Evaluation of Moisture Susceptibility of Nanoclay-Modified

Asphalt Binders through the Surface Science Approach

Zahid Hossain, A.M.ASCE 1; Musharraf Zaman, P.E., F.ASCE 2; Takumi Hawa 3; and Mrinal C. Saha 4

Abstract: Due to an increasing rate of traffic volume and truckloads in recent years, asphalt binders are often modified with synthetic
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polymers to increase stiffness and sustain excessive heat during hot summer days. However, the cost of polymer-modified binders (PMBs)
is significantly higher than unmodified binders. Nanoclays, on the other hand, are relatively inexpensive and naturally abundant, and have
favorable intrinsic properties, such as nanoscopic size and high surface area. To this end, the research reported in this paper investigated
moisture resistance properties of a commonly used Performance Grade (PG) 64-22 binder modified with different dosages of two selected
nanoclays [(1) Cloisite 15 A, and (2) Cloisite 11B]. The state of dispersion of the nanoclay in the binder was examined using a scanning
electron microscope and small-angle x-ray diffraction. The morphological analyses of scanning electron microscope scans and inter-gallery
distances (d-spacing values) of small-angle x-ray diffraction data of the two selected nanoclays are effective in evaluating the state of ex-
foliated microstructure of nanoclays in asphalt binders. In particular, the small-angle x-ray diffraction data of two of the tested samples [(1)
4% of Cloisite 11B, and (2) 6% of Cloisite 11B] showed fully exfoliated microstructure. Moisture resistance of nanoclay-modified binders
was evaluated through the surface free energy (SFE) technique. The adhesive energies and compatibility ratios (CRs) of nanoclay-modified
binder and selected aggregate (four acidic and four basic) systems were also evaluated. The total SFE increases when the asphalt binder is
modified by nanoclays. When the asphalt binder is modified with nanoclays, the wetting ability decreases. A 4% Cloisite 15 A and a 6%
Cloisite 11B (by the weight of the binder) showed the highest adhesive energy in maintaining good wetting ability, with different acidic and
basic aggregates. The work-of-adhesion values under dry and wet conditions of nanoclay-modified binders were highly dependent on the
nature (acidic or basic) of aggregate. The CR, an indicator of moisture resistance or bond strength in wet conditions, of the nanoclay-modified
asphalt binder decreased for all aggregates except for granite, which showed a slight increase of the CR values. Thus, unless modified with an
antistripping agent or other additives, nanoclay modified binders are expected to have poorer moisture resistance than the base binder. While
maintaining a dosage level of 4% (by weight) nanoclay, Cloisite 15 A, consisting of smaller particle size than Cloisite 11B, is more com-
patible with different aggregates than Cloisite 11B. At a lower dosage level (2% by weight), Cloisite 11B is more compatible than Cloisite
15 A. Furthermore, the nanoclay technology is expected to be a cost saving approach, which can reduce the cost per metric ton of asphalt
binder from 22–33% compared to the polymer-modified binders. Findings of this paper are expected to assist pavement professionals in
evaluating moisture resistance of nanoclay-modified asphalt binders through a fundamental science approach. DOI: 10.1061/(ASCE)MT
.1943-5533.0001228. © 2014 American Society of Civil Engineers.

Introduction a small amount (about 5% by weight), asphalt binder plays a major

Background and Research Need
Over 90% of paved roads in the United States are asphalt pavements
and the annual expenditures for the maintenance of these pavement
infrastructures exceed U.S. $100 billion [Northeast Center of
Excellence for Pavement Technology (NECEPT) 2012]. Although
1
Assistant Professor of Civil Engineering, Arkansas State Univ., P.O.
Box 1740, Lab Science West No. 239, State University, AR 72467 (corre-
sponding author). E-mail: mhossain@astate.edu
2 Grade (PG) 64-22 binder was U.S. $532.50 (ODOT 2013). The
David Ross Boyd Professor and Aaron Alexander Professor of Civil
Engineering, and Alumni Chair Professor of Petroleum Engineering,
202 W. Boyd St., Room No. 334, Univ. of Oklahoma, Norman, OK
73019. E-mail: zaman@ou.edu
3
Assistant Professor of Aerospace and Mechanical Engineering, Asp
Ave., Felgar Hall, 212, Univ. of Oklahoma, Norman, OK 73019. E-mail:
hawa@ou.edu
4
Associate Professor of Mechanical Engineering, 865 Asp Ave., Felgar
Hall, 212, Univ. of Oklahoma, Norman, OK 73019. E-mail: msaha@ou.edu
Note. This manuscript was submitted on December 9, 2013; approved
on October 21, 2014; published online on December 9, 2014. Discussion
period open until May 9, 2015; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561/04014261(9)/$25.00.
role on the performance of the hot mix asphalt (HMA) pavements.
Surface properties and temperature susceptibility characteristics of
the asphalt binder influence pavement stiffness (and moisture resis-
tance), and thereby can dramatically affect the performance of the
asphalt mixes.
Currently, polymer additives such as styrene-butadiene-styrene
(SBS) are used to enhance properties and functional characteristics
(e.g., increased rut resistance) of asphalt binders, which increases
the overall cost of the asphalt binder (Gierhart 2011; ODOT 2012).
As of December 2013, the cost per metric ton of Performance
cost per metric ton of a polymer-modified binder ranges from
50–100% more than that of the neat asphalt binder, translating to
an increase of 10–20% in the cost of the in-place asphalt (Michael
Thomas, personal communication, T. J. Campbell Construction
Company, 2011). In general, excessive clay-like fine particles in
HMA can contribute to a lack of stability (rutting or shoving),
or moisture damage and stripping (Anderson 1996). The coatings
of aggregates by clay particles are likely to inhibit stripping and for
this reason the Superpave mix design procedure includes the sand
equivalency test to ensure that the fine aggregate fraction does not
contain clay particles. Due to these detrimental effects of excessive
fines, the use of high reclaimed asphalt pavement (RAP) content

© ASCE 04014261-1 J. Mater. Civ. Eng.

