Fuel 97 (2012) 603611

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Fuel
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The effect of long-term aging on the rheology of warm mix asphalt binders q
Ambarish Banerjee a,, Andre de Fortier Smit b,1, Jorge A. Prozzi a,2
a
Department of Civil, Architectural and Environmental Engineering, The University of Texas at Austin, ECJ Bldg., Ste. 6.10 (C1761), Austin, TX 78712, United States
b
Center for Transportation Research, The University of Texas at Austin, ECJ Bldg., Ste. 6.10 (C1761), Austin, TX 78712, United States

a r t i c l e i n f o a b s t r a c t

Article history: The study described in this paper aims at quantifying the long-term aging effects on the rheological
Received 13 October 2011 properties of warm mix asphalt (WMA) binders. Under the scope of this study, the authors focused
Received in revised form 29 January 2012 on four warm mix asphalt additives: Sasobit, Rediset, Cecabase and Evotherm, of which the rst one
Accepted 30 January 2012
is an organic and the latter three are synthetic additives. The rheology of the aforementioned additives
Available online 22 February 2012
added to a PG 64-22 binder were studied using a frequency sweep test performed over a range of ten
different loading frequencies and three different temperatures with different degrees of exposure to
Keywords:
oxidative aging.
Long-term aging
Rheology
The paper proposes a more efcient methodology for developing master curves for asphaltic materi-
Warm mix asphalt als based on joint estimation of the model parameters that eliminates any possible propagation of
Master curve biases from one model to the other. The developed master curves accommodate the simultaneous
quantication of the effect of loading time, temperature and aging on the rheological properties of
the WMA binder.
The paper nally addresses the effect of aging on different WMA binders. Results indicated that the
Rediset WMA binder had the lowest shear modulus, followed by the Evotherm, Cecabase and Sasobit
WMA binders. However, a different rate of gain trend was observed in the modulus values where,
again, Rediset was slowest of all but followed by Sasobit, Evotherm and Cecabase binders. This implies
that, of all the binders investigated in this study, the Sasobit WMA binder will have a signicantly
lower modulus over time as compared to the control PG 64-22 binder and the Rediset WMA binder will
have the lowest modulus in the short-term as well as over time.
Published by Elsevier Ltd.

1. Introduction
The area of pavement engineering has been steadily evolving
over the last two decades due to growing concerns over global
q
Importance of Paper: This paper proposes a novel methodology for developing
master curves for the complex shear modulus of asphalt binders. Traditionally, the
shift factor equation has been estimated outside the master curve equation which
has led to propagation of biases from one model to the other. The methodology
proposed in this paper uses joint estimation to determine the effect of loading time,
temperature and aging duration on the rheological properties of the asphalt binder.
Furthermore, the study analyzes the effect of aging on the rheological properties of
a control PG 64-22 binder and four different WMA binders. It was observed that the
Rediset WMA binder has the lowest stiffness in short-term and also gains stiffness
rather slowly as compared to the other binders included in this study. In addition, it
was noticed that the Sasobit WMA binder though has a higher initial stiffness than
the PG 64-22, due to its slower rate of gain in stiffness; it will have a lower stiffness
than the control over time. It is therefore expected that the reduced effect of aging
on the rheology of WMA binders will translate to better fracture resistance.
Corresponding author. Tel.: +1 512 507 8605; fax: +1 512 475 7314.
E-mail addresses: ambarish03@yahoo.com (A. Banerjee), asmit@mail.utexas.edu
(A. de Fortier Smit), prozzi@mail.utexas.edu (J.A. Prozzi).
1
Tel.: +1 512 906 5495; fax: +1 512 475 7314.
2
Tel.: +1 512 471 4771; fax: +1 512 475 7314.
warming and air quality. Until recently, the effort has been to-
wards increased use of emulsied asphalt technologies in order
to reduce the carbon footprint of the highway construction indus-
try. Over the last decade, researchers around the world have
started exploring another signicant area that promises to serve
identical needs. This new technology attempts to reduce the mix-
ing and compaction temperatures through the incorporation of
warm mix additives to conventional asphalt binder.
Prominent warm mix technologies can be primarily classied
into three groups based on the technique used to lower the mix-
ing and compaction temperature. These include: (1) organic addi-
tives like Sasobit and Asphaltan, (2) synthetic zeolite-based
additives like Advera and Aspha-Min and (3) emulsion based
technologies like the Evotherm 3G and Evotherm DAT. A fourth
group includes the injection of water to produce a foaming effect,
but this group is out of the scope of this paper since it does not
use additives.
Advocates in favor of WMA technologies suggest that the re-
duced mixing and compaction temperatures improve the long-
term durability of the mix due to reduced short-term aging. This
work also studied the effects of oxidative aging on the mechanical
properties of four different WMA binders.

