , Hz

G- Storage modulus
- Frequency
5
 Part 2

1 Time-temperature superposition in frequency domain

Frequency sweep of polymer melt Reference temperature is 140o C
110o C
120o C
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5

3 4
150o C

160o C
4

170o C Shift violet curve

to the right and
4 3
-3 -2 -1 green
0 to
1 the
3
left-3 -2 -1 0 1
such that all
Log , Hz curves collapses Log , Hz
into a single
curve by means
G- Storage modulus of horizontal
- Frequency
5 shift.
 Part 2

1 Time-temperature superposition in frequency domain

Frequency sweep of polymer melt Reference temperature is 140o C
110o C
120o C at
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5
at

3 4
150o C

160o C
4

170o C

4 3
-3 -2 -1 0 1
3
-3 -2 -1 0 1

Log , Hz Log , Hz

G- storage modulus
- frequency
5
 Part 2

1 Time-temperature superposition in frequency domain

Frequency sweep of polymer melt Generation of master curve at 140o C
110o C
120o C at
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5
at

3 4
150o C

160o C
4

170o C

4 3
-3 -2 -1 0 1
3
-3 -2 -1 0 1

Log , Hz Log at + Log , Hz

G- storage modulus
- frequency at horizontal shift factor
5
 Part 1: Step 1

1 Time-temperature superposition in frequency domain

Frequency sweep of polymer melt Master curve at 140o C
at
110o C
120o C at
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5
at

3 4
150o C

160o C
4
at

at
170o C

4 3
-3 -2 -1 0 1
3
-3 -2 -1 0 1

Log , Hz Log at + Log , Hz

G- storage modulus
- frequency at horizontal shift factor
5
 Part 2

1 Importance of time-temperature superposition

Frequency sweep of polymer melt Master curve at 140o C

110o C
120o C
6 6
2 130o C
Log G, dyne/cm2

Log G, dyne/cm2
140o C
5 5

3 4
150o C

160o C
4 at horizontal shift factor

170o C

4 3
-3 -2 -1 0 1
3
-3 -2 -1 0 1

Log , Hz Log at + Log , Hz

G- storage modulus Storage modulus at 170o C at higher frequency

- frequency is equivalent to storage modulus at 140o C at
5 lower frequency.
 Part 2

1 Time-temperature superposition in frequency domain

1.1

2 The inefficiency of measuring the polymer

behavior at longer time scale is avoided by
utilizing the fact that, the polymer behavior at
higher temperature and smaller time scale will
3 be the same.

5
 Part 2

1
Action Description of the action Audio Narration
As shown in 1. Picture should appear one after another 1. We will now consider two
animation as shown in the slides. examples of time temperature
superposition principle in both
frequency and time domain. Let
us , first discuss the this principle
2 in frequency domain.
2. Consider the plot of storage
modulus as a function of
frequency for a polymer melt
system at different temperatures

3 3.
ranging from one hundred and ten
degree celsius to one hundred
and seventy degree celsius.
You can see that at any frequency,
modulus is increasing with
decrease in temperature and over
all behavior of each curve is the
same.
4 4. That is modulus is increasing with
frequency at any temperature.
5. Due to the sensitivity of the
instrument, data at very low
frequency cannot be obtained.
That is if you are interested in
probing sample behavior at longer
5 time scale, then it is not possible
to predict behavior with the help
of instrument.
 Master Layout
1 This animation consists of three parts:
Part 1: Importance of time-temperature superposition (TTS)
Part 2: Time-temperature superposition in frequency domain
Part 3: Time-temperature superposition in time domain
2 Part 4: Calculation of shift factor

5o C Master curve
1.1
10 1.1
10
3
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8
25o C
35o C
4 6 45o C 6

at horizontal shift factor

55o C
4 4
-4 2 4 5 -4 2 4 5
-2 0 -2 0

5 Log t, hrs. Log at + Log t, hrs.

 Part 3

1 Time temperature superposition in time domain

Relaxation modulus data of polymer Reference temperature is 25o C

2 5o C
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C
35o C
6 45o C 6

55o C
4 4
-4
-2 0 2 4 5
4
-4
-2 0 2 4 5

Log t, hrs. Log t, hrs.

E - Relaxation modulus
t - Time
5
 Part 3

1 Time temperature superposition in time domain

Relaxation modulus data of polymer Reference temperature is 25o C

2 5o C
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C
35o C
6 45o C 6

55oShift
C the blue
curve to the left
4 4
-4
-2 0 2 and4
the yellow
5
4
-4one
-2 0 2 4 5
to the right such
Log t, hrs. that all curves Log t, hrs.
collapses into a
E - Relaxation modulus single curve by
t - Time means of
5 horizontal shift.
 Part 3

1 Time temperature superposition in time domain

Relaxation modulus data of polymer Reference temperature is 25o C

2 5o C
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C
35o C
6 45o C 6

55o C
4 4
-4
-2 0 2 4 5
4
-4
-2 0 2 4 5

Log t, hrs. Log t, hrs.

E - Relaxation modulus
t - Time
5
1 Time temperature superposition in time domain
Relaxation modulus data of polymer Generation of master curve at 25o C

2 5o C at
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C at
35o C
6 45o C 6

55o C
4 4
-4
-2 0 2 4 5
4
-4
-2 0 2 4 5

Log t, hrs. Log at + Log t, hrs.

E - Relaxation modulus
t - Time at horizontal shift factor
5
1 Time temperature superposition in time domain
Relaxation modulus data of polymer
Master curve at 25o C

at
2 5o C at
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C at
35o C
6 45o C 6
at
at
55o C
4 4
-4
-2 0 2 4 5
4
-4
-2 0 2 4 5

Log t, hrs. Log at + Log t, hrs.