J. Mater. Civ. Eng.

 has been hindered in HMA (Al-Qadi et al. 2012). On the other
hand, when mixed dispersed at a nanoscopic level, nanoclays
can potentially improve the performance of asphalt binders and as-
phalt mixes due to their nanoscale phenomena such as the quantum
effects, structural features, high surface energy, spatial confine-
ment, and large fraction of surface atoms (Liu et al. 2010; Yao et al.
2013). Moreover, nanoclays are fairly inexpensive, naturally abun-
dant, and sustainable materials for the construction of asphalt pave-
ments. Thus, a significant portion of the current usage of the
polymer-modified binder (PMB) can potentially be replaced by
nanoclay-modified binders for improved mechanical and functional
characteristics of the asphalt pavements.
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Nanoclays are layered silicates that are found naturally and
hence they are environmentally safe, economical, and sustainable.
One of the most frequently used layered silicates is montmorillonite
(MMT), which has a 2:1 layered structure with two silica tetrahe-
dron layers sandwiching an alumina octahedron layer (Hauser and
Colombo 1953; Ray and Okamoto 2003). These three layers to-
gether form one clay sheet that has a thickness of 0.96 nm, thus
the individual clay sheets are classified as a nanomaterial, although
the lateral dimensions of the individual clay sheet can vary from
100 nm to a few micrometers [National Nanotechnology Initiative
(NNI) 2013]. A number of physical, mechanical, and rheological
properties such as fracture toughness, moduli, strength and heat
resistance, gas permeability and flammability, and biodegradability
of polymer-modified binders are successfully enhanced by the ad-
dition of a small amount of nanomaterials, 1–5% by weight (Ray
and Okamoto 2003; Ratna et al. 2005; Saha et al. 2009; Saha and
Nilufar 2010). Due to their enormous surface area and energy,
nanoclays have a huge potential as a modifier to improve asphalt
binder’s performance properties (e.g., rutting). However, under-
standing and controlling interactions, between the asphalt binder
and nanoclays, are of significant interests for the development
of superiorly performing pavements.
Untreated nanoclay sheets are held together due to a high met-
allic cation presence on the surface, giving a low intergallery spacing
(about 11.7 Å). Organic treatments are often used to increase the
intergallery spacing so that polymer molecules can penetrate the in-
tergallery spacing of the silicate layers. When the polymer molecules
penetrate the adjacent layers of the nanoclay sheets, the gallery spac-
ing is increased and the resulting morphology is called an interca-
lated structure (Hussain et al. 2006; Barick and Tripathy 2010). An
exfoliated morphology occurs when the clay platelets are exten-
sively delaminated and completely separated as a result of through
polymer penetration. Although various dispersion techniques (in
combination with coupling agents) are used, creating an exfoliated
nanoclay structure in a stable manner is a challenging task. Thus,
naturally occurring nanoclays may require further treatment to pre-
pare exfoliated structure when blended with asphalt binders.
Even though the advancement of nanotechnology research
has increased exponentially in recent years, limited studies have
attempted to investigate the application in asphalt pavements.
You et al. (2011) studied effects of two unspecified nanoclays
on a PG 58-34 binder for conditions prevailing in Michigan.
The complex shear modulus (G
) increased about 66% for the
2% nanoclay-modified binder while the G
values increased by
125% for the 4% nanoclay-modified binder. That study also re-
ported a significant increase in viscosity of the nanoclay-modified
binders. In Jahromi and Ahmadi (2011), it was reported that
both the Cloisite 15 A and Nanofil15 modifications on a Viscosity
Grade AC-10 binder increased the stiffness and rutting resistance,
indirect tensile strength, and resilient modulus, but the fatigue
performance decreased. These researchers also reported that
nanoclay increased the viscosity of the neat binder. Findings of
© ASCE 04014261-2
J. Mater. Civ. Eng.
some early-stage experimental data focusing on viscoelastic and
performance properties of one of the additives (Cloisite 15 A)
used in the research reported in this paper have been published else-
where (Hossain et al. 2013, 2014). A few other recent studies
(e.g., Khattak et al. 2011; Xiao et al. 2011; Yao et al. 2012; Nazzal
et al. 2013) have focused on performance of asphalts modified with
nanocomposite materials (e.g., carbon nanotube and nanofillers).
However, none of these studies focused on the performance of
nanoclay-modified binders against moisture damage (stripping).
While some rheological data of nanoclay-modified binders from
limited studies show positive results, moisture susceptibility of
nanoclay-modified binders is yet to be investigated. Traditionally,
tensile strength ratio (TSR) data is used to investigate the moisture
susceptibility of asphalt mixes. However, outcome of these tech-
niques are often misleading as they lack mechanistic rigor. Recent
studies (e.g., Cheng et al. 2002; Bhasin et al. 2005, 2007; Bhasin
and Little 2006) have introduced a similar parameter called com-
patibility ratio (CR) in the surface free energy (SFE) theory, which
is based on the surface science approach. The CR is defined as the
ratio of work of adhesion of an aggregate and binder system (dry
condition) to the work of adhesion of the same system in presence
