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Generating Mastercurves
revised A.J. Franck, TA Instruments
Keywords: t-T superposition, WLF, Arrhenius, activation energy, mastercurve, transition,
reduced variables

THE EQUIVALENCE OF TIME AND 10

10
TEMPERATURE EFFECTS1
9 T=-40
The rheological behavior of viscoelastic materi- 10
T=-20
als varies with both time and temperature. Re-

Relaxation Modulud E(t) [Pa]

8
10
peating DMA tests with the same material at dif- T=-10

ferent temperatures shifts the tan d peaks in the 10

7 T=0
transition region to shorter times (higher frequen- T=10
cies) with increasing temperature.This is evident 10
6
T=20
T=30
from figure 1, showing stress relaxation meas- T=40
5
T=50
urements made on a polymer at a series of tem- 10

peratures over a time span of a minute to a week. 4

T=75
10
Large differences are seen, yet only a small range T=100
of the viscoelastic response manifests itself 10
3

within these time (frequency) spans. A broader 0 1 2 3

10 10 10 10 10 10
4 5

picture of the time-related response is needed to Time[min]

understand this behavior fully.
But this is easier said than done, for the infor-
Fig. 1. Stress relaxation date as a function of
mation is not equally accessible experimentally. temperature
While measurements that span a wide range of
pertinent temperatures can be made with rela-
tive ease, it is not as easy to achieve measure- tion. Conversely, elevating the temperature
ments outside the range of mentioned times: speeds these processes in proportion to the tem-
Changes that occur in less than a second are dif-
perature increase.
ficult to measure, and time spans longer than a
week are inconveniently long. Furthermore, it was observed that the princi-
pal effect of changing the temperature is to
A solution arizes from the experimental find-
rescale the time: Temperature changes shift the
ings that time and temperature of time-depend- viscoelastic functions along the modulus and
ent processes have equivalent effects on the time (or frequency) scales without changing their
rheological properties of linear viscoelastic ma- shapes. A result of the foregoing observation was
terials. Thus, if the temperature of a flexible poly- the finding that a composite curve called a “mas-
mer is lowered, stress relaxation or creep recov- ter curve’ could be generated from a series of
ery (as well as dynamic mechanical responses) curves of overlapping data collected at different
take longer than they would at a higher tem-
temperatures.
perature, and the extent these processes are
slowed is proportional to the temperature reduc- This procedure is referred to as time-tem-

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perature superposition (TTS). therefore a parallel shift along the logarithmic
time or frequency axes 3.
TIME-TEMPERATURE This is shown schematically in figure 2 for
SUPERPOSITION (TTS) the shear modulus G(t). The parallel shift can be
expressed as :
Increasing temperature shifts the transition
area, which shows as a drop in the modulus or a G(t,T)=G(tr,To) with tr=t/aT (T,To)
The factor aT is the horizontal shift factor and
tr the reduced time. In order to shift the dynamic
moduli G’ or G’’ the reduced angular frequency
wr=aT (T,To)w has to be used.
The sign of aT (the direction of the shift) de-
pends on the sign of the temperature difference
G(t,T) log a T
(T-To)
G(t,T)

G(t r,To) For the various material parameters the TTS

can be expressed as:
G(tr,To ) T To G(t,T)=GTo(tr)=GTo(t/aT)
G(t,T)
G’(w,T)=G’ To(wr)=G’To(w a T)
log t log tr G’’(w,T)=G’’To(wr)=G’’To(w a T)
tan d(w,T)=tan dTo(wr)=tan dTo(w a T )
GTo is the relaxation modulus at the reference
Fig. 2. Experimental determination of the temperature To.
shift factor aT
Figure 3 shows the master curve as a result of
shifting the curves in Figure 1 along the hori-
zontal axis and superimposing them in regions
damping peak in tan d, to shorter times or higher
of modulus overlap. The net effect is a compos-
frequencies. The shape of G(t), G’, G’’ and tan d
ite curve over a much wider range of time (fre-
however are not altered. The superposition is

10 10
10 10

T=0
9 T=-40 10
9
10
Relaxation Modulus E(t) [Pa]

T=-20
Relaxation Modulud E(t) [Pa]

8 8
10 10
T=-10

7
10
7 T=0 10

T=10
6 6
10 T=20 10
T=30
T=40
5 5
10 T=50 10

T=75 4
4
10 10
T=100
3 3
10 10
0 1 2 3 4 5 -4 0 4 8 12
10 10 10 10 10 10 10 10 10 10 10

Time[min] Time t [min]