E - Relaxation modulus
t - Time at horizontal shift factor
5
1 Time temperature superposition in time domain
Relaxation modulus data of polymer Master curve at 25o C

2 5o C
1.1
10 1.1
10
Log E, dyne/cm2

Log E, dyne/cm2
15o C
8 8

3 25o C
35o C
6 45o C 6

at horizontal shift factor

55o C
4 4
-4
-2 0 2 4 5
4
-4
-2 0 2 4 5

Log t, hrs. Log at + Log t, hrs.

E - Relaxation modulus Relaxation modulus at 45o C at lower time
t - Time scale is equivalent to relaxation modulus at
25o C at higher time scale.
5
 Part 3

1
Time-temperature superposition
1.1

2 If the relaxation behavior of the polymer at 25o C

were to obtained in the similar time scale, then
this behavior will be the same as the curve
produced by superimposing different curves

3 obtained at several temperatures.

5
 Part 3

1
Action Description of the action Audio Narration
As shown in 1. Picture should appear one after another 1. Let us now discuss this
animation as shown in the slides. superposition principle in time
domain.
2. For this, consider a log log plot of
relaxation modulus versus time for
2 a polymer at different
temperatures.
3. In this experiment, the material is
subjected to rapid deformation
and the stress on the material is

3
monitored with time. Since stress
is a function of time, therefore
tensile relaxation modulus is also
a function of time.
4. To capture the behavior of stress,
relaxation modulus is plotted
against time and it is observed
that modulus is decreasing with
time at a given temperature.
4 5. We can see that relaxation
modulus is decreasing for a given
temperature, but it decreases as
temperature increases.
6. This experiment has been carried
for time scale of two decades.
But, what if, we want to see the
5 relaxation behavior for time scale
over four decades ?
 Master Layout
1 This animation consists of three parts:
Part 1: Importance of time-temperature superposition (TTS)
Part 2: Time-temperature superposition in frequency domain
Part 3: Time-temperature superposition in time domain
2 Part 4: Calculation of shift factor

WLF equation Arrhenius equation

3

-C1 (T-To ) at = exp[(Ea /R)(1/T 1/To )]

Log at =
4 [C2 + (T-To )]

5
 Part 4

1 Calculation of shift factor

Horizontal shift factor can be calculated based on Williams-
Landel-Ferry (WLF) and Arrhenius equations.

2 WLF equation
C1 and C2 are constants
-C1 (T-To ) T is temperature in Kelvin
Log at =

3
[C2 + (T-To )]
To is reference temperature in Kelvin

WLF equation is applicable for system having glass transition temperature, T g .

If To Tg then C1 17.44 and C2 51.6 K.

4
Arrhenius equation
Ea is activation energy
at = exp[(Ea /R)(1/T 1/To )]
R is universal gas constant
5
 Part 4:

1
Action Description of the action Audio Narration
As shown in As shown in animation 1. We will learn now how to
animation calculate shift factors. Shift
factors are used for shifting raw
data to generate master curve. By
incorporating horizontal shift
2 factor into raw data, new sets of
data are produced, which when
plotted shows behavior of the
material property at several
decades of time or frequency.

3
2. For example, if you have a plot
of modulus vs time at different
temperatures, then by
incorporation of shift factors,
reduced modulus vs reduced time
can be plotted.
3. Horizontal shift factor can be
calculated by using WLF equation
and Arrhenius equation.
4

5
APPENDIX 1
Questionnaire
1. Time temperature superposition is a tool used for determination of material
property preferably at
a) longer time scale
b) Smaller time scale
2. In a log-log plot of relaxation modulus vs. time, modulus obtained at 50o C is
100 Pa at time T1 . If you want to observed the same modulus at 25o C, then
this will be observed at time scale (T2)
a) T2 > T1 b) T2 < T1 c) T2 = T1
3. Arrhenius equation for calculating horizontal shift factor is valid near glass
transition temperature
a) True b) False
4. A student wishes to apply the technique of time temperature superposition
to determine the long time rheological behavior of polymer solution, but
during the experiment it is found that solvent is evaporating. Would this
render him violation of assumption involved in time temperature
superposition principle ?
a) Yes b) No
5. Heterogeneity in the polymer sample should not be there for time
temperature principle to be valid.
a) True b) False
APPENDIX 1
Answers
1. Time temperature superposition is a tool used for determination of material
property preferably at
a) longer time scale
2. In a log-log plot of relaxation modulus vs. time, modulus obtained at 50o C is
100 Pa at time T1 . If you want to observed the same modulus at 25o C, then
this will be observed at time scale (T2)
a) T2 > T1
3. Arrhenius equation for calculating horizontal shift factor is valid near glass
transition temperature
b) False
4. A student wishes to apply the technique of time temperature superposition
to determine the long time rheological behavior of polymer solution, but
during the experiment it is found that solvent is evaporating. Would this
render him violation of assumption involved in time temperature
superposition principle ?
a) Yes
5. Heterogeneity in the polymer sample should not be there for time
temperature principle to be valid.
a) True
APPENDIX 2

Links for further reading

References:

Kumar, A.; Gupta, R.K. Fundamentals of polymers, Tata-McGraw

Hills international, pp 389-392
http://en.wikipedia.org/wiki/Timetemperature_superposition
APPENDIX 3
Summary

Time-temperature superposition is a tool to determine material

properties over broad range of times and temperatures by
shifting data.

The inefficiency of measuring the polymer behavior at longer

time scale is avoided by utilizing the fact that, the polymer
behavior at higher temperature and smaller time scale will be
the same.

Shift factor can be calculated by WLF and Arrhenius

equations.