of water (wet condition). The higher the CR value, the higher the
moisture resistance of the aggregate-binder system.
Towards evaluating the SFE of asphalt binders, Cheng et al.
(2002) first proposed the SFE theory and used the Good-van
Oss-Chaudhury theory to evaluate the free energies of the asphalt
binder and aggregates, and subsequently the free energy of adhe-
sion between them for the assessment of moisture susceptibility of
asphalt mixes. According to the Good-van Oss-Chaudhury theory
(Van Oss et al. 1998), the SFE of a material is divided into three
separate components based on the source of the intermolecular
forces, as follows: (1) monopolar acidic component (Γþ ), (2) mo-
nopolar basic component, (Γ− ), and (3) apolar [or Lifshitz-van der
Waals (ΓLW )] component. The total SFE (Γtotal ) for a single phase is
divided into a Lifshitz-van der Waals (LW) component (ΓLW ) and
an acid-base (AB) component (ΓAB )
Γtotal ¼ ΓLW þ ΓAB ð1Þ
where the acid-base part of the free energy (ΓAB ) can be written as
pffiffiffiffiffiffiffiffiffiffiffiffi
ΓAB ¼ 2 Γþ Γ− ð2Þ
Similarly, the Gibb’s free energy of adhesion (ΔGad ) also con-
sists of two components
ΔGad ¼ ΔGLW
ad þ ΔGad
AB
ð3Þ
The individual components of Eq. (3) are given by
qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi
ΔGABad ¼ −2 Γþi Γj þ
−
Γ− i Γj
þ
ð4Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ΔGLW
ad ¼ −2 ΓLWi Γj
LW
ð5Þ
Combining Eqs. (1)–(5), the Young-Dupre equation [Eq. (6)] for
the work of adhesion can be expressed as
W a ¼ −ΔGad
dry ¼ ΓL ð1 þ cos θÞ
total
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi
¼2 ΓLWL ΓS þ
LW
ΓþL ΓS þ
−
Γ− L ΓS
þ
ð6Þ
where the subscripts L and S represent liquid and solid phases,
respectively.
J. Mater. Civ. Eng.
 The previously mentioned relationship [Eq. (6)] is used in
this paper in interpreting the SFE components of the asphalt binder
with reference to a solvent by evaluating the respective contact
angle. To determine the three unknown free energy components
of the asphalt binder, the contact angle of the asphalt binder is mea-
sured with three reference solvents [(1) water, (2) glycerin, and
(3) formamide] of known SFE properties (Bhasin and Little
2006). Similarly, the free energy of adhesion between asphalt
binder (designated as a) and aggregate (designated as A) in the
presence of water (designated as W), is given by
 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ΔGad ¼ 2Γ þ 2 Γ Γ − 2 Γ Γ − 2 ΓLW
LW LW LW LW LW
wet w a A a W
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qffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffi
þ 4 Γþ − þ − − þ
W ΓW þ 2 Γa ΓA − 2 Γa ΓA þ 2 Γa Γw
þ −
pffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi 
þ −
− 2 Γ− þ
a Γw − 2 ΓA Γw
The free energy of cohesion (ΔGc ) is the creation of a unit area
of crack within a material under a vacuum condition. The free en-
ergy of cohesion of the asphalt binder can be calculated by (Bhasin
et al. 2007)
ΔGc ¼ 2Γtotal
Several researchers have developed SFE databases for different
aggregates and asphalt binders, and drawn conclusions on their
performance based on the free energy of adhesion. Cheng et al.
(2002) used the SFE of the asphalt binder to estimate the wetting
ability of aggregates by asphalt binder. The writers of the research
reported in this paper used the protocol proposed by Cheng et al.
(2002) to determine the contact angles of asphalt binders modified
with warm mix asphalt additives and amine antistripping agents
(Hossain et al. 2009; Budhala et al. 2012). In a few other studies
(e.g., Cheng et al. 2002; Bhasin et al. 2007), researchers examined
the effect of different additives on the cohesive strength of asphalt
binders and adhesive strength, between asphalt binders and aggre-
gates. While the tested materials of the research reported in this
paper differ from those of the previously mentioned studies, it is
emphasized that the SFE and other surface properties are in accor-
dance with a complex phenomenon and depend on various factors
such as the type of asphalt binder, type of aggregate, and the type of
additive used.
Objectives
The main objectives of the research reported in this paper are to the
following: (1) examine the exfoliation of nanoclays in asphalt bind-
ers through spectroscopy analyses, and (2) investigate the effects
on nanoclays on moisture resistance properties through a surface
science approach.
Materials and Methodology
The research reported in this paper evaluated a commonly used
unmodified PG 64-22OK (a PG 64-22 asphalt binder that meets
the performance specifications of the Oklahoma DOT) binder
modified with different dosages of the following two nanoclays:
(1) Cloisite 15 A (2 and 4% by the weight of the binder), and
(2) Cloisite 11B (2, 4, and 6% by the weight of the binder).
The PG 64-22OK binder used in the research reported in this paper
was obtained from the Valero refinery at Ardmore, Oklahoma. The
nanoclay powder was obtained from Southern Clay Products as a
donation. The cost of nanoclays varies significantly depending on
© ASCE
the quality and volume. When research grade nanoclays of a very
small quantity are purchased, the estimated cost is about U.S. $10
for 100 g [U:S:$100=kg (U:S:$50=lb); IM 2014). The cost is sig-
nificantly low when a large amount (minimum order 22 metric
tons) of nanoclays is purchased and it ranges from U.S. $240–
295=metricton (BBI 2014). The cost of medium quantity nanoclays
varies from U:S:$4.96–$7.16=kg (U:S:$2.25–$3.25=lb) (Sherman
2004). The Cloisite 15 A is a natural montmorillonite modified
