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Equivalent Slope Method for Construction of Master Curves

Article · February 2018

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 TECHNICAL PAPER

EQUIVALENT SLOPE METHOD FOR CONSTRUCTION

OF MASTER CURVE

DR NIKHIL SABOO1 DR PRAVEN KUMAR2

ABSTRACT
Time Temperature Superposition (TTSP) has been used since a long time for construction of master curves
for polymers which are thermorheologically simple. A new method has been developed through MATLAB
program which can automatically create master curve at any reference temperature provided the material
obeys thermorheological simplicity. The new method has been compared with other existing shift factor laws
using graphical interpretations. It was found that this method can be successfully employed for master curve
construction at any reference temperature chosen. Relationship between shift factor and temperature was
established using mathematical equations.

1 INTRODUCTION temperatures for a measurable range of frequency,

Engineering behavior of any material can be judged
by its stress and strain analysis. Dynamic Shear
Rheometer (DSR) has been used since a long time
for judging and describing the rheological properties
of polymers like bitumen. A single rheometer can be
operated to give values only over a range of three
to four decades at a particular temperature (Dealy
and Plazek). For bitumen and modified binders
comprising polymers, this data is insufficient to
describe the complete rheological and viscoelastic
response from the high frequency end of the plateau
zone to the low-frequency terminal zone. Time
Temperature Superposition (TTSP) is a competent
tool for describing the viscoelastic behavior of linear
polymers over a broad range of time and frequency,
by shifting data obtained at several temperatures to
a common reference temperature (Benedetto et al.,
Airey G.D). In linear polymers viscoelasticity arises
from a molecular rearrangement process, which
occurs from a stress or from a diffusion process
under stress. The speed of these processes depends
on the speed of molecular motion, where temperature
is a measure. In such materials, all the processes
contributing to the viscoelasticity of a material
are accelerated to the same extent by temperature
rise (Lakes). Thus, by obtaining data at several
1
Ph.D. Scholar, Transportation Engg Group, Civil Engg Deptt. IIT Roorkee
2
Professor and Coordinator, Transportation Engineering Group, Civil Engg Deptt., IIT Roorkee, email:pkaerfce@iitr.ac.in
a master curve could be plotted at a single reference
temperature that could cover many decades of
frequency/time. A material to which this technique is
applicable is said to be thermorheologically simple
(Maxwell., Airey).
Temperature dependent shift factors are used for
the magnitude of stresses (vertical shift) and time/
frequency (horizontal shift) on log-log plots of
material functions, like complex modulus, phase
angle and creep compliance. The temperature
dependent, vertical shift factor multiplies a stress,
determined at temperature T to yield a “reduced
stress”, that is the value at the reference temperature
chosen. Similarly, the horizontal shift factor divides
a time or multiplies a frequency to yield a reduced
frequency/time scale of ω aT or t / aT . This principle
can be mathematically written as
bT E (ZaT , T ) E (Z, T0 )
(1.1)
1.1 Shift Factors
1.1.1 Vertical shift factor
Research (Doi and Edwards) has shown that
stress functions of linear viscoelastic materials
are proportional to the product of density and
temperature. The vertical shift factor represents