Fig. 3. Master curve generated by horizontally shifting data from fig 1

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quency) than was accessible in the original test. log aT (T,To)= - c 1(T-To)/c2 + T - T o
The time-temperature superposition can be This equation is well known as the Williams,
applied to amorphous, non modified polymers Landel, Ferry (WLF) equation. To is the refer-
to obtain modulus and damping information in ence temperature, c 1 and c2 are material constants,
the frequency range, not accessible through the which also depend on To. Every reference tem-
experiment at a constant temperature. However perature has its associated parameter set c1 and
not all relaxation processes shift in the same way c2. The following parameter combinations how-
and the t-T superposition cannot be applied ever are invariants for the WLF equation:
across several relaxation processes. A material To’- c2’=To- c2=Too and
is referred to as thermo-rheological simple, if all c1’.c2’=c1.c2
the relaxations times shift with the same shift
For any amorphous material, if the reference
factor a T ,.
temperature To is selected to be the mid point of
If the t-T-shift is known for a process at the the transition, then T is material independent
oo
reference temperature To, it can easiy be reduced and equal to T -30o with T the glass transition.
g g
to another reference temperature To’ using fol- The invariant c .c represents the curvature of the
1 2
lowing conversion: aT (T,To) factor.
log a T (T,To’) = log a T (T,To) - log a T (To’,To)
TIME TEMPERATURE SHIFT IN THE
TIME TEMPERATURE SHIFT FLOW REGION
THROUGH A TRANSTION (THE
WILLIAMS, LANDEL, FERRY The time temperature shift in the flow region
EQUATION) of an amorphous uncrosslinked polymers is very
different from the shift in the glass transition re-
During a glass transition, a small change in gion. Instead of the modulus G(t), the expres-
temperature goes along with a significant drop sion G(t)/(rT) shifts parallel with time i.e fre-
in the modulus, sometimes over several decades. quency. The density-temperature correction can
However the magnitude of the change (slope on be significant in the flow region (20 to 30% for
the logarithmic plot m=dlog G(t)/dlog t) through- PS)
out the the transition is significant and can be The governing equations for the TTS in the
described by the following expression: flow region change to:

-PMMA PMMA
g g b b

PS
-PVC
10 -PBuMA PVC
0.1
-PCHMA PC
at 1 Hz
1000/T [K ]
-1

d 0.01
5
tan

1E-3
0

10
-5 0
10 10
5
10
10 15
10 50 100 150 200 250 300 350 400 450

Frequency [Hz] Temperature T [K]

Fig. 4. Arrhenius diagram for different Fig. 5 Damping behaviour of various

secondary relaxation processes of a variety of polymers as a function of temperature
materials

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 (ρoTo/ρT)G(t,T)=GTo(t/aT) DIAGRAM
(ρoTo/ρT)G’(ω,T)=G’To(ω aT)
Figure 5 shows the damping function of a se-
(ρoTo/ρT)G’’(ω,T=G’’To(ω aT) ries of commercial polymers including PMMA,
tan δ(ω,T)=tan δTo(ω r)=tan δTo(ω aT) PVC, PC and PS as a function of temperature.
PMMA shows a broad b relaxation which can
Note,thatthe equation for tanδ does not t be attributed to the rotation of the methyl-ester
PHASE BEHAVIOUR OF AMORPHOUS group around the -C-C- bond connecting the side
POLYMERS IN A TIME-TEMPERATURE group to the main chain. The b transitions of PC
and PVC have to be attributed to local transla-
tional displacements of short sections of the main
chain. PS has a very low damping in the glassy
state. A relaxation, related to the rotation of the
200
phenyl ring can be be seen at very low tempera-
ture only. The low temperature transitions are
100 directly related to the impact resistance of poly-
Temperatrure T [oC]

Melt state
mers. The short time damping correlates with the
Rubbery state
0 energy absoption during the impact. Materials
without significant low temperature damping are
a

brittle. This is the case for PS. Impact resistant

b

-100 Glass state

PS is a co-polymer of polystyrene and poly-
g

flow transition
transition
butadiene, the poly-butadiene adding significant
g b a

-200 transition damping to the low temperature transition.

transition
12 7 2 -3
Transitions of amorphous polymers are asso-
10 10 10 10
Frequency [Hz]
ciated to regions with pronounced damping char-
acteristics. Figure 6 shows the typical transition
temperatures as a function of the test frequency
in a WLF and Arrhenius representation for an
amorphous polymer. Notice, that the secondary
flow transition
transition transitions in the Arrhenius representation are
g b a

transition
10
transition
represented by a straight lines.
g

The flow transition separates melt and rub-

b

bery plateau, the glass transition (α) the rubbery

1000/T [K-1]

Glass state
region and the glass.
5
a

CONCLUSION
Rubbery state
Melt state
Master curves are helpful for understanding
0
the rheological behavior of a polymer: The su-
per-position process separates the two main vari-
-7
10 10
-2
10
3
10
8
ables - time and temperature - upon which the
Frequency [Hz] viscoelastic properties depend, expressing the
properties in terms of a single function for each.
The master curve shows the time dependence (in
Fig. 6a Phase transitions represented in a terms of frequency) of the material at a constant
frequency-temperature diagram according to reference temperature To; the temperature de-
WLF pendence of the viscoelastic properties is shown
Fig. 6b. Phase transitions represented in a
frequency-temperature diagram according to
by the variation of the shift factor with tempera-
Arrhenius ture.

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This method of generating master curves is not
limited to variations with temperature. Shift fac-
tors have been defined in terms of concentration,
applied strain, etc.2 and the WLF equation has
been generalized to yield a shift factor a21 for a
relaxation time li in state 2 to that in state 1. 1

REFERENCES
1. Ferry, J. D., Viscoelastic Properties of
Polymers 3rd edition, Wiley, 1980.
2. Nakajima, N. and Harrell, E. R., “Effect of
Extending Oil on Viscoelastic Behavior of
Elasto-mers,” J. Rheol. 26(5), 427-458 (1982).
3. Schwarzl, R., “Polymer Mechanik”, Springer
Verlag, ISBN 3-540-51965-3

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