with a quaternary ammonium salt (2M2HT). The average particle
size of Cloisite 15 A is about 13 μm with average d-spacing of 31.5
Å. The average density is about 1.66 g=cm3 . The Cloisite 11B is
another natural montmorillonite modified with a different
A ΓW
LW
quaternary ammonium salt (2MBHT). Its average particle size is
about 37 μm with average d-spacing of 18.4 Å. The average density
is about 2.0 g=cm3 .
ð7Þ
Mixing Nanoclay and Asphalt Binder
About 200 g of the neat binder was heated in a glass container to
130°C for about 2 h to achieve the processing viscosity. Then the
nanoclay was added to the heated asphalt binder and mixed using a
high shear mixer. The speed of high shear mixer was gradually in-
creased and fixed to about 3,000 rpm while maintaining the mixing
ð8Þ temperature of 130°C. The mixing was continued for about 2 h to
achieve uniform dispersion of the nanoclay in the asphalt binder. At
the very early stage of the research reported in this paper, a combi-
nation of a lower speed (500 rpm) and higher temperature (150°C)
was maintained using a mechanical mixer. To reduce the aging ef-
fect, the mixing temperature was reduced to 130°C in the research
reported in this paper.
Dispersion Characterization
The dispersion of nanoclay in asphalt binders was examined at a
nanoscale level using both scanning electron microscope (SEM)
and small-angle x-ray diffraction (SAXD) techniques. Morphology
of the nanoclay sheets on the surface of the asphalt sample was
studied using a scanning electron microscope [Zeiss NEON field
emission (FE) SEM]. For this purpose, a small drop of asphalt
binder sample was placed on the SEM sample holder, coated with
gold using an ion sputter (JFC-1100), and scanned using an accel-
erating voltage of 15–20 kV. The SEM provides a qualitative mea-
sure of the dispersion directly from the microstructural image.
The SAXD is used to provide a quantitative analysis of the
interlayer gallery spacing and it provides a way to determine the
extent of dispersion of the nanoclays in the binder. A pinhole-
collimation SAXS system from Rigaku with a copper wire detector
was used for diffraction analysis. The SAXS diffraction intensity
was recorded as a function of 2θ, where θ is the diffraction angle
(between 0 and 15°), and the corresponding basal spacing or d001
reflection of the samples was calculated from Bragg’s equation.
Asphalt binder samples were initially mounted on rectangular plate
sample holders with round holes in the center. The sample was held
on the sample holder using a scotch tape so that the sample went
across the opening. The transmittance for each sample was man-
ually recorded and sample positions calibrated. Scattering data de-
pending on the spatial was detected using a two-dimensional (2D)
wire detector at a distance of about 1.5 m (59 in.) from the sample.
Both SEM and SAXD data are compared, to achieve a conclu-
sion on the level of dispersion and efficiency of the blending pro-
cess. In the SAXD technique, Bragg’s law of diffraction is used to
measure d-spacing between the nanoclay sheets. Spacing change
(increase or decrease) information can be used to determine the
level of dispersion. For example, no d-spacing change indicates
04014261-3 J. Mater. Civ. Eng.
J. Mater. Civ. Eng.
 immiscible, an increase in d-spacing indicates intercalated, and no
distinct peak in the signal indicates exfoliation. In the case of peak
in the signal, the d-spacing can be determined
λ
d¼ ð9Þ
2 sin θ
where λ is the wavelength of the x-ray source (λ ¼ 1.54Å).
Evaluation of SFE
The SFE characteristics of the original and modified binders were
evaluated using the dynamic contact angle measurements. Effect
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of moisture on the theoretical bond strength (adhesive and cohe-
sive) was evaluated based on SFE components using the Good
Van Oss-Chaudhury theory (Van Oss et al. 1998). A dynamic con-
tact angle analyzer (DCA, No. 322) from Cahn was used in the
research reported in this paper for measuring the contact angles
with three reference solvents [(1) water, (2) glycerin, and (3) forma-
mide]. This analyzer is in accordance with the Wilhelmy plate
method, which determines the contact angle at the solid-liquid in-
terface by measuring the force exerted by the meniscus on the sam-
ple. The DCA samples were prepared in accordance with the
protocol established by researchers (Little and Bhasin 2006) at
the Texas Transportation Institute (TTI). The DCA sample prepa-
ration steps consisted of decontaminating a thin glass plate and
coating it with the liquid asphalt binder. The decontamination of
the glass plate was achieved by passing the end of the glass slide
intended for coating 6× on each side through the blue flame of a
propane torch to remove any moisture. The coating of the glass
plate was provided by dipping it into the liquid asphalt binder
to a depth of approximately 15 mm and allowing excess binder
to drain from the plate, until a very thin (0.18–0.35 mm) and uni-
form layer remained on the plate. The thickness of asphalt binder
was maintained uniform on both sides of the glass plate throughout
its width and for at least 10 mm from the edge that was to be im-
mersed in the probe liquid. At least three replicate samples were
tested for each reference liquid to assure repeatability of the contact
angle measurements.
Test Results and Discussions
Dispersion of Nanoclay in Asphalt Binder
A sample SEM showing the state of nanoclay dispersion and ag-
glomerates size is shown in Fig. 1(a). Nanoclays are fairly distrib-