0016-2361/$ - see front matter Published by Elsevier Ltd.

doi:10.1016/j.fuel.2012.01.072
604 A. Banerjee et al. / Fuel 97 (2012) 603611
2. Objective
This research study investigates the long-term aging of WMA
binders in comparison to HMA binders. The specic objectives of
this study are:
 To investigate the rheological properties of one organic (Sas-
obit) and three synthetic (Rediset, Cecabase and Evotherm)
additives of WMA binders. Please note that the Rediset WMA
additive is an organic additive that needs to be processed and
therefore, for most purposes, is classied as a synthetic additive
[1].
 To quantify the effects of aging on Sasobit, Cecabase, Rediset
and Evotherm WMA binders and develop a predictive model
based on experimental data that captures the long-term effects
of aging on the rheological properties of the binder.
3. Literature review
The effects of aging on the mechanical properties of the WMA
binders were investigated for the following four additives:
 Sasobit is a long chain aliphatic hydrocarbon produced by
FischerTropsch synthesis from coal or natural gas [2]. It forms
a homogeneous solution with the asphalt binder and produces a
signicant reduction in its viscosity, which results in a reduc-
tion of 1030 C in the mixing and compaction temperatures.
Between 115 C and 70 C, Sasobit solidies into microscopic,
regularly distributed, stick-shaped particles that increase Sas-
obit modied WMA binder stiffness [2].
 Cecabase is an articial additive manufactured by the Arkema
Group. It reduces the asphalt binder surface tension to improve
its wetting characteristics.
 Evotherm is a chemistry package that includes adhesion pro-
moters and emulsication agents to improve workability [3].
Its bulk properties, like viscosity and particle size distribution,
are similar to those of bituminous emulsions. However, this
warm mix surfactant formulation allows complete coating of
dense-graded aggregate at temperatures as low as 60 C [4].
 Rediset is a chemical additive from AkzoNobel that allows the
asphalt mixing temperature to be reduced by as much as
35 C. By design, it is a surface active agent that improves wet-
ting properties by signicantly reducing the surface tension of
an asphalt binder at temperatures below its typical mixing tem-
perature. However, Rediset differs from the other chemical
additives (Evotherm and Cecabase) because it is also an anti-
stripping agent, which is likely to improve its resistance to
moisture damage. It should be noted that the effect of long-
term aging on the rheological properties of the WMA binders
is the primary focus of this study and therefore secondary fac-
tors, such as moisture damage, are not addressed in this paper.
Xiao et al. [5] studied the effects of non-foaming WMA additives
on asphalt binder rheology. The study looked at the effect of four
different additives, Rediset WMX, Evotherm, Cecabase and Sasobit,
on ve different PG binders. Each of the WMA binders slightly re-
duced the viscosity of the binder, with Rediset and Sasobit achiev-
ing the highest reduction. However, the Sasobit WMA additive
noticeably increased the true grade for all the binder samples. At
the other end, the Cecabase WMA additive reduced the true grade
of the binder sample. The study reports that the Sasobit WMA
additive reduced the phase angle of the asphalt binder and in-
creased the complex modulus for the same strain level at 60 C
among other WMA additives. Therefore, all the evidence presented
in this study indicates that the addition of the Sasobit WMA addi-
tive will likely result in increased asphalt binder stiffness while the
addition of Cecabase will cause the opposite.
Akisetty et al. [6] studied the high temperature properties of
rubberized binders containing warm asphalt additives, namely As-
pha-Min and Sasobit. Their results indicated that the use of Aspha-
Min in rubberized asphalt binders translated into a higher viscosity
when compared to the control binder, whereas the use of Sasobit
helped lower the viscosity of the asphalt binder. The study sug-
gested that the viscosity measured for the WMA binders will grad-
ually increase as the reaction period between the additives and the
neat binder increases. The authors also investigated the effect of
Aspha-Min and Sasobit on the binders high temperature grade. Re-
sults showed that the high temperature grade signicantly in-
creased for both the aged and unaged Sasobit specimens when
compared to the control experiment, which indicates increased
binder stiffness due to the addition of WMA additives. The use of
Sasobit warm mix additive and its impact on the high temperature
properties of the binder was also reported by Hurley and Prowell
[7]. Their study showed that the improvement in the rutting prop-
erties of the binder was accompanied by a lower tensile strength
ratio (TSR) which, in the authors opinion, was mostly due to the
anti-aging properties of the Sasobit additive. The TSR values were
measured from moisture-conditioned specimens, in which case
the reported TSR values might were affected by moisture damage
also.
Lee et al. [8] investigated the effect of warm mix additives in as-
phalt binders containing long-term aged binders. Their study
showed that the addition of Sasobit reduced the viscosity of the as-
phalt binder, while the addition of certain other additives, like As-
pha-Min, was likely to increase its viscosity. Secondly, their
research also found out that the asphalt binders high temperature
properties were improved with the addition of certain warm mix
additives, such as Sasobit and Aspha-Min. The incorporation of
these additives, however, was likely to have an adverse effect on
the intermediate and low temperature properties of the binder
when compared to the control binder.
Kanitpong et al. [9] reported that Sasobit helps lower the mixing
and compaction temperatures by signicantly reducing the poly-
mer modied binder viscosity. Their study noted that the addition
of 3% Sasobit greatly improved binder resistance to permanent
deformation and fatigue. On the down side, Sasobit modied as-
phalt binders mixed at low temperatures could have a lower TSR
than hot asphalt mixtures due to possible entrapped moisture in
the aggregates.
Diefenderfer et al. [10] reported that the air void content in Sas-
obit warm mixes was slightly lower than the hot asphalt mixtures,
but the difference was statistically insignicant. The rutting perfor-
mance of the Sasobit WMA mixtures and the HMA mixtures were
almost the same. TSR results for the Sasobit WMA and HMA mix-
tures were inconclusive. The authors found that the TSR and per-
manent deformation resistance for Evotherm WMA mixtures
were relatively poorer than the control HMA mixtures. In another
study, however, the authors found that plant produced Sasobit
WMA mixtures showed a lower order of rutting than the control
HMA mixes [11]. The relatively improved performance of the Sas-
obit mixes was attributed to the stiffening properties of Sasobit at
temperatures below their melting point. Field trial studies showed
that the stiffness gain rate after construction was reduced in the
Sasobit produced WMA as compared to the HMA [12] due to as-
phalt binder in-service aging. For Evotherm WMA mixes, the
authors did not observe any difference in the recovered binder per-
formance grade when compared to the control HMA mixes, except
for an increase in one low temperature grade after being in service
for two years.
Vaitkus et al. (2009) noticed that the addition of Cecabase RT
WMA additive has a negative impact on the Marshall Stability
 A. Banerjee et al. / Fuel 97 (2012) 603611
value when compared to the control HMA mix [13]. In addition, the
author also witnessed lower ow numbers compared to control
mixes, which is unexpected for mixes with lower stability values.
However, contrary to the observation made by Diefenderfer, Vait-
kus and his associates reported higher air void content in Cecabase
RT WMA mixes at the same compaction temperature. While the re-
sults presented in their paper was based on a limited dataset, it is
worth noting that the compaction effort required might differ sig-
nicantly between different warm mix technologies.
Hurley and Prowell (2006) noticed that the addition of WMA
additives signicantly reduced rutting potential when compared
against the trial HMA mixes [3]. The authors observed that adding
Evotherm WMA additive increased the mixs resilient modulus
when compared to trial mixes prepared with the same base binder.
However, as pointed out by Kanitpong et al. (2007), the researchers
reported that Evotherm WMA mixes rutting potential was sensi-
tive to the mixing and compaction temperature [9]. Kanitpong
et al. argued that the WMA mixes rutting performance is affected
by the amount of in-place aging that they are subjected to over
their service life. Additionally, the study observed lower TSR values
in Evotherm WMA mixes than in control mixtures, which might be
due to the inherently low tensile strengths of the Evotherm mixes.
Wasiuddin et al. (2007) studied the effect of WMA binder addi-
tives, especially Sasobit and Alpha-Min, on PG 64-22 and PG 70-28
binder viscosity and mechanical properties [14]. Results showed
that Sasobit WMA binder viscosity was signicantly lower than
the HMA binders viscosity, which suggested that the mixing and
compaction temperatures could be lowered by 16 C and 7 C
respectively without compromising the required workability of
the binder for proper coating of aggregates or the desired air void
percentages. However, the Superpave G = sin d parameter, used for
measuring the high temperature performance of the asphalt bin-
der, was found to be higher than the HMA binder for both the aged
and unaged samples. This indicates that the Sasobit WMA binders
are stiffer than the regular HMA binders at high temperatures. As
expected, the Asphalt Pavement Analyzer (APA) rut depth mea-
sured at 8000 cycles were seen to show the same trend as the
Superpave G = sin d parameter.
Prowell et al. (2007) studied the rutting potential of WMA (Evo-
therm) and HMA surface mixes [4]. Their study pointed out that
WMA mixes rut more than HMA surface mixes. Their results
showed that the increased rutting in WMA mixes could be attrib-
uted to the tenderness of the mix. However, the improved work-
ability imparted by the Evotherm additive helped attain a lower
air void percentage, which effectively compensated for the lower
stiffness of the mix and thus improved its resistance to permanent
deformation.
4. Experimental design
This research focuses on quantifying the effects of long-term
aging on the rheological properties of the asphalt binder. The PG
64-22 obtained from Jebro Inc. served as the control experiment
for the rst dataset while the PG 76-22 from Valero Ardmore
was the control for the second dataset. The warm mix additives
considered for this study include the following:
 Sasobit
 Cecabase RT 945
 Rediset WMX
 Evotherm 3G
Each of the two control binders were subjected to short-term
aging in the Rolling Thin Film Oven (RTFO) at 163 C. The warm
mix binders were short-term aged at 143 C based on the premise
605
that the addition of warm mix additives allows a reduction of
20 C on average in the mixing temperature. Both the control
and warm mix binders were long-term aged within pans placed
in an environmental room at 60 C with lm thicknesses not
exceeding one millimeter. To evaluate the long-term aging effects
on the binders rheological properties, it was necessary to obtain
experimental data on asphalt binders exposed to varying degrees
of aging. Therefore, the rheological testing of the binder samples
aged in the environmental room was conducted at the following
time intervals:
 0 days (unaged sample)
 2 days
 5 days
 11 days
 22 days
 35 days
 67 days
 132 days
This aging duration was based on pilot studies that determined
the effect of aging on the rheological properties of the binder. It
was noticed that on a loglog scale, the duration of aging bears a
linear relationship with the complex shear modulus. This observa-
tion led the study team to select the aging duration evenly spaced
on a logarithmic scale such that errors due to extrapolation are
minimized.
The mechanical properties of the asphalt binder samples were
evaluated using a frequency sweep test on the dynamic shear rhe-
ometer (DSR) at three different temperatures (i.e. 40 C, 52 C and
64 C) and at ten different frequencies that ranged from 0.1 Hz to
25 Hz. However, the PG 76-22 binder produced stiffness values
that were higher than the torque capacity of the instrument. This
led the study team to abandon that specic dataset because it
could not be used for further analysis due to issues caused by
extrapolation errors.
5. Methodology
A master curve is used to express the rheological properties of
asphalt binder as a function of temperature and loading rate. A
standard reference temperature is selected; in this case 60 C
(140F), then the measured data at various temperatures is
shifted with respect to loading frequency until the curves merge
into a single smooth function [15]. There are two primary math-
ematical forms that have been proposed for modeling the master
curve of asphalt binders. Jongepier and Kuilman (1970) proposed
that the relaxation spectrum for asphalt binders follow a log-nor-
mal distribution [16]. This model is quite accurate when the
phase angle varies from 10 to 70. The model works well for
temperatures and frequencies extending into the glassy region,
but at low frequencies, where the response of the material ap-
proaches that of a viscous uid, the models predictions are
inconsistent with measured values. Dickinson and Witt (1974)
proposed a practical hyperbolic model, but the fundamental
parameters, (e.g. the glassy modulus and the steady state viscos-
ity) are statistically estimated, which can lead to miss-estimation
of modulus in certain cases [17].
The inaccuracy of the model proposed by Jongepier and Kuil-
man at low frequencies led the authors to adopt the statistical
model proposed by Dickinson and Witt. The expression of Wil-
liams, Landel and Ferry (WLF) is widely used to describe the tem-
perature dependence of the rheological properties of the material,
as given in Eq. (1) [18].
logaT e h60  T 1
606 A. Banerjee et al. / Fuel 97 (2012) 603611

where aT is the shift factor corresponding to the temperature T in C where G is the complex shear modulus (kPa), f the frequency (Hz),
0
and e, h the model parameters that are estimated statistically. T the temperature (C), and a, b , c, d, h is the model parameters.
In developing master curves for asphalt binders, researchers The effect of aging on the rheological properties was a key as-
have traditionally used a reference temperature and the model pect of this study and the properties of the material have been
has been developed to capture the dependence of the complex studied at different points in time. Therefore, a master curve was
modulus on the loading time, while the shift factors were calcu- developed to account for age-dependency of the materials rheo-
lated using the WLF equation. In this context, the use of a reference logical properties.
temperature does not make a difference as the same model can be Long-term aging due to polar functional group oxidation in-
represented without a reference temperature as shown below. creases the binders complex shear modulus which causes the
material to harden over time. Thus, aging affects the rheological
logaT e h60  hT
2 properties in a similar fashion as that of loading frequency. The
logaT e0  hT age dependence of the material can be represented using an
expression that accounts for the necessary shift in the frequency
Since the model parameters for the shift factor and the master due to age difference between samples similar to that of the WLF
curve are estimated separately, the standard error of the shift fac- equation. Instead of proposing a separate model to estimate the
tors is reected in the master curve, which results in a higher error shift factors for age dependence, an alternative approach could
in the predictions obtained. Joint estimation of the model parame- be revising the master curve equation to account for long-term
ters will produce unbiased parameters and can signicantly reduce aging effects. It was observed that aging has a linear relationship
the standard error, thus improving the overall accuracy of the pre- with the complex shear modulus in a logarithmic scale. The rela-
dictions obtained from the model. Therefore, for the purpose of this tionship between the logarithms of the two parameters becomes
study, the Dickinson and Witt model was modied as given below. non-linear at high levels of exposure to the aging conditions, but
the effect of one on the other can be approximated with a straight
a
logG d dhT
line without losing signicant accuracy. Fig. 1 illustrates the rela-
1 ebc logf 10 
tionship between log (G) and frequency as well as age. It is evident
a
) logG d d
from the gure that both frequency and age have a similar effect on
1 ebc log f c log10 hT
G, but their respective magnitudes differ. Therefore, the effect of
 a 3 age in the master curve can be captured by correcting the model
) logG d
1 ebc log f cehT in light of the aforementioned discussion. The revised master curve
a
) logG d 0 0
equation proposed is given below.
1 eb c log f h T
a a
) logG d logG d 4
1 ebc log f hT 1 ebc log f hTk log Age

Fig. 1. Effect of frequency (left) and Age (right) on the complex shear modulus of the Cecabase WMA binder on PG 64-22 (up) and PG 76-22 (down).
 A. Banerjee et al. / Fuel 97 (2012) 603611 607

where Age is the number of days of aging for the specied sample, Table 1
and k the model parameter to account for the effect of aging on the Lower and upper tangents (d, a) to the master curve for different binders.

loading frequency. Coefcient Control Cecabase Rediset Sasobit Evotherm

The model parameters in Eq. (4) can be estimated individually d 0.32 0.52 0.82 0.52 0.89
for each of the different binders. However, it is unlikely that the
Parameter assumed to be zero
differences between binders in the model parameters will be sta- a 7.54 7.56 7.58 7.57 7.52
tistically signicant. Based on the information presented in the Averaged to 7.55
previous section, one can expect similarity in the model parame-
ters between the control PG 64-22 and the Sasobit WMA binder.
While the control PG 64-22 was exposed to higher levels of short sumed to be 3 GPa [19]. Although the test environment chosen
term aging in the RTFO to simulate the real world scenario, the Sas- for this study does not extend into the glassy region, the shear
obit WMA binder has been reported by many to have higher stiff- modulus of the different binders approaches the same value at
ness values due to the composition of the additive [11,14]. On the high frequencies and low temperature over extended period of
contrary, the chemical additives Cecabase RT, Rediset and Evo- aging. This suggests that a can be substituted with a single value,
therm 3G have all been reported on different occasions to have rel- irrespective of the WMA additive. In addition, preliminary estima-
atively lower modulus values. For example, Vaitkus et al. (2009) tion suggests that the parameter d approaches zero for each of the
reported noticeably lower Marshall Stability values for Cecabase ve different binders. The parameters d and a can be interpreted as
warm asphalt mixes. Prowell et al. (2007) and Diefenderfer et al. the lower and upper tangents to the sigmoidal curve used for mas-
(2007) both reported poorer rutting performance for Evotherm ter curves. The physical interpretation of d approaching zero is that
warm asphalt mixes. Although it is not necessary that the poor rut- at high temperature and loading time, the complex shear modulus
ting performance of these mixes is due to the lower modulus of the of the binder approaches zero. The estimates for d and a for the
asphalt binder, it has been pointed out on many occasions that the different binders are provided in Table 1.
properties of dense-graded asphalt mixtures are dictated more by In the light of the results presented in Table 1, Eq. (4) can be
the asphalt binder than by the aggregates. It can be hypothesized modied as given below.
that the poorer laboratory rutting performance of the Evotherm
7:55
and Cecabase warm mixes is due to the relatively lower complex logG 5
moduli of the warm asphalt binder, which can partly be attributed 1 ebc log f hTk log Age
to reduced exposure to oxidative aging. There seems to be a clear 7:55
) 1 ebc log f hTk log Age
distinction between the ve binders that were studied as part of logG
this research and similarities between the model parameters of 7:55
) ebc log f hTk log Age 1
certain binders are expected. logG
 
Factor analysis is a statistical method used to describe variabil- 7:55
ity among observed variables in terms of a potentially lower num- ) b c log f hT k log Age ln 1
logG
ber of unobserved variables called factors. It was used in this study
as a data reduction technique to segregate variables that have a
statistically signicant effect on the response variable from those
) b c log f hT k log Age y
that do not. As mentioned, the study aims to develop a master
curve for the complex shear modulus as a function of time, temper- ) y b c log f hT k log Age 6
ature and aging conditions for the control PG 64-22 binder and the
four different WMA additives included in this study. The use of fac-
tor analysis helps the authors meet this objective by identifying where
variables that do not have a statistically signicant effect on the  
7:55
complex shear modulus so that the proposed equation includes y ln  1 :
logG
only those variables that inuence the G.
The second objective of this study is to quantify the effect of
aging on different warm mix additives. To meet this objective, The model presented in Eq. (6) represents a linear relationship
the authors calculated the marginal value of the complex shear between G and the loading frequency, temperature and aging per-
modulus with respect to the duration of aging in order to quantify iod and, therefore, the parameters in the equation can be estimated
its effect on the rheological properties of warm mix additives. Mar- through linear regression individually for the different binders. The
ginal value is the ratio of the dependent variables change to that of model parameters for the control PG 64-22 binder and the Rediset
the independent variable and, therefore, it is a measure for the WMA additive are summarized in Table 2.
slope of the function with respect to the independent variables. A Having determined the master curve parameters for the indi-
higher marginal value indicates a greater change in the response vidual binders, the next step involved combining the different
variable due to unit change in the independent variable and vice models into a single master curve that accommodated all the bind-
versa. ers. The authors used factor analysis to distinguish between the
signicant and the non-signicant variables. The nal master curve
that was developed to accommodate the ve different binders,
6. Results and discussion including the control PG 64-22, is given in Table 3.
The proposed model allows someone to predict the complex
Shear testing of the control and warm mix binders were con- shear modulus as a function of loading time, temperature and
ducted in the laboratory using the Dynamic Shear Rheometer aging conditions for each of the four different WMA additives as
(DSR). The experimental data was analyzed using statistical tools well as the control PG 64-22 binder. In addition, the model cap-
to estimate the model parameters, as presented in Eq. (4). tures the marginal effect of the loading frequency, temperature
Past research studies have indicated that the complex shear and aging conditions on the complex shear modulus for each of
modulus of the binder approaches the glassy modulus at low tem- the WMA additives with respect to the control PG 64-22. The vari-
peratures and high loading frequency, which in most cases is as- ables Ceca, Redi, Saso and Evo serve as binary variables in
608 A. Banerjee et al. / Fuel 97 (2012) 603611

Table 2 ological properties of binders will be dictated by the choice of

Master curve parameters for control PG 64-22 and Rediset WMA binders. temperature and loading frequency.
Parameter Coefcient t-Stat p-Value The selection of temperature and loading frequency was made
Control PG 64-22 after giving due consideration to the three most prominent forms
b 2.10 123 <0.00 of distresses seen in bituminous pavements: rutting, fatigue
c 0.47 116 <0.00 cracking and low temperature cracking. High pavement tempera-
h 0.04 122 <0.00 tures and loading times present the most critical conditions for
j 0.30 65.2 <0.00
plastic deformation or rutting. The Superpave performance grad-
Master curve for PG 64-22: logG 1e2:140:47 7:55
log f 0:04T0:8 log Age
ing (PG) uses two numbers representing temperatures in degree
Rediset WMA Celsius: the rst is the average seven-day maximum pavement
b 2.02 95.4 <0.00
temperature and the second is the minimum pavement design
c 0.48 99.8 <0.00
h 0.04 102 <0.00 temperature likely to be experienced. For example, a PG 64-22
j 0.27 45.4 <0.00 is intended for use where the average seven-day maximum pave-
Master curve for Rediset WMA: logG 1e2:020:48 log
7:55
f 0:04T0:27 log Age ment temperature is 64 C and the expected minimum pavement
temperature is 22 C. Therefore, the temperature and loading
frequency corresponding to 60 C and 1 Hz will be appropriate
to study the effect of aging on the rheological properties, with
Table 3 rutting as the governing form of distress. Unlike rutting, low tem-
Master curve for G for PG 64-22 and Cecabase, Rediset, Sasobit and Evotherm WMA
binders.
perature thermal cracking is critical at low pavement tempera-
tures and loading times. Therefore, the timetemperature
Parameter Coefcient t-Stat p-Value contour chosen to study the effect of aging on the shear modulus
b 2.14 195 <0.00 with low temperature thermal cracking as the dominant distress
c 0.475 231 <0.00 criteria analysis was 0.1 s and 5 C, respectively., While low tem-
h 0.0388 204 <0.00
j 0.298 92.4 <0.00
perature cracking is the result of fracture due to thermal stresses
b (Cecabase) 0.117 5.91 <0.00 in the material that are induced by the restraint provided against
b (Rediset) 0.122 14.4 <0.00 dimensional variations, fatigue cracking is a progressive and
b (Sasobit) 0.0157 2.04 0.04 localized structural damage that occurs when a material is sub-
b (Evotherm) 0.133 6.39 <0.00
jected to cyclic loading. Fatigue cracking in asphalt binders is
c (Rediset) 0.00922 1.96 0.05
h (Cecabase) 0.000799 2.15 0.03 mostly associated with intermediate temperatures and high load-
h (Evotherm) 0.00110 2.96 <0.00 ing frequencies [20], so the timetemperature regime correspond-
j (Rediset) 0.0272 4.34 <0.00 ing to 0.1 s and 25 C is ideal for studying the effect of aging on
j (Sasobit) 0.0325 5.56 <0.00 the shear modulus with fatigue cracking serving as the dominant
j (Evotherm) 0.0123 2.21 0.03
distress mechanism.
The complex shear modulus was evaluated under each of these
the model for the Cecabase, Rediset, Sasobit and Evotherm WMA three conditions and the results corroborated some of the ndings
additives, respectively. from other research studies. For example, the complex shear mod-
As stated in the objective, the study quantied the relative ef- ulus of the control PG 64-22 is higher than any of the WMA addi-
fect of aging on the rheological properties of the WMA binder. It tives (see Fig. 2). The Sasobit WMA additive was next to the control
is important to realize that asphalt binder has a viscoelastic re- binder while the Cecabase and Evotherm WMA binders had similar
sponse when subjected to dynamic loads, which implies that its trends. The Rediset WMA binder was subjected to the least amount
properties will vary depending on the temperature and loading fre- of aging over time. In fact, Fig. 2 shows that the G for the Rediset
quency. Therefore, it is evident that the effect of aging on the rhe- WMA binder was less than half the G predicted for the control PG

Fig. 2. Predicted G with aging time for different binders at 60 C, 1 Hz.

 A. Banerjee et al. / Fuel 97 (2012) 603611 609

Fig. 3. Predicted G vs. aging time for different binders at 5 C, 10 Hz.

Fig. 4. Predicted G vs. aging time for different binders at 25 C, 10 Hz.

64-22 binder. This results presented in Fig. 2 also explain the re-
ported tenderness in WMA mixtures by Prowell et al. (2007).
It is important to note that the materials were subjected to
accelerated aging and do not directly relate to the time scale for
in-service pavements. The lm thicknesses used for this experi-
mental study was restricted to a maximum of one mm with
constant exposure to 60 C; previous studies showed that an aging
duration of 38 days in an environmental room maintained at 60 C
is equivalent to 1 year of eld-aging [21]. Therefore, the results re-
ported in this study are almost an order of magnitude higher than
what would be expected under eld aging conditions.
Although the tenderness in WMA binders compromises the
rutting performance to some degree, the use of WMA binders is
especially benecial from a cracking perspective as the reduced
aging results in lower stiffness which implies improved fracture
resistance. The complex shear modulus calculated at low temper-
ature and high loading frequencies is illustrated through Fig. 3.
The control and Sasobit WMA binders have the highest moduli
over time while the Evotherm and Rediset WMA binders were sub-
jected to least aging. It is therefore expected that WMA binders
with the chemical additives would be most resilient to low
temperature cracking. Although the Sasobit WMA binder has a
signicantly higher modulus than the other additives, it is still
expected to perform better than the control PG 64-22 at low tem-
peratures over time.
Similar trends were observed while assessing the effect of aging
on G from a fatigue cracking perspective. While the control and
Sasobit WMA binders had the highest moduli over time, the
610 A. Banerjee et al. / Fuel 97 (2012) 603611

Table 4
Marginal values of G w.r.t. duration of aging (at 70 C and 1 Hz).