INDIAN HIGHWAYS│FEBRUARY 2018 19

 TECHNICAL PAPER
temperature induced density changes and involves
shift along the modulus or stress function axis. This
implies that the vertical shift factor can be written
as
bT (T0 U0 ) / (T U )
(1.2)
Where, T0 is the reference T temperature, is the
temperature at which shift factor has to be applied,
ρ0 and ρ are the corresponding densities.
The vertical shift factor is also sometimes determined
directly from the variation with temperature of
a distinctive value of a modulus or compliance,
such as a maximum or minimum in loss modulus.
Plateau of the material functions can also be used.
Determining horizontal shift of loss angle, in loss
angle versus log |G*| plot (Van Gurp-Palmen plot)
is another way of determining vertical shift factor
that is independent of time or frequency shift.
However, most of the research to date on binders
and bituminous materials, mastercurve construction
does not normally consider vertical shift and it is
assumed to be unity (Airey).
1.1.2 Horizontal shift factor
Horizontal shift factor aT is a number which is
required to be multiplied to the time/ frequency
to shift data at a particular temperature T to the
reference temperature T0. Different researches had
been conducted in finding a suitable value of aT for
bituminous materials which could be employed
based on its thermal behavior. These studies focuses
from the physical molecular aspect of the binder to
its chemical behavior.
1.1.2.1 Shift based on viscosity
Viscosity is a parameter which comprises of stress
and time. It requires the application of both the
shift factors. If complex viscosity η is used as the
*
rheological parameter then the master curve for
bT
complex viscosity is plotted between aT η (T ) and
*
ω aT . This implies that if zero shear viscosity is taken
into consideration one can write,
bT (T )
η0 (T ) = η0 (T0 )
aT (T ) (1.3)
Considering the vertical shift factor as unity, vertical
shift factor can be written as,
η (T )
aT (T ) = 0
η0 (T0 ) (1.4)
20 INDIAN HIGHWAYS│FEBRUARY 2018
1.1.2.2 Arrhenius equation
Observation of the dependence of viscosity of
liquids on temperature led to the empirical Arrhenius
relationship that can be expressed as
Ea
aT (T ) = exp[ (1/ T − 1/ TR )] (1.5)
2.303R
Where Ea is called the activation energy, typically
250 kJ/mol for bituminous binders (Airey). It is the
minimum energy required for any intermolecular
movement. R is the universal gas constant 8.314
J/0K-mol. Arrhenius equation has been found to
fit data at the terminal and plateau zones for linear
polymers as long as the temperature is well above
the glass transition temperature Tg. Also meaningful
activation energy has not been defined so far.
Variation in Ea with frequency and modulus has also
been reported. So a logical value must be chosen
which could have some significance regarding the
physical and/or chemical nature of bitumen.
1.1.2.3 William-Landel-Ferry equation
This equation is based on the free volume concept
of Doolittle. It has been widely used to describe
relation between aT and temperature dependency of
bitumens.
−C1 (T − Tref )
log aT = (1.6)
C2 + (T − Tref )
Where, C1 and C2 are empirical constants. The
implication of this model lies in the determination
of these constants. Moreover, this equation has been
mainly found suitable when reference temperature
is close to Tg. Many universal constants have been
proposed based on the reference temperature. The
most famous and frequently used values are 8.86 and
101.6 for C1 and C2 as proposed by Williams et al.
These values have shown good fit when T-Tr>-20oC.
Another values proposed by Anderson were 19 and
92 which were based on some defining temperature
Td. This defining temperature is not very clear and is
bitumen specific.
Williams et al. proposed that the reference
temperature is related to glass transition temperature
as
Tr − Tg = 500 C (1.7)
But master curve should be such that, one must
be able to view the rheological behavior at any
reference temperature desired. This limits the use of
 TECHNICAL PAPER

WLF equation which has strong dependence on the
selection of reference temperature.
1.1.2.4 Manual shift procedure
This is a simple procedure in which the data are
shifted manually in MS EXCEL or similar workbook
till a best and smooth fit is obtained. The smoothness
of the curved is judged visually. If smooth curve
cannot be obtained, it implies that the binder is not
thermorheologically simple.
1.2 Equivalent Slope Method (ESM)
The shift factor laws, as given by Arrhenius and
WLF equations give satisfactory results provided the
reference temperature is chosen properly. Mostly the
laws are valid near the glass transition temperature
of the polymer, which is very low for bitumen as well
as polymer modified binder. Bitumen as a binder is
exposed to service temperatures ranging from about
-50C to 600C. So, it is more appropriate to construct
the master curve at a reference temperature which
is under service conditions. Given the rheological
data, a user should be able to construct master curve
at any reference temperature under interest.
Appreciating the fact that thermorheological
simplicity can be validated if a smooth curve
is obtained after shifting the data at a particular
reference temperature, it would be more convenient
to introduce a process which will provide shift till a
best fit is obtained, and will return the shift factors
once the shifting process is accomplished. Finally,
the graph so obtained can be analyzed visually to see
if the material obeys time temperature superposition
principle.
A new procedure was hence introduced and was
programmed using MATLAB. The method is named
as ‘Equivalent Slope Method’ (ESM) and could
be used to plot master curve for any rheological
parameter requiring horizontal shift at any reference
temperature. The base behind the development of
this procedure is that, the stress function for two
different temperatures merges to a single or nearly
similar value, but at different frequency. So, shifting
the curve till the slope at few desired points become
similar would yield a smooth master curve, provided
thermorheological simplicity prevails.
The algorithm adopted for preparing the program for
obtaining shift factor is presented below. Few terms
are defined formerly to understand the procedure.
i → Frequency , i ∈ [1, k ]
j → Temperature, j ∈ [10, 70]
TR → Reference Temperatrure
, R⊂ j
Yi , j → Value of Y variable at Frequency i and Temperature j

Input Frequency sweep data from excel sheet and p lot Parameter Y versus Frequency i
↓
Select the reference temperature, TR
↓
For curve R and R +1, calculate [Yi , R − Yi −( k +1−i ), R +1 ]
↓
Find the value of i for which the above is minimum. let it be x th p oint, x ∈ [1,k]
↓
th th
Take (x +1) and (x - 1) p oint and assuming a straight line find 25 points between them
Let it be called cm th p oint, c ∈ [x +1,x - 1],m ∈ [1,25]
↓
Find [Yc , R − Yx −( k +1− x ), R +1 ]
↓
Find the value of m for which the above is minimum. Let it be called pth point, p ∈ c
↓
Frequency p , R
Shift factor f or temperature TR +1 = [ ]
Frequencyx −( k +1− x ), R +1

INDIAN HIGHWAYS│FEBRUARY 2018 21

 TECHNICAL PAPER

The above concept is extended similarly for other 3.1 Validation of Shift Factors
temperatures, below and above the reference Manual shift was employed first at each reference
temperature. This method can be used to construct temperature to obtain a smooth complex modulus
master curve for stress functions in which horizontal master curve. Next, different shift factors as
shift is required. mentioned above were used to make a comparison
2 MATERIALS and their validation in obtaining master curves at
Three binders were used in the study for validation any reference temperature chosen. Variation of shift
of different shift factor laws in construction of factor was found by plotting the manual shift factors
master curves, at any chosen reference temperature. as the abscissa and the shift factors of various other
A VG-10 viscosity graded binder was used models as ordinate. Deviation from the equality line
and was modified with an elastomer SBS and a would mean poor correlation.
plastomer EVA. The concentration of polymers William-Landel-Ferry (WLF) shift factors were
were optimized in an earlier study with respect to obtained using the universal constants given by
proper homogeneity to be obtained. The respective Williams et al. (8.86 and 101.6). These values were
percentages for SBS and EVA were 3% and 5%. used to see its application at different reference
The conventional properties of these binders are temperatures considered in the study. The value of
presented in Table 1. Ea in Arrhenius equation was found by optimizing
Table 1. Conventional Properties of Binders the sum of least squares with respect to manual shift
using SOLVER function in MS EXCEL.
Properties Standard VG 10 VG 10+ VG 10+
SBS - EVA - 4 RESULTS AND ANALYSIS
3% 5% From the isothermal plots, it was found that for
Penetration ASTM 82 62 55 modified binders the decrease in stiffness with
D5 increase in temperature is lower as compared to
Softening ASTM 46 55 63 base binder. This indicates that higher shift factor
point D36 has to be employed at each temperature to obtain
Specific ASTM 1.01 0.99 1 master curve. This may be attributed to the fact
Gravity D70 that modification leads to increase in viscoelastic
Penetration - -1.07 0.52 1.86 response of the base binder.
Index Figs. 1, 2 and 3 shows the deviation of different shift
3 EXPERIMENTAL factor laws with respect to the manual shift for VG-
10, SBS PMB and EVA PMB. The graphical plots
Frequency sweep test was done on all the binders are shown for reference temperatures of 10, 30, 50
using a Dynamic Shear Rheometer (DSR). In the
and 70°C. The plots at other reference temperature,
initial part of the study, linear viscoelastic (LVE)
though plotted, but are not shown for space limits.
strain was measured using strain sweep test at
different frequencies and temperatures for all the WLF equation showed the highest deviation at all
binders. The magnitude of strain in the frequency reference temperatures. As the reference temperature
sweep test was chosen to ensure that the asphalt increased the shift factor obtained by WLF equation
binders remain in the LVE domain. The following were found to be much higher than that required for
test variables were chosen for the study getting a smooth curve. This may be due to the fact,
Frequency: 0.1-100 rad/sec that the Williams constant adopted is only suitable
for temperatures near the glass transition temperature
Test Temperature: 10, 20, 30, 40, 50, 60 and of the binder. The deviations were found to be least
70 °C.
at 30 and 40 °C. So, these constants cannot be used
Spindle specification: 8mm dia. and 2mm gap at operating temperatures and the constants need to
for 10-30 °C. be found by optimization techniques for different
25mm dia. and 1mm gap for 40-70 °C. reference temperatures.

22 INDIAN HIGHWAYS│FEBRUARY 2018

 TECHNICAL PAPER
Arrhenius equation gave better results than the
WLF equation. The optimized value of Ea were
found to be higher for modified binders, the highest
value being obtained for EVA PMB. This should
be true because modification leads to increase in
stiffness and crosslinking of polymers, which will
require higher energy for triggering intermolecular
movements. Though the deviation were not very
high for Arrhenius plot, still a smooth master curve
was not obtained.
Both WLF and Arrhenius plot were found to be
sensitive to the reference temperature chosen. As an
example, master curve obtained by using these shift
factor laws are presented in Figs. 4 and 5 at three
different reference temperature of 10, 30 and 70 °C
for VG 10. These shift factor laws were found to be
(a)
(c)
Fig. 1 (a-d) Validation of Shift Factor Laws for VG 10
poor for construction of master curves at pavement
working temperatures, though they have been found
successful at temperatures near to the glass transition
of the polymer.
It can be seen that ESM yielded the best fit
at all the reference temperatures. The shift
factors almost coincided with the equality line
indicating least deviation from the manual shift
factors. Fig. 6 shows the master curve plots
obtained from MATLAB program using this
method at three different reference temperatures
for VG 10. Very smooth master curves were
obtained by using the shift factor obtained by
the method. It was found to be successful tool
for plotting master curve for thermorheological
simple binders.
(b)
(d)
INDIAN HIGHWAYS│FEBRUARY 2018 23
 TECHNICAL PAPER

(a) (b)

(c) (d)
Fig. 2 (a-d) Validation of Shift Factor Laws for SBS PMB

(a) (b)

24 INDIAN HIGHWAYS│FEBRUARY 2018

 TECHNICAL PAPER

(c) (d)
Fig. 3 (a-d) Validation of Shift Factor Laws for EVA PMB

(a)

(b)

(c)
Fig. 4 (a-c) Master Curves Obtained Using WLF Shift Factor

INDIAN HIGHWAYS│FEBRUARY 2018 25

 TECHNICAL PAPER

(a)

(b)

(c)
Fig. 5 (a-c) Master Curves Obtained Using Arrhenius Shift Factor

(a) (b)

Fig. 6 (a & b) Master Curves Obtained Using ESM in MATLAB

26 INDIAN HIGHWAYS│FEBRUARY 2018

 TECHNICAL PAPER

(c)
Fig. 6 (c) Master Curves Obtained Using ESM in MATLAB

4.1 Modelling of Shift Factor

The factors obtained by the equivalent slope
method were used for plotting log-log graph
between aT and Temperature. It was found
that the plot followed a polynomial function
irrespective of the type of binder and reference
temperature. As an example plot for VG 10, SBS
and EVA PMB at all three reference temperatures
are shown in Fig. 7 (a-c). The shift factor can be
written mathematically as
Y = A1 X 2 + A2 X + A3 (b)

Where,

Y = log aT ; X= logT
A1, A2, A3 are the coefficients whose value
depend on the type of binder and the reference
temperature. The constants represent the amount
of shift required for any particular binder at a
specific temperature. So no universal constants
could be assumed for them. It should be found
with curve fitting techniques. (c)
Fig. 7 (a-c) Log aT versus Log T at the three
reference Temperatures Chosen in the Study for all
the Binders.

5 CONCLUSIONS
The study mainly focused on the validation of
various shift factor laws most commonly used
for construction of master curves. The study
also attempted in development of an automated
process for construction of master curve for
polymers resembling thermorheological simplicity
(a) and modelling the same. It has been named as

INDIAN HIGHWAYS│FEBRUARY 2018 27

 TECHNICAL PAPER
“Equivalent Slope Method”. It was found that WLF
and Arrhenius laws for obtaining shift factors cannot
be used for plotting master curves at operating
temperatures. The laws are very sensitive to the
choice reference temperature. Value of Ea obtained
by optimization for Arrhenius equation were higher
for polymer modified binders indicating presence of
tough polymer network after modification. ESM was
found to give excellent fit with respect to manual
shift. The shift factors obtained using ESM can be
successfully used in construction of master curves
at any reference temperature.
With higher interest in study of rheological
properties of polymer such as bitumen,
construction of master curve is one of the starting
steps in characterizing the enhanced viscoelastic
response. The method so developed can hence
be practically and successfully employed in
understanding the complex behavior at ambient
working temperatures, at which the most
common methods fails to give a smooth master
curve. Also, the same can be used in judging
whether or not the material under consideration is
thermorheologically simple.
The methodology developed in this study can
hence be used to judge the thermorheological
simplicity of asphalt binders and will aid in smooth
construction of mastercurves at any desired reference
temperature. In addition, appropriate shift factors
could be arrived at using this methodology. Indian
Roads Congress currently has limited guidelines
which use the rheology of asphalt binders to assess
the performance of bitumen. However, in the near
future it is expected that studying the rheology of
bitumen will be an inherent part of various upcoming
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specifications, where knowledge regarding the
construction and study of mastercurves will become
important.
REFERENCES
1. Airey G.D. (1997). Rheological Characteristic
of Polymer Modified and Aged Bitumens. Ph.D
Thesis, University of Nottingham.
2. Airey G.D., Rahimzadeh B. and Callop A.C.
(2003). Viscoelastic Linearity Limits for
Bituminous Materials. Materials and Structures
3. Benedetto H.D., Sauzeat C., Bilodeau K.,
Buannic M., Mangiafico S., Nguyen Q.T., Pouget
S., Tapsoba N., Rompu J.V. (2010). General
Overview of Time-Temperature Superposition
Principle Validity for Materials Containing
Bituminous Binder. International Journal of Roads
and Airports.
4. Dealy J and Plazek D. (2009). Time-Temperature
Superposition- A Users Guide. Rheology
Bulletin.
5. Doi M. and Edwards S.F. (1986). The Theory of
Polymer Dynamics. Clarendon Press, Oxford.
6. Ferry J.D. (1980). Viscoelastic Properties of
Polymers. John Wiley & Sons, 3rd edition.
7. Lakes R.S. (2009). Viscoelastic materials.
Cambridge University Press.
8. Maxwell J.C. (1886). Linear Viscoelasticity.
9. Yusoff N.I.M., Jakarni F.M., Nguyen V.H.,
Hainin M.R., Airey G.D. (2013). Modelling the
Rheological Properties of Bituminous Binders
Using Mathematical Equations. Construction and
Building Materials, 174-188.