uted uniformly in the binder matrix; no visible nanoclay clusters are
seen in the SEM image but further investigations were considered
necessary. Fig. 1(b) shows the SAXD data in the form of intensity
as a function of 2θ angle for the nanoclay modified binders. The
Cloisite 15 A samples with 2 and 4% show peak, at 2θ values of
1.934 and 1.991°. The corresponding d-spacing values are 45.7 and
44.3 Å. Comparing the d-spacing value of Cloisite 15 A of 31.5 Å,
the increased value of the d-spacing indicates that the 2 and 4%
Cloisite 15 A-modified samples show intercalated microstructure.
The Cloisite 11B samples with 2% show peak at 2θ value of
1.891° (46.67 Å). Compared to the d-spacing of Cloisite 11B of
18.4 Å, the 2% nanoclay modified sample show intercalated micro-
structure as well. On the other hand, both 4 and 6% samples do not
show any distinct peaks in the SAXD data, which is an indication of
exfoliated microstructure. As mentioned previously, one of the ma-
jor processing challenges in nanocomposites research is to achieve
uniform dispersion of nanoclays in the asphalt binder and there
are two major reasons behind this challenge, as follows: (1) the
© ASCE 04014261-4
J. Mater. Civ. Eng.
(a)
4
3.5
2% Cloisite 15A
Intensity (arbitrary units)
3
4% Cloisite 15A
2.5
2% Cloisite 11B
2 4% Cloisite 11B
6% Cloisite 11B
1.5
1
0.5
0
0 1 2 3 4 5
(b) Scattering Angle
Fig. 1. Dispersion analysis of nanoclay in asphalt binder: (a) SEM im-
age showing uniform distribution of nanoclay; (b) SAXD data showing
the intensity as a function of scattering angle
nanoclay platelets form microscale agglomerates of different sizes
due to high surface charge, and (2) the viscosity of the asphalt
binder increases with the addition of nanoclays (which further hin-
der dispersion of nanoclay platelets).
Contact Angles
As noted previously, the wetting ability of any surface by a solvent
can be determined by the contact angle made by the solvent with
the surface. A general trend is if the contact angle is close to zero,
then the solvent is spreading on the surface completely; if it is
less than 90°, then it is wetting the surface of the material; if it
is greater than 90°, it is not wetting the surface completely. Results
for the contact angle measurements with three solvents are shown
in Table 1. Average contact angles along with error bars (1 SD) of
replicate specimens of different binder samples with references sol-
vents (water, glycerin, and formamide) are presented in the form of
bar charts in Fig. 2(a). A trend was observed in the contact angle of
the nanoclay-modified PG 64-22 with formamide and glycerin. In
the case of water, the contact angles of nanoclay-modified binders
decreased except for the 2% Cloisite 15 A. Two-tailed unequal vari-
ance Student’s t-test results at 95% confidence interval (p ¼ 0.05)
showed significant differences in the contact angles in all cases
except water and Cloisite 11B (2, 4, and 6%) with the addition
of nanoclay compared to unmodified binder. The highest variation
of contact angles was observed for 2% Cloisite 15 A samples
with water. An increase in contact angle implies less wetting of
J. Mater. Civ. Eng.
 Table 1. Contact Angles, in Units of Degrees, of Different Binder Samples with Reference Solvents
Water Glycerin Formamide
Binder and t-statistics, t-statistics, t-statistics,
nanoclay type and dose Average SD p ¼ 0.05a Nb Average SD p ¼ 0.05a Nb Average SD p ¼ 0.05a Nb
PG 64-22 105.3 0.9 Control 4 87.5 1.37 Control 3 84.6 1.08 Control 3
PG 64 − 22 þ 2% Cloisite 15 A 110.9 1.5 −13.11 4 96.0 2.31 −10.58 3 92.4 2.90 −3.44 3
PG 64 − 22 þ 4% Cloisite 15 A 94.8 2.3 6.29 4 97.0 2.67 −3.45 3 93.5 1.48 −6.82 3
PG 64 − 22 þ 2% Cloisite 11B 103.0 6.4 0.75 4 99.1 2.06 −4.41 3 95.6 0.87 −11.57 3
PG 64 − 22 þ 4% Cloisite 11B 103.7 5.4 0.58 4 96.7 1.19 −7.70 3 94.5 1.53 −4.97 3
PG 64 − 22 þ 6% Cloisite 11B 98.0 8.1 1.80 4 100.3 6.55 −1.99 3 93.9 2.33 −6.02 3
a
t-critical for Nðof 4Þ ¼ 3.18; t-critical for Nðof 3Þ ¼ 4.30.
b
N = number of observations.
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the substrate when nanoclay is mixed with the binder. Using the increase of the nonpolar Lifshitz-van der Waals component (ΓLW a ).
contact angles of nanoclay-modified asphalt binders in the previ- The highest increase (about 56%) of the total SFE was observed in
ously mentioned reference liquids, SFE components were esti- the case of 4% Cloisite 15 A, and the least amount (about 5%) of
mated and are discussed next. increase of the total SFE was estimated for 2% Cloisite 15 A. In the
case of Cloisite 11B, its dosage level of 6% had the largest increase
(about 45%) of the total SFE compared to the base binder. The
Surface Free Energy
acidic nature of the asphalt binder (Γþ a ) decreased and basic
The variations in the SFE characteristics of PG 64-22 binder SFE components (Γ− a ) increased with the amount of nanoclay. Even
modified with selected percentages of nanoclay are presented in though the acidic nature of the binder decreases with the addition of
Fig. 2(b) and Table 2. The total SFE of PG 64-22 increased with nanoclay, the net increase of the total SFE is due to the significant
addition of nanoclays, which is mostly due to the significant increase of the ΓLWa component. The ΓLW a does not vary signifi-
cantly among the types and dosage levels of nanoclays. However,
the acid-basic (combined) SFE value is significantly higher in the
130 case of 4% Cloisite 15 A, compared to the 2% Cloisite 15 A. Thus,
PG 64-22 PG 64-22+2%Cloisite® 15A
Contact angle (degree)

