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superposition
Time-temperature superposition is a tool to
determine the material properties over broad range
of times and temperaturesby shifting data.
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.
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
3 A+ B
T = 60o C
C
Conversion = 70%
5
Part 1: Step 1 Slide 2
1 Importance of time-temperature
superposition
1.1
Temperature = 110o C
2 A+ B C Conversion = 70%
3 If the desired conversion is 80%, then this conversion can be obtained either by
1
Action Description of the action Audio Narration
As shown in 1. Picture should appear one after another 1. To understand the principle of
animation as shown in the slides. time temperature superposition,
2. Maroon call out ( in slide 1) should appear let me start with a chemical
in sync with the sentence highlighted in reaction as an analogy.
red in audio narration para 3. 2. Consider a chemical reaction
2 3. Green call out ( in slide 1) should appear between A and B which gives C as
in sync with the sentence highlighted in a product. Let us assume that this
pink in para 3. reaction is taking place at one
4. In slide 2, both yellow and pink item hundred and ten degree Celsius
should appear in sync with sentence for two hours, and conversion is
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.
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
4 hours. Similarly, when reaction is
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
5 combinations of temperature and
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
5
Part 1:
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
5
Part 1: Step 1
3 change.
2. There is no phase transition as a result of
change in temperature.
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
Log G, dyne/cm 2
Log G, dyne/cm2
3 140o C
5 5
150o C
170o C
3 3
-3 -2 -1 0 1 -3 -2 -1 0 1
5 Log , Hz Log at + Log , Hz
Part 2
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
Log G, dyne/cm2
140o C
5 5
3 4
150o C
160o C
4
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
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
G- storage modulus
- frequency at horizontal shift factor
5
Part 1: Step 1
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
G- storage modulus
- frequency at horizontal shift factor
5
Part 2
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
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
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
E - Relaxation modulus
t - Time
5
Part 3
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
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
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
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
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
1
Time-temperature superposition
1.1
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
5
Part 4
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
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
References: