Journal of Cleaner Production 112 (2016) 2342e2353

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Surface free energy and moisture susceptibility evaluation of asphalt

binders modified with surfactant-based chemical additive
Muhammad Rafiq Kakar a, d, Meor Othman Hamzah a, *, Mohammad Nishat Akhtar b,
David Woodward c
a
School of Civil Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
School of Electrical and Electronic Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
c
Highway Engineering Research Group, University of Ulster, Jordantown BT37 0QB, Northern Ireland, United Kingdom
d
National Highway Authority of Pakistan, NHA HQ 27, Mauve Area, G-9/1, Islamabad, Pakistan

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

Article history: Warm mix additives are used to lower the production and application temperature of asphalt mixtures.
Received 29 October 2014 Moisture damage is one of the main reported issues with warm mix asphalt due to its lower production
Received in revised form temperature and the possible presence of moisture being trapped during the mixing process. This paper
19 October 2015
considers the use surface free energy evaluation as a fundamental material property to assess mixture
Accepted 23 October 2015
performance. Cecabase® chemical surfactant additive was used to prepare warm mix asphalt binders.
Available online 31 October 2015
Contact angle measurements were determined with a Goniometer to evaluate surface free energy
measures such as work of adhesion, work of debonding and compatibility ratio. The results show that the
Keywords:
Warm mix asphalt
use of the surfactant-based additive reduces surface free energy. It increases after short-term (Rolling
Surface free energy Thin Film Oven) and reduces after long-term (Pressure Aging Vessel) aging. The analytical measurements
Physico-chemical properties based on surface free energy results illustrate that the surfactant-based warm mix additive improves the
Moisture susceptibility spreadibility of asphalt binder over the aggregate particles. The work of adhesion slightly improves with
the addition of Cecabase® content. Compatibility ratio is an indicator of moisture susceptibility and in-
dicates that the granite aggregates are less resistant to moisture damage compared to the limestone
aggregates used in this laboratory study.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Warm mix asphalt (WMA) is now an important asphalt mix in
many countries around the world. Compared to hot mix asphalt
(HMA) it has qualities that make it attractive to the changing world
in which we live. It has less environmental impact in terms of
green-house gas emission. Less energy is required during mixing. It
may be hauled greater conditions to site and compacted in cooler
conditions (Hamzah et al., 2014). Increased amounts of Recycled
Asphalt Pavement (RAP) may be used (Rubio et al., 2012, 2013). One
of its most important benefits is that workers involved in manu-
facture and particularly laying are exposed to less potentially fumes
compared to conventional HMA.
WMA is made and compacted at lower temperatures compared
to HMA. There are three main methods to reduce mixing and laying
* Corresponding author. Tel.: þ60 4 5996210; fax: þ60 4 5941009.
E-mail address: cemeor@yahoo.com (M.O. Hamzah).
temperatures (Capit~ ao et al., 2012). They may reduce mixture vis-
cosity of the bitumen using a foaming processes, which can either be
water-based (direct method technologies) or water-containing (in-
direct method technologies) (Rubio et al., 2012). The use of organic
or synthetic additives such as Sasobit and Asphamin add waxes to
the mixture. Chemical additives such as Cecabase® contain combi-
nations of emulsification agents, surfactants, polymers and adhesion
promoting (anti-stripping agents) additives. These help to improve
coating of the aggregate particles, workability and compaction
(Rubio et al., 2012). Of these three main methods, the use of chemical
additives has been found to be more practical and convenient as they
can be added directly to the bitumen prior to mixing without any
modification of the asphalt plant. It is also claimed, that unlike
foaming or organic based WMA additives, the chemical surfactant-
based additive does not significantly affect the mechanical/rheo-
logical properties of the bitumen i.e. its stiffness and low tempera-
ture properties (Oliveira et al., 2013).
In asphalt mixtures the purpose of bitumen is to bind the ag-
gregates together and transfer the stresses of traffic loading during

http://dx.doi.org/10.1016/j.jclepro.2015.10.101
0959-6526/© 2015 Elsevier Ltd. All rights reserved.
 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353
its in-service life (Hamzah et al., 2015). Good adhesion bond be-
tween bitumen and aggregate surface is therefore very important
and anything that lessens this bond will reduce the life of the
asphalt mixture layer. The development of a good bond between
asphalt and aggregate is primarily dependent on the ability of the
asphalt to wet the aggregate. The aggregate wettability increases
when the surface tension or Surface Free Energy (SFE) of adhesion
decreases (Kakar et al., 2015). The presence of water either con-
tained within the aggregate particle or external to the bitumen
coated particle is probably the main cause for failures at this critical
interface (Bhasin and Little, 2009).
One of the main concerns relating to the durability of WMA is
the potential for water/moisture induced failure of the bond. This is
primarily due to issues with the lower temperatures involved
during mixing that may not adequately reduce the aggregate
moisture contents to an acceptable level. Despite extensive
research to understand the behavior of WMA and its obvious
beneficial characteristics, the risk of moisture damage related fail-
ure still remains a problem. The types of aggregates used in asphalt
production are varied and reflect the many different types avail-
able. A simple classification is based on how they were formed i.e.
igneous, sedimentary and metamorphic. Within each of these there
are many different types that can be described in terms such as
their overall bulk chemistry, mineralogy, grain size and degree of
weathering. With regard to most aggregate/bitumen research, bulk
chemistry is typically used to describe the aggregate. Mineral fillers
such as fly ash are also used as adhesion promoter, however due to
its increase in coating difficulty, fly ash is not recommended to
mitigate the stripping problems (Pasandín et al., 2015).
In simple terms, the surface of different types of aggregate will
have different chemical affinities with bitumen. For example, ag-
gregates with higher SiO2 contents such as granite and quartz are
typically termed acidic. They are classified as hydrophilic or water
loving and can be difficult to coat with bitumen. In contrast, basic
aggregates with high CaCO3 content such as limestone are hydro-
phobic. They tend to repel water and be less affected by moisture
induced problems (Tarrer and Wagh, 1991).
Terms such as wettability and adhesion are used to explain the
bitumen/aggregate interface mechanism (Wasiuddin et al., 2008).
The interface can be explained using descriptive terms such as
wettability of bitumen over aggregate, free energy of adhesion and
solubility of adhesion bond. With respect to the chemical in-
teractions occurring at the interface, the polar (hydrophilic) and
non-polar (hydrophobic) nature of aggregate and bitumen control
the wettability of bitumen over aggregate. Most types of bitumen
are considered to be non-polar. Most basic and acid aggregate types
have high polarity surfaces (Wasiuddin et al., 2010). Therefore, it is
difficult to wet a polar aggregate surface with most non-polar types
of bitumen. The wettability of most non-polar types of bitumen
over polar aggregate can be improved by altering the aggregate
surface from being polar to become non-polar i.e. hydrophilic to
hydrophobic. This is best done by reducing the bitumen non-polar
component and the polar component of the aggregate.
This paper uses SFE measurements to study the effects of WMA
Cecabase® surfactant-based additive on the aggregate/bitumen
bond. Since warm mix asphalt is a technology that produces asphalt
mixtures at low temperature, which therefore reduces greenhouse
gas emission and low fumes during pavement construction making
it more environment friendly. Asphalt mixtures production at high
temperatures can contribute to air quality problems due to the
emission of reactive organic gases (ROGs) and particulate matter.
The emissions released through asphalt plant stacks in the United
States are regulated and controlled by the Environmental Protec-
tion Agency [EPA AP-42, Section 11.1 Hot-Mix Asphalt Plants
(Kinsey, 1986)]. Reduction in reactive organic gases and nitrogen
2343
oxide emissions will reduce ozone formation potential in urban
areas and subsequently this is a high priority nationwide. According
to the California Air Resources Board (CARB) record, the largest
source of ROG is emissions from light-duty vehicles and in 2005
accounted for 600 tons per day (tpd) or 24.6 percent of the total
ROGs in the state (California Air Resources Board, 2015). In 2010,
these emissions have decreased up to 400 tpd or 18.9 percent of the
total ROGs. As emissions from these major sources decreased over
time, emission reduction from smaller sources has become a higher
priority for achieving clean air standards (Farshidi et al., 2013).
Furthermore, research has been carried out for many years on
health concerns with a recent focus on potential exposure to car-
cinogens with respect to asphalt fume exposure. A very important
group of chemical carcinogens in asphalt is potentially represented
by Polycyclic aromatic hydrocarbons (PAH). Many of the lower
molecular weight PAH compounds might also be removed during
the refinery process, but this depends on the crude oil source and
the process used to refine it (Farshidi et al., 2013). Studies
(Newcomb, 2007; D'Angelo et al., 2008) have proven that WMA
plants would reduce CO2 and SO2 by 30%e40%, volatile organic
compounds (VOC) by 50 percent, CO by 10%e30%, NOx by 60%e70%
and dust by 20%e25%. Hence, in the context of warm mix asphalt
which is also called green technology with sustainable asphalt
production can be the prime interest of environmental protection
agencies and pavement researchers. Two different aggregate with
differing in-service moisture related performance were used in the
calculations. Blends of Cecabase® were prepared with 2 different
bitumen grades which were subjected to short and long term aging.
Changes in SFE were investigated using the contact angle
technique.
2. Surface free energy using the contact angle technique
Surface free energy (SFE or g) is defined as the amount of
external work done on a material to create a new unit surface area
in a vacuum. SFE is normally presented in units of ergs per square
centimeter (Bhasin et al., 2006). Four types of test equipment are
available to measure SFE of bitumen and aggregate i.e. the Goni-
ometer, the Wilhelmy Plate Device, the Micro-calorimeter and the
Dynamic Vapor Sorption System. The measurement of contact
angle with the bitumen using different probe liquids is performed
using the Goniometer and the Wilhelmy Plate Device. The Micro-
calorimeter and the Dynamic Vapor Sorption device are used to
measure the heat of adhesion and adsorption of different probe
liquids/vapours respectively with aggregate. The measurement of
contact angle using the Goniometer is the most common and
simple approach used to determine the SFE characteristics of
bitumen and was the method used in this study.
The contact angle approach was described by Young to deter-
mine the SFE properties of a solid (Ahmad, 2011). The contact angle
was defined by the three surface tensions (solid, liquid and air/
vapour). Young's equation shown in Fig. 1 is used to summarize the
calculations (Ahmad, 2011). Young's equation can be written as Eq.
(1):
gLA cos q þ gSL ¼ gSA (1)
where L, S and A denotes liquid, solid and air respectively.
Van Oss et al. (1988) identified two main interactions of a sur-
face energy components for a solid i.e. LifshitzeVan der Waals in-
teractions and AcideBase interactions (Erbil, 2006). Polar
components are divided into Lewis acid and base component,
which encompass all the electron donor and electron acceptor type
interactions (Van Oss et al., 1988).
The surface energy, gT, can be calculated from Eq. (2):
2344 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353
Fig. 1. Young's contact angle formula (http://www.ramehart.com/contactangle.
htm,2014).

. 
gT ¼ gLW þ gAB Unit; erg cm2
where,
gLW ¼ LifshitzeVan der Waals component
gAB ¼ AcideBase component
The arrangement of atoms in a polar molecule is such that it
possesses a positive charge at one end and a negative charge at the
other end. This is due to an uneven distribution of electrons in the
orbits, making them unstable to interact with other polar mole-
cules. In contrast, the electrons are evenly/symmetrically distrib-
uted in non-polar molecules. Therefore all the charges nullify each
other. LifshitzeVan der Waals forces are assumed to be the non-
polar or dispersive force. These forces are considered to be
composed of three main components; London dispersion forces,
Debye induction forces and Keesom orientation forces (Kim, 2009,
Rieke, 1997). All these forces correspond to different types of
dipole/induced dipole interactions between neighboring molecules
and electronic shells. Water and aggregates are polar substances
whereas bitumen is mostly a non-polar material. Therefore, water
has greater attraction for aggregate surfaces than bitumen. Indeed,
most liquids have a tendency to spread over high energy surfaces
such as aggregate.
The polar component is composed of AcideBase interactions
which include electron acceptor-electron donor interactions and
hydrogen bonding (Morrison and Boyd, 1983). Eq. (3) represents
Good, Van Oss and Chaudhury acidebase theory.
pffiffiffiffiffiffiffiffiffiffiffiffi
AB
g ¼2 gþ g
where,
gþ ¼ Lewis acid component of surface interaction
g ¼ Lewis base component of surface interaction
According to surface physical chemistry theory, SFE is the en-
ergy separating and solid or liquid to produce a new interface in a
vacuum. If the separated material is homogenous, the energy is
described as cohesion. If the separated material is not homogenous,
and two different surfaces are produced, then the energy is
described as Work of Adhesion (W) (Tan and Guo, 2013). The
adhesion property of bitumen with aggregate may be computed
analytically by evaluating SFE results in terms of W. Bitumen and
aggregate W in dry and wet interface conditions may be calculated
using Eqs. (4) and (5) respectively.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi
dry
WAS ¼ gAS ¼ 2 gLW g LW þ 2 gþ g þ 2 g gþ (4)
A S A S A S
wet
WWAS ¼ gAW þ gSW  gAS (5)
where,
dry wet represent the work of adhesion in dry and wet
WAS and WWAS
condition respectively.
The surface energy of bitumen is indicated with subscript A.
The subscripts W and S refer to surface energy of water and
aggregate respectively.
The physical adhesion component probably contributes more
than mechanical interlocking and chemical interactions to the
overall adhesion at bitumen/aggregate interfaces. This physical
adhesion and its loss due to the presence of water can be calculated
using the SFE components of bitumen and aggregate (Alvarez et al.,
(2)
2012). The Coefficient of Spreadability or Spreading Coefficient (SC)
is a quantitative index of the wettability of the bitumen over the
aggregate. It can be calculated using Eq. (6) (Alvarez et al., 2012).
dry
SC ¼ WAS  WAA (6)
where; WAA is the Work of Cohesion of bitumen and is given by
Eq. (7).
WAA ¼ 2gT (7)
The ratio of Work of Adhesion in dry conditions to the free en-
ergy released in wet conditions is referred to as the Compatibility
Ratio (CR). This parameter has been used to rank bitumen/aggre-
gate mixtures in terms of their moisture susceptibility (Bhasin,
2004). A higher CR is desirable as it indicates high bond energy in
dry conditions and a lower release of free energy in the presence of
moisture. Compatibility Ratio is calculated from Eq. (8).
dry
WAS
Compatibility Ratio ¼  wet  (8)
W 
WAS
The tendency of bitumen to strip from the aggregate surface
may be quantified as the amount of free energy released when
water displaces bitumen at the bitumen/aggregate interface (Hefer,
2004). The higher magnitude of the absolute value of bond energy
indicates a stronger adhesion between the binder and aggregate.
The desirable Compatibility Ratio varies from 0.5 to 1.5.
3. Materials and methods
(3)
Two bitumen's were supplied by Shell Bitumen Singapore i.e.
PG-64 and PG-76. The surfactant-based chemical additive used is
manufactured by CECA and has the proprietary name CECABASE®
RT 945 (Leon et al., 2009). Bitumen/additive blends were prepared
using a laboratory overhead mechanical blender. The blending
parameters are given in Table 1. The bitumen blends were subjected
 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353
Table 1
Dosage, blending time and temperature of additive.
Additive Dosage by weight Blending time Blending
of bitumen (%) (min) temperature ( C)
Cecabase RT® 975 0.2 15 120e130
0.3 PG-64
0.4 170e180
PG-76
to artificial short-term aging using Rolling Thin Film Oven (RTFO)
equipment and long-term aging using a Pressure Aging Vessel
(PAV).
Test specimens for contact angle testing were prepared by
dipping microscope glass slides in each of the unaged and aged
bitumen blends. Before dipping, each slide had been exposed to the
flame of a propane torch to remove any atmospheric moisture.
After dipping in the hot bitumen, the glass slides were left to hang
vertically for a few minutes. This drained excess bitumen from the
glass slide and ensured a smooth surface for contact angle mea-
surements. All coated slides were stored in a desiccator prior to
contact angle measurements. Fig. 2 shows the bitumen samples
and coated glass slides used for the determination of contact angle
measurements.
3.1. Sessile drop method
The Sessile Drop Method is an optical measurement method
based on contact angle which is used for the characterization of
solid surface energies and wettability. A schematic diagram of the
Sessile Drop Method is shown in Fig. 3. According to Tan and Guo
(2013) the fundamental assumptions while using the Sessile Drop
Method are:
I. The droplet has vertical symmetry.
II. The droplet shape is only related to interfacial tension and
droplet gravity.
The Sessile Drop Method is best suited for low-energy surfaces
such as bitumen. The static contact angles of probe liquids with any
solid surface are measured directly by dispensing a drop of the
probe liquid on the solid surface and capturing an photographic
image of the drop.
There are a number of methods available to analyze the SFE of
bitumen using contact angles measurements. Kim et al. (2003)
adopted the GoodeVan-OsseChaudhury (GVOC) theory to eval-
uate the surface free energy of bitumen. Drelich et al. (1994) used
the Neumann State Equation to compute bitumen surface tension.
Inverse gas chromatography has also been used to determine
Fig. 2. Bitumen samples and binder coated glass slides.
2345
bitumen surface energy. However, this method needs a set of
chromatographic columns making it quite complex.
In this study, the bitumen SFE was measured using the Goni-
ometer device manufactured by Rame-Hart Inc., U.S.A. The equip-
ment is shown in Fig. 4. A series of liquid drops were formed on the
bitumen surface and their contact angles measured immediately.
The volume of liquid dispensed was 5 ml to ensure consistency and
avoid the gravitational effects. This allowed calculation of surface
tension and/or surface free energy parameters to characterize each
bitumen surface and its wettability.
3.2. Selection of probe liquid
Contact angle measurement involves the use of probe liquids
with known surface energy. It is important to use the appropriate
probe liquids. There are approximately 60 liquids (Bhasin, 2006).
Most of these liquids may dissolve bitumen and so detrimentally
affects the measurement of contact angle. Bhasin (2006) identified
five combinations of polar and non-polar liquids as appropriate
probe liquids for the determination of reliable bitumen surface
energy characteristics i.e. deionized water, ethylene glycol, form-
amide, glycerol and methylene iodide (diiodomethane). Ahmad
(2011) identified the following factors when selecting a probe
liquid:
1. It should not dissolve or have a chemical reaction with bitumen
at the test temperature.
2. The surface energy components of the probe liquid should be
known.
3. The liquid must be pure and homogenous.
4. The surface energy value of a probe liquid should be greater than
that of the solid for contact angle measurements.
5. The substrate should be tested with a combination of at least
one non-polar and two polar liquids.
These considerations are necessary to minimize errors due to
the use of probe liquids with similar surface energy properties. The
concept of Condition Number was used by Hefer (2004) for the
selection of appropriate probe liquid. This is a function of the SFE
components of the selected probe liquid and can be calculated prior
to performing the experiments. A Condition Number greater than
10 indicates that the calculated results are very sensitive to small
experimental errors and vice versa (Bhasin, 2006).
On the basis of these, three probe liquids were selected i.e.
deionized water, ethylene glycol and methylene iodide (diiodo-
methane). Their physico-chemical properties are shown in Table 2.
The SFE components of granite and limestone aggregates used in
this study are shown in Table 3. The SFE dimension corresponds to
force per unit area i.e. mJ/m2 or erg/cm2.
2346 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353

Fig. 3. Schematic layout for the Sessile Drop Method (Little et al., 2006).

Three parameters were considered i.e. the measured Contact

Angle (CA) parameter, probe liquid of known SFE parameter and the
SFE components of the bitumen blends. The following shows the
pseudo code used to compute SFE components of the bitumen's
using the Contact Angle and probe liquid surface energy input
parameters.

//Declaration of Values

CA parameter: angpara1, angpara2, angpara3;

SFE (Known): para1......para9;

SFE (Asphalt Binder): misval1, misval2, misval3;

//Input

User Input: angpara1, angpara2, angpara3;

//Calculate Determinant (D):

Fig. 4. Goniometer device used to measure contact angle.
4. Algorithm developed for the calculation of surface free
energy components
An algorithm was developed to calculate the SFE components of
the bitumen blends. This was based on Crammer's Rule which
works on the principle of an explicit formula for the solution of
‘n  3’ system of linear equation with ‘n  3’ variables. It states that
each component/entity of the solution to the linear system of the
form Ax ¼ b is given by Eq. (9):
D = ((para1*para5*para9) + (para2*para7*para6) + (para3*para4*para8)) -
((para1*para6*para8) + (para2*para4*para9) + (para3*para5*para7));
//Compute SFE (Asphalt Binder):
misval1 = (((para2*para9*(-angpara2)) + (para3*para5*(-angpara3)) + ((-
angpara1)*para6*para8)) - ((para2*para6*(-angpara3)) + (para3*para8*(-angpara2)) + ((-
angpara1)*para5*para9))) / D;
misval2 = (((para1*para6*(-angpara3)) + (para3*para7*(-angpara2)) + ((-
angpara1)*para4*para9)) - ((para1*para9*(-angpara2)) + (para3*para4*(-angpara3)) + ((-
angpara1)*para6*para7))) / D;
misval3= (((para1*para8*(-angpara2)) + (para2*para4*(-angpara3)) + ((-
angpara1)*para5*para7)) - ((para1*para5*(-angpara3)) + (para2*para7*(-angpara2)) + ((-
angpara1)*para4*para8))) / D;

//OUTPUT THE GENERATED VALUES

Xi ¼ detðAi ðbÞÞ=detðAÞ (9)

where, Ai (b) represents matrix A with its ith column replaced by

the entity b (Ken and Itamar, 2012).

Table 2
Surface free energy characteristics of probe liquids.

Type of probe Non-polar component Basic component Acidic component Polar component Total SFE
liquid gSLW (ergs/cm2) g (ergs/cm2) gþ (ergs/cm2) gab(ergs/cm2) gT (ergs/cm2)
Water 21.8 25.5 25.5 51.0 72.8
Ethylene glycol 29.0 1.92 47.0 19.0 48.0
Methylene iodide1 50.8 0.0 0.0 0.0 50.8
1
Note: also known as Diiodomethane.
 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353 2347

Table 3
Surface free energy characteristics of aggregate.

Type of Non-polar component Basic component Acidic component Polar component Total SFE GT
aggregate gSLW (ergs/cm2) g (ergs/cm2) gþ (ergs/cm2) Gab (ergs/cm2) (ergs/cm2)

Limestonea 58.01 401.07 1.76 53.14 111.15

Granitea 44.30 46.37 678.98 354.88 399.18
a
Adopted from Howson et al. (2011) and Hesami et al. (2013).

Eq. (10) is used to measure the required surface energy com- The analysis algorithm program is run in Cþþ visual studio with
ponents of bitumen. the values of contact angle, measured in Radians keyed in one by
one. Fig. 5 shows an example output of values for ‘x1, x2 and x3’.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi
gL ð1 þ cos qÞ ¼ 2 gLW g LW þ g  gþ þ gþ g (10)
b L b L b L 5. Results and discussion

where; This section presents the results and analysis of the surface
energy components of bitumen evaluated from the contact angles
gL is the total surface energy of probe liquid, q is the angle of measured using the Goniometer device and its interfacial charac-
þ  þ 
contact measured in degree, gLW LW
L ; gL ; gL and gb ; gb ; gb are
teristics with aggregate. The results are presented in terms of
the Lifshitzevan der Waals, acid and base surface energy com- Spreadibility coefficient (wettability of the asphalt over the aggre-
ponents of probe liquid and bitumen respectively. gate), work of adhesion in a dry condition (resistance to fracture),
work of adhesion in a wet condition and compatibility ratio
Eq. (10) can be rearranged as shown in Eq. (11); (moisture resistance). The measured contact angles of unmodified
and Cecabase-modified bitumen with water, Ethylene Glycol and
qffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffi Methylene Iodide under different aging conditions are presented in
qffiffiffiffiffiffiffiffiffi gLW pffiffiffiffiffiffi gþ qffiffiffiffiffiffi pffiffiffiffiffiffi
g
L L Table 5. The SFE components are summarized in Table 6. Fig. 6
ð1 þ cos qÞ ¼ 2 gLW þ 2 g þ 2 gþ L
b gL b gL b gL shows that the total surface energy of the 2 bitumens assessed in
(11) this study reduces when different Cecabase® contents. Silva et al.
(2010) stated that Cecabase® additive acts as a surfactant and re-
The equation is divided into known and unknown components duces surface tension. This allows a reduction of mixing tempera-
as follows: ture without changing its viscosity. Surface energy was found to
qffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffi increase the short-term and decrease when long-term aged
pffiffiffiffiffiffi
ð1 þ cos qi Þ¼ Yi ; 2 gLWb
¼ X1 ; 2 g b
¼ X 2 ; 2 gþ b
¼ X3 bitumen was assessed. According to Little et al. (2006) the LW
component is the most significant contributor to the total surface
energy of bitumen while the magnitudes of acid and base compo-
where; ‘i’ denotes the values obtained for probe liquid 1, 2 or 3
nents are very small. This is consistent with the fact that most bi-
which, for this example, are water, ethylene glycol and methylene
tumen's are weakly polar materials.
iodide.

qffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffi 5.1. Effects of surfactant-based additive on the work of adhesion

pffiffiffiffiffiffi
gLWL
gþ L g energy of asphalt binder
L
Similarly; for any liquid i; A1i ¼ ; A2i ; A3i
gL gL gL
The work of adhesion for the PG-64 bitumen blends is shown
The divided components are then written as three separate in Fig. 7. This illustrates that with the addition of Cecabase®, the
equations Eqs. (12)e(14) of the form; Work of Adhesion improves compared to the unmodified bitumen.
The results illustrate that simulated bitumen aging has an adverse
ðA11 þ A21 þ A31 ÞX1 ¼ y1 (12) effect on the adhesion property. The decrease in Work of Adhesion
becomes more prominent for RTFO and PAV aged conditions for
PG-64 bitumen interaction with granite aggregate. However, un-
ðA12 þ A22 þ A32 ÞX2 ¼ y2 (13)
der RTFO aging conditions, Cecabase® improves the adhesion of
binder as compared with corresponding PAV aged binder. The
ðA13 þ A23 þ A33 ÞX3 ¼ y3 (14) adhesion of the PG-64 bitumen with limestone aggregate was
greater than that with the granite aggregate after RTFO and PAV
where, ‘x1,x2 and x3’ represents the three unknowns. aging. This suggests that the limestone aggregate used in this
The surface energy components of the probe liquids used are study has better bonding ability with bitumen compared to
presented in Table 2. The contact angles measured with each probe granite aggregate used. There was a consistent decrease in Work of
liquid are given in Table 4: Adhesion found for the unaged Cecabase® blends and granite
aggregate. According to Cheng et al. (2001) the granite has a much
smoother surface texture whereas at the same gradation, the
Table 4
limestone has three times more surface area and almost three
Contact angle results (example solution).
times Gibbs free energy than granite. Thus, it is much easier to
No. Probe liquid Contact angle Contact angle induce adhesive fracture at the asphaltegranite interface under
(degree) (Radian)
the same wheel load and environmental stresses as a result
1 Water 97.40 1.6999 granite is more likely to strip.
2 Ethylene glycol 69.80 1.2182 Fig. 8 shows that the adhesion energy of the PG-76 bitumen is
3 Methylene iodide 89.15 1.5559
slightly improved by the addition of Cecabase®. This improvement
2348 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353

Fig. 5. Output snapshot of the developed algorithm using Microsoft visual studio.

was better with the limestone aggregate compared to granite.
Similar to the PG-64 bitumen blend, the interaction with granite
aggregate has a consistent decrease in adhesion energy for short-
term and long-term aged samples. The adhesion energy of both
the PG-64 and PG-76 bitumen blends with limestone aggregate is
higher compared to granite.
5.2. Effect of surfactant-based additive on bitumen spreadibility
coefficient
The Spreadibility Coefficient (SC) of bitumen over an aggregate
surface is calculated using Eq. (7). The results determined for the
bitumen blends and aggregates are shown in Figs. 9 and 10. This

Table 5
Contact angle of unmodified and Cecabase® modified bitumen in various aging states.

Binder Cecabase Solvent Contact angle (degree)

type additive
Original sample RTFO-Aged sample PAV-Aged sample
(%)
Average %CV Average %CV Average %CV

PG-64 0.0 Water 97.40 0.56 102.66 0.39 108.66 0.25

Ethylene glycol 69.80 0.43 69.39 0.62 74.10 0.79
Methylene 89.15 0.45 81.60 0.20 86.60 0.44
iodide
0.2 Water 98.20 0.27 103.54 0.20 108.86 0.30
Ethylene glycol 68.10 0.75 74.94 0.45 75.20 0.69
Methylene 89.30 0.37 82.37 0.54 86.90 0.31
iodide
0.3 Water 98.70 0.42 104.21 0.13 109.24 0.36
Ethylene glycol 68.70 0.32 75.07 0.37 76.10 0.91
Methylene 89.10 0.28 83.16 0.57 87.30 0.24
iodide
0.4 Water 98.81 0.36 104.85 0.44 109.24 0.36
Ethylene glycol 70.20 0.56 76.47 0.38 76.10 0.91
Methylene 89.46 0.31 83.16 0.86 87.30 0.24
iodide

PG-76 0.0 Water 104.50 0.97 105.10 1.12 110.10 0.47

Ethylene glycol 74.40 0.38 75.40 0.72 80.40 1.02
Methylene 89.50 0.42 88.90 0.32 92.90 0.97
iodide
0.2 Water 104.90 0.46 105.30 1.17 111.20 0.98
Ethylene glycol 75.40 0.59 74.90 0.21 81.10 1.29
Methylene 92.80 0.29 89.00 0.84 93.40 1.24
iodide
0.3 Water 105.30 0.54 108.60 0.42 114.30 0.89
Ethylene glycol 75.70 1.28 75.30 2.25 82.10 1.43
Methylene 93.20 0.57 88.70 0.92 93.30 0.12
iodide
0.4 Water 105.60 0.76 109.30 0.98 115.60 0.54
Ethylene glycol 76.10 1.42 76.20 0.50 81.10 1.18
Methylene 93.80 1.11 88.90 0.52 95.10 0.55
iodide
 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353 2349

Table 6
SFE components of unmodified and Cecabase® modified bitumen in various aging states.

Binder Cecabase Aging Non-polar component Basic component Acidic component Polar component Total SFE gT
type additive % gSLW (ergs/cm2) g (ergs/cm2) gþ (ergs/cm2) gAB (ergs/cm2) (ergs/cm2)

PG-64 0.0 Unaged 13.08 1.791 2.55 4.28 17.36

RTFO 16.68 0.168 2.08 1.18 17.86
PAV 14.25 0.011 2.30 0.32 14.57
0.2 Unaged 13.01 1.193 3.07 3.83 16.84
RTFO 16.30 0.473 1.21 1.51 17.81
PAV 14.11 0.002 2.11 0.14 14.25
0.3 Unaged 13.10 1.113 2.95 3.62 16.72
RTFO 15.91 0.363 1.32 1.38 17.29
PAV 13.92 0.001 2.01 0.08 14.01
0.4 Unaged 12.94 1.321 2.65 3.74 16.69
RTFO 15.91 0.372 1.13 1.30 17.20
PAV 13.83 0.002 1.99 0.14 13.97

PG-76 0.0 Unaged 12.92 0.334 2.25 1.74 14.66

RTFO 13.19 0.307 2.01 1.57 14.76
PAV 11.45 0.049 1.91 0.61 12.06
0.2 Unaged 11.49 0.393 2.54 2.00 13.49
RTFO 13.15 0.238 2.15 1.43 14.58
PAV 11.24 0.014 1.92 0.32 11.56
0.3 Unaged 11.32 0.351 2.57 1.90 13.22
RTFO 13.28 0.000 2.32 0.05 13.33
PAV 10.87 0.062 2.08 0.72 11.58
0.4 Unaged 11.07 0.340 2.59 1.88 12.95
RTFO 13.19 0.000 2.21 0.06 13.25
PAV 10.54 0.252 2.54 1.60 12.14

shows that the spreadibility of unaged PG-64 is slightly improved
by the addition of Cecabase® and illustrates how asphalt mix pro-
duction can be achieved at lower mixing temperatures. Surface
active agents, the so-called “surfactants” are used as anti-strip ad-
ditives (Wasiuddin, 2007). The addition of liquid anti-strip agents
typically reduced the surface free energy and consequently the
work of cohesion of the asphalt binders (Howson, 2011). A reduc-
tion in the gLW component of the surface free energy allows better
coating of the aggregate by the asphalt, improving interfacial
adhesion and, thus, improving the fracture resistance of the
mixture matrix. This can indirectly improve the fracture resistance
by promoting better adhesion between the fines and the binder
during the mixing and compaction process (Howson, 2011). Since
Cecabase® is surfactant and acts like surface active agent, therefore
increased wettability gives increased surface area to be wetted and
promotes adhesion between the binder and the aggregate. Better
values were obtained with limestone aggregate compared to
granite after the bitumen had been subjected to RTFO and PAV
aging conditions. Simulated aging of the bitumen caused an
adverse effect on its spreadibility. An example of modifications due
to environmental effects is oxidative aging, which significantly al-
ters the chemistry of the binder and consequently its mechanical
properties (Howson, 2011). It is believed that in addition to bonding
interactions, the ultimate adhesive strength is influenced by the
chemistry of the interface between aggregate and the binder
(Hamzah et al., 2013). Therefore aging can have different impacts
on different asphalt binders depending on the initial chemistry of
the asphalt binder. Under long-term PAV aging conditions, inter-
action with limestone aggregate improved compared to short-term
aging. This was consistent for all amounts of Cecabase® additive
used. However, this effect was not observed for the granite aggre-
gate and needs further investigations.
Fig. 10 shows that the Spreadibility Coefficient improved for the
PG-76 SBS bitumen and limestone aggregate, after both RTFO and

Fig. 6. Total surface free energy of the bitumen's in an unaged condition.

2350 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353

Fig. 7. Work of adhesion energy for the PG-64 bitumen blends.

Fig. 8. Work of adhesion energy for the PG-76 bitumen blends.

Fig. 9. Spreadibility coefficient for PG-64 bitumen blends.

 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353
Fig. 10. Spreadibility coefficient for PG-76 bitumen blends.
PAV aging conditions with the addition of Cecabase®. Bitumen
spreadibility decreased due to both short and long-term aging
conditions. The overall spreadibility of PG-76 binder over limestone
aggregate was higher as compared with granite. Unlike PG-64, the
spreadibility of long-term aged PG-76 binders is lower than both
unaged and short-term aged binders. The spreadibility of PG-76
binder over limestone is comparatively higher than granite
aggregate.
5.3. Effect of surfactant-based additive on bitumen compatibility
ratio
Figs. 11 and 12 present the calculated Compatibility Ratio data.
Fig. 11(a) shows high resistance against moisture damage for the
PG-64 bitumen and limestone aggregate combinations. This resis-
tance is greater for unaged bitumen compared with RTFO and PAV
aged bitumen. Cecabase® additive improves resistance to moisture
damage for the unaged bitumen. The calculated Compatibility Ra-
tios for the bitumen/granite combinations is presented in Fig. 11(b).
This indicates that the resistance to moisture damage for the
granite combinations is lower compared to the limestone combi-
nations. However, the unaged bitumen/granite combinations re-
sults are still greater than the minimum requirement of 0.5.
Fig. 11. Compatibility ratio of PG-64 bitumen blends.
2351
The compatibility ratios for the PG-76 bitumen/limestone and
granite aggregate combinations are as shown in Fig. 12. The values
for the granite aggregate combinations are lower than limestone
aggregate combinations. This is because of the silica (SiO2) content
present in aggregate which is an important factor to the adhesion
properties. It has been generally observed that, limestone being
alkaline aggregates has low silica content and provide better
adhesion to bitumen. This can be well explained by the fact that
bitumen (particularly those of Venezuelan origin) contains naph-
thenic acids (Glozman and Akhmetova, 1970). The naphthenic acids
have a carboxylic acid group, COOH, and a hydrocarbon part which
is similar in structure to the bitumen itself. When such a molecule
comes in contact with an alkaline aggregate, the carboxylic acid
part will be absorbed on the surface with the hydrocarbon part
pointing outward. This will change the surface of the aggregate
enough to enable the binder to adhere to it even if water should be
present. Though, one of the major disadvantages with limestone
aggregates is that they normally get polished under traffic action
and should therefore be avoided in surface courses. However, sili-
ceous aggregates such as granite are normally not so sensitive to
polishing but have another disadvantage. Being acidic, they do not
respond to the action of the naphthenic acids in the bitumen. In
fact, the acids counteract each other and a good bond is difficult to
2352 M.R. Kakar et al. / Journal of Cleaner Production 112 (2016) 2342e2353
Fig. 12. Compatibility ratio of PG-76 bitumen blends.
obtain between a siliceous aggregate and bitumen. Sometimes
there are also alkaline components in the binder but they are very
weak and cannot give a better bond to silica (Tarrer and Wagh,
1991). Hence, lower values of granite aggregate combinations are
obtained compared with limestone aggregate. The resistance to
moisture damage becomes slightly lower when the bitumen is aged
under RTFO and PAV conditions. The addition of Cecabase® slightly
improves resistance against moisture damage compared to the
unmodified bitumen. The use of Cecabase® is less effective for the
granite combinations and both types of bitumen used. This is
consistent with the general observation that granite is more sus-
ceptible to stripping than limestone (Cheng et al., 2003).
6. Conclusions and recommendations
Surfactant based chemical additives are typically used to reduce
bitumen surface energy and enhance its wettability over the sur-
face of aggregate particles. This needs to be optimized to minimize
the effects of premature failure particularly in wet conditions. This
is particularly relevant for asphalt mixtures such as Warm Mix
Asphalt that are mixed at lower temperatures to conventional hot
mix asphalt. Better understanding of fundamental material prop-
erties of bitumen/aggregate mixtures play an important role in
improving confidence in these materials. The results based on the
research presented in this paper showed that the Cecabase® sur-
factant based chemical additive reduced bitumen surface energy
and increased the ability of bitumen to wet the aggregate. The
overall surface free energy increased with RTFO bitumen aging,
whereas surface free energy was reduced after PAV aging. The re-
sults further illustrated that both the PG-64 and PG-76 bitumen's
used in the study were acidic in nature. The work of adhesion was
found to be slightly improved for unaged bitumen when Cecabase®
additive was added. The compatibility ratio for PG-64 and PG-76
bitumen/limestone aggregate combinations was higher compared
to the granite aggregate combinations. This indicates that bitumen/
limestone aggregate combinations had better moisture suscepti-
bility compared to the granite aggregate combinations. The authors
recommend testing different bitumen's and warm mix additives
using Goniometer and Wilhelmy plate device method. It is also
recommended that mixture based performance studies should be
carried out to further co-relate the results obtained from surface
free energy measurements.
Acknowledgments
The authors would like to acknowledge the Malaysian Ministry
of Higher Education through the Fundamental Research Grant
Scheme (FRGS grant number 203/PAWAM/6071277) and Institute
of Postgraduate Studies, IPS, Universiti Sains Malaysia for the Global
Fellowship [USM.IPS/USMGF/(06/14)] that enabled this paper to be
written. The authors would also like to mention the support and
special assistance provided by Dr. Irman Abdul Rahman, Senior
Lecturer in the School of Applied Physics, Faculty of Science and
Technology, Universiti Kabangsaan Malaysia (UKM). In addition,
many thanks are also due to the technical facility provided by the
Nuclear Science Department, UKM, for conducting the contact
angle measurements experiments.
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