120 PG 64-22+4%Cloisite® 15A PG 64-22+2%Cloisite® 11B

4% Cloisite 15 A is considered the most effective dosage solely
PG 64-22+4%Cloisite® 11B PG 64-22+6%Cloisite® 11B
based on SFE data. In the case of Cloisite 11B, the acid-basic
110
SFE value is lower in the cases of 2 and 4% nanoclay. With further
100 increase of the amount (6%) of Cloisite 11B, the acid-basic SFE
value increases.
90
Even though the interactions between asphalt binder and nano-
80 clays (montmorrilonite mineral) are unknown, the SFE components
70
of asphalt binder are expected to increase in the nanoclay-modified
(a) Water Glycerin Formamide binders. This has been the cases for the ΓLWa components of all types
and dosage levels of tested nanoclays, and the same holds true for
Surface free energy (mJ/m2 )

30 4% Cloisite 15 A and 6% Cloisite 11B. As mentioned previously,

25 Acid Component Ba se Component Liftshitz-va n der Wa a ls Component Tota l SFE montmorillonite clays usually have very high surface free energies
compared to asphalt binders. The ΓLW
17.0

a (nonpolar or dispersive) and

15.4

20
13.6

13.3

ΓAB
11.5
10.9

(polar or nondispersive) values of montmorillonite mineral

10.4

10.1
10.1

10.0
10.0

15 a
7.1

10 (solid) from Crook County, Wyoming, obtained from contact angle

3.3
3.3
3.1

3.0
2.4

data using the sessile drop method (Zisman 1964), were reported to
1.8
1.7

1.7
1.6

5
1.2

0.8
0.7

0 vary from 85.5 to 95.9 and 83.0 to 135.7 mJ=m2 , respectively

PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

(Janczuk and Biae-Piotrowicz 1988). The estimated ΓLW

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B

a and
ΓAB
a values of montmorillonite covered with a water film
(b)
obtained from hydrocarbon adsorption isotherms were 37.4 and
65.5 mJ=m2 , respectively. Jouany (1991) evaluated Ca-monmorri-
lonite mineral from the same source and reported the total SFE of
Work of cohesion (mJ/m2 )

50
110 mJ=m2 , in which the ΓLW a (dispersive) and Γa (polar) values
AB
34.0

2
were 75 and 35 mJ=m , respectively. Jouany (1991) also reported
30.9

40
27.2

26.7
22.9
21.8

30 significant changes in SFE when a small amount of polymer

20 (e.g., polycondesate catechol) is added to montmorillonite mineral.
10 Therefore, it is possible that the molecular orientation of asphalt
0 binder has changed in the process of dehydration of the adsorbate
PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

due to the addition of a small amount of montmorillonite clays.

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B

(c) Work of Cohesion

The SFE components were used to calculate the works of cohesion
Fig. 2. Variation of DCA data for neat and nanoclay-modified PG 64-
for different nanoclay-modified binders [Fig. 2(c)]. In general,
22 binder: (a) contact angle; (b) SFE components; (c) work of cohesion
the work of cohesion increases when the binder is modified with

© ASCE 04014261-5 J. Mater. Civ. Eng.

J. Mater. Civ. Eng.

 Table 2. Surface Free Energy Data for Different Binders and Aggregates
Surface free energy components (mJ=m2 )
Binder/aggregate Binder/aggregate type ΓAB ΓLW Γ− Γþ Γtotal Γþ =Γ− (%)
Binder PG 64-22 3.8 7.1 1.16 3.14 10.89 2.7
PG 64 − 22 þ 2% Cloisite 15 A 1.5 10.0 0.8 0.7 11.5 0.9
PG 64 − 22 þ 4% Cloisite 15 A 6.6 10.4 3.3 3.29 16.98 1.0
PG 64 − 22 þ 2% Cloisite 11B 3.5 10.1 1.77 1.74 13.60 0.9
PG 64 − 22 þ 4% Cloisite 11B 3.3 10.0 1.72 1.61 13.33 0.9
PG 64 − 22 þ 6% Cloisite 11B 5.3 10.1 2.97 2.39 15.45 0.8
Aggregate Sandstonea 250.3 43.5 555.2 28.2 293.7 5.1
Gravelb 299.2 57.5 973 23 356.7 2.4
Granitec 96.2 133.2 96 24.1 229.4 25.1
Downloaded from ascelibrary.org by North Carolina State University on 05/14/15. Copyright ASCE. For personal use only; all rights reserved.

Basaltd 20 52.3 164 0.6 72.3 0.4

Limestone 1e 168 51.9 540.7 13 219.9 2.4
Limestone 2f 21.4 86.5 285.5 0.4 107.9 0.1
Limestone 3g 9.1 79.9 206.5 0.1 89 0.1
Limestone 4h 50 44.1 259 2.37 94.1 0.9
a
From Oklahoma (Wasiuddin et al. 2010).
b
From Texas (Little and Bhasin 2006).
c
From Georgia (Cheng et al. 2001).
d
From Texas (Little and Bhasin 2006).
e
From Oklahoma (Wasiuddin et al. 2010).
f
From Texas (Cheng et al. 2001).
g
From Colorado (Cheng et al. 2001).
h
From Texas (Little and Bhasin 2006).

either of the nanoclay material. Among all nanoclay-modified
binders, 4% Cloisite 15 A showed the highest work of cohesion
(33.96 mJ=m2 ), and next is 6% Cloisite 11B (30.89 mJ=m2 ).
The corresponding works of cohesion of the unmodified, 2%
Cloisite 15 A, 2% Cloisite 11B, and 4% Cloisite 11B binders are
21.78, 22.93, 27.19, and 26.67 mJ=m2 , respectively. Thus, the in-
crease of work of cohesion in the case of 2% Cloisite 15 A is only
5% whereas that in the case of 4% Cloisite 15 A is about 56%.
aggregates, the reduction of the ΔGdry value is the least for basalt.
Among the four basic aggregates (limestones), (1) the highest in-
crease is noticeable for Limestone 1, (2) next is Limestone 2,
(3) next is Limestone 3, and (4) the least reduction occurred for
Limestone 4. In general, the work of adhesion values under wet
conditions (ΔGwet ) of aggregate binder systems in presence of
water increased with addition of nanoclay for all types of aggregate
except for a few cases [Figs. 4(a and b)]. For instance, the ΔGwet

Work of Adhesion
300
The work-of-adhesion values under dry condition (in absence of 250 Sandstone Gravel Granite Basalt
Δ G dry (mJ/m2 )

water) of nanoclay-modified binders and different aggregates are

180
161

161
200
147

143

140
shown in Figs. 3(a and b). The SFE components (Table 2) of these

133
128

121
119

118

115
112
150

111
109
107

acidic (sandstone, gravel, granite, and basalt) and basic (lime-

98

96
91

88
86

82

80
100
69

stones) aggregates are obtained from the literature (Cheng et al.

2001; Little and Bhasin 2006; Wasiuddin et al. 2010). From Figs. 3 50
(a and b), the work-of-adhesion values under dry conditions 0
PG 64-22

PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B
(ΔGdry ) of aggregate binder systems increases with the addition
of 4% Cloisite 15 A and 6% Cloisite 11B irrespective of the nature
of the aggregate (acidic or basic). The increase of ΔGdry values in
the case of 4% Cloisite 15 A is significant (from 12% for basalt to (a)
24% for sandstone), whereas that in the case of ΔGdry is not no- 300
ticeable for all aggregates except for granite, which shows up to a 250 Limestone1 Limestone2 Limestone3 Limestone4
13% increase. A higher value of ΔGdry is desirable to resist mois-
ΔG dry (mJ/m2 )

200
ture damage and it implies that more work is required to separate
144

130
129

124

117

114

114
111
111

150
107

105

103

the asphalt binder from its interface with the aggregate (Bhasin et al.
102
99

97
96

96

94
91

89
88

87
81

2007). In cases of other nanoclay-modified binder and aggregate 100

72

systems (2% Cloisite 15 A, and 2 and 4% Cloisite 11B) the 50

ΔGdry values decrease slightly. In regard to the size of nanoclay, 0
4% Cloisite 15 A tends to show higher ΔGdry values compared to
PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B

4% Cloisite 11B. On the other hand, with 2% nanoclay, Cloisite

11B shows higher ΔGdry values than Cloisite 15 A. Among the
4% Cloisite 15 A and acidic aggregate systems [Fig. 3(a)], the (b)
ΔGdry value is seen to be the highest in the case of gravel
Fig. 3. Variations of ΔGdry for different aggregate-binder systems:
(180 mJ=m2 ), next is sandstone (147 mJ=m2 ), next is granite
(a) acidic aggregates; (b) basic aggregates
(128 mJ=m2 ), and next is basalt (96 mJ=m2 ). Among the acidic

© ASCE 04014261-6 J. Mater. Civ. Eng.