Type of additive
None (PG 64-22) Cecabase Rediset Sasobit Evotherm
Marginal of G at # days of Aging 1 4.42 4.22 3.69 3.97 4.05
2 2.33 2.24 1.95 2.08 2.14
4 1.22 1.18 1.03 1.09 1.13
8 0.64 0.62 0.54 0.57 0.59
16 0.33 0.32 0.28 0.29 0.31
32 0.17 0.17 0.15 0.15 0.16
64 0.09 0.09 0.08 0.08 0.08
128 0.04 0.04 0.04 0.04 0.04

Cecabase, Evotherm and Rediset additives showed the least sign of
aging over the same interval of time (see Fig. 4). This further high-
lights the fact that WMA binders are expected to deliver superior
fracture resistance at conditions critical for fatigue or low temper-
ature thermal cracking.
While Figs. 24 illustrate the effect of aging under conditions
considered critical for plastic deformation, low temperature ther-
mal cracking, and fatigue cracking, it is essential to assess the asso-
ciated benet in quantitative terms. The marginal value of the
shear modulus would help quantify the increase in G correspond-
ing to unit change in the duration of aging. The marginal value of
the shear modulus for the PG 64-22 is as given below.
d G
EG ;Age
d Age
k log Age
7:55  1 ebc log f hTk log Age 2 G ke
EG ;Age  8
 7
log10 Age
k log Age
7:55 ke G
EG ;Age   
1 ebc log f hTk log Age 2 log810 Age
The marginal values were calculated at 1, 2, 4, 8, 16, 32, 64 and
128 days of aging and are summarized through Table 4.
The results presented in Table 4 suggest that, irrespective of the
duration of aging, the control PG 64-22 ages faster than any of the
warm mix binders. On the other extreme of the spectrum, the Red-
iset WMA binder has the slowest rate of aging followed by the Sas-
obit and Evotherm WMA binders. Interestingly, the mixing and
compaction temperatures for hot mix asphalt binders are higher
than those for warm mix binders. These temperature effects were
simulated in the laboratory by selecting a higher aging tempera-
ture for the Rolling Thin Film Oven. This translates into reduced
short-term aging, which is reected by lower moduli for WMA
binders. In addition to short-term aging effects, the warm mix
additives have a signicant inuence on the long-term aging char-
acteristics of the binder. The warm mix binders not only have low-
er initial complex shear moduli but they also age at a signicantly
lower rate than the PG 64-22.
7. Conclusion
This paper reports the ndings from an investigation of the long
term effects of aging on WMA binders. The authors evaluated the
effect of aging on the rheological properties, namely the complex
shear modulus, of the binders in a laboratory environment. The
scope of this study included four different warm mix additives:
one was an organic additive (Sasobit), while the other three were
synthetic additives (Cecabase, Rediset and Evotherm).
The research objective included investigating the long term ef-
fects of aging when subjected to varying degrees of oxidative aging.
Binder specimens were subjected to a frequency sweep on a dy-
namic shear rheometer and the complex shear modulus was mea-
sured at ten different loading frequencies and three different
temperatures at periodic intervals of time in accordance with the
experimental design. The major ndings from this study were as
follows.
 The authors proposed an approach for developing master curves
for asphalt binders based on joint estimation that does not
propagate the WLF equation bias to the sigmoidal master curve,
thus improving the efciency of the model. Given that the effect
of aging on the rheological properties is similar to that of tem-
perature, an additional shift factor was introduced in the model
to account for differences in age between specimens. The effect
of time, temperature and aging differs between binders depend-
ing on their respective thermo-rheological characteristics; the
model used switch variables to account for these differences.
 The studys ndings suggest that, irrespective of the timetem-
perature envelope or the duration of aging, the control PG 64-22
had the highest expected shear modulus due to the selection of
a higher temperature for short-term aging on the Rolling Thin
Film Oven. The Sasobit wax-based additive had the second
highest shear modulus for the timetemperature-age proles
used in this study. The Rediset WMA binder was on the other
extreme of the spectra with the lowest shear modulus of all
the individual binders, followed by the Evotherm and Cecabase
WMA binders. The observations were consistent across the
timetemperature proles selected for this study, which sug-
gests that the synthetic additives studied in this research are
less affected by oxidative aging.
 The marginal value of the shear modulus (G) with respect to
the duration of aging was calculated in order to quantify the
effect of aging on the long term rheological properties of the
individual binders. Results suggest that the rate of aging for
the PG 64-22 is higher than any of the other binders. The Red-
iset WMA binder exhibited the slowest rate of gain in the mod-
ulus values, followed by Sasobit, Evotherm and Cecabase.
Although the Sasobit WMA binder is closest to PG 64-22 in
terms of the early-age shear modulus, its slow rate of gain in
stiffness suggests that over time it will have a signicantly
lower modulus than the control experiment. In general, the
WMA additives not only reduce short-term aging effects on
the rheological properties of the binder but they also retard
the rate at which the stiffness grows over time. While reduced
mixing and compaction temperature partly explains this nd-
ing, the other half is attributed to the molecular composition
of the additive.
Acknowledgment
The authors extend their sincerest thanks to Patricia Trujillo for
conducting all the necessary laboratory measurements.
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