J. Mater. Civ. Eng.

 300 5.0

Compatibility Ratio (CR)

Sandstone Gravel Granite Basalt Sandstone Gravel Granite Basalt

227
250

205
202
4.0

3.15
190
-ΔG wet (mJ/m2 )

181

176

2.86

2.64
200

154

154

154

154

2.44
148

2.40
2.25
3.0
131

2.13
2.04

1.98

1.95
1.86
150

1.72
100 2.0

0.96
0.89

0.86
0.84
59
57

0.77

0.76
55

0.75
55

53

0.9

0.67
50

0.66
0.61
0.53
37

34
34

34
30
50 27 1.0
0
0.0
PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B

PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B
(a)
(a)
Downloaded from ascelibrary.org by North Carolina State University on 05/14/15. Copyright ASCE. For personal use only; all rights reserved.

300
5.0

Compatibility Ratio (CR)

250 Limestone1 Limestone2 Limestone3 Limestone4 Limestone1 Limestone2 Limestone3 Limestone4
-ΔG wet (mJ/m2 )

200 4.0
149

135
133

125

2.45
118

2.35
116

150 3.0

2.17
2.03

1.99
1.83
1.81

1.75
1.71

1.67

1.61
77

1.52
1.49

1.46
100
70
70

69

1.39
67

1.36
63
62
61
61

1.26
60
2.0
54

1.15
52

1.09
52

1.03
48
47

46

0.94
42
41

0.84

0.82
0.68
50
1.0
0
PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B
0.0

PG 64-22+2%

PG 64-22+4%

PG 64-22+2%

PG 64-22+4%

PG 64-22+6%
PG 64-22

Cloisite® 15A

Cloisite® 15A

Cloisite® 11B

Cloisite® 11B

Cloisite® 11B
(b)
(b)
Fig. 4. Variations of ΔGwet values for different aggregate-binder sys-
tems: (a) acidic aggregates; (b) basic aggregates Fig. 5. Variations compatibility ratios for different aggregate-binder
systems: (a) acidic aggregates; (b) basic aggregates [CR > 1.5 denotes
A (good), CR from 0.75 to 1.5 denotes B, CR from 0.5 to 0.75 denotes
C, and CR < 0.5 denotes D (poor)]
value for 4% Cloisite 15 A with gravel or granite system slightly
decreased compared to the corresponding base binder-aggregate
system. However, such reductions of the ΔGwet values are not stat-
istically significant based on the Student’s two-tail tests with a 95%
from 0.53 to 0.89). Among basic aggregates, Limestone 3 (CR
confidence level. The increase of the ΔGwet value in the case of
ranges from 2.03 to 2.45) is the most compatible, next is Limestone
Cloisite 11B remained steady (from 131 mJ=m2 for the base binder
2, next is Limestone 4, and next is Limestone 1. As mentioned pre-
to 154 mJ=m2 , which is about an 18% increase from the former) for
viously, a majority of the aggregate and nanoclay-binder systems
sandstone. A high magnitude of ΔGwet indicates a high thermody-
experiences a reduction in CR values, indicating a reduced moisture
namic potential for water to cause debonding (Bhasin et al. 2007).
Thus, a low ΔGwet is desirable to reduce moisture sensitivity. For a resistance. Thus, to improve the compatibility of nanoclay-
better understanding of the combined effects of ΔGdry and ΔGwet , modified binders with common aggregates, an antistripping agent
compatibility ratios of these aggregate binder systems were esti- (e.g., lime, AD-Here, or HP Plus) can be investigated, and the writ-
mated, and are discussed next. ers intend to pursue it in next phase of the research reported in
this paper.

Compatibility Ratio
Cost Analysis
As mentioned previously, the CR indicates the compatibility of an
asphalt binder and aggregate system. A high CR is desired for a Even though a comprehensive cost analysis is required to make
good moisture resistance aggregate-binder system. The moisture any conclusive remark, an attempt has been made to compare costs
resistance of the aggregate-binder system is predicted by using between polymer-modified and nanoclay-modified binders. It is
the CR criteria (thresholds) proposed by Bhasin et al. (2006). assumed that the existing plant facility will be utilized to manufac-
The proposed criteria classify aggregate-binder systems into four ture nanoclay-modified binders. As mentioned previously, the cost
categories, as follows: (1) A (good) if the CR value is greater than per metric ton of PG 64-22 binder is about U.S. $532.50. Based on
1.5, (2) B if CR ranges from 0.75 to 1.5, (3) C if the CR ranges from the market data provided previously, the cost per metric ton of PG
0.5 to 0.75, and (4) D (poor) if the CR is less than 0.5. From the CR 70-28 and PG 76-28 binders are U.S. $798 (i.e., 50% more than PG
values, as shown in Figs. 5(a and b), nanoclay is expected to reduce 64-22) and U.S. $1,064 (i.e., 100% more than PG 64-22), respec-
the moisture resistance of all of the asphalt and aggregate systems tively. Based on limited findings of the research reported in this
except for a few systems, which include sandstone and 4% Cloisite paper and ongoing research of the writers, the corresponding
15 A, gravel and 4% Cloisite 15 A, gravel and 2% Cloisite 11B, required amounts of nanoclays to manufacture PG 70-28 and
granite and 4% Cloisite 11B, and gravel and 6% Cloisite 11B, with PG 76-28 binders are 2 and 4%, respectively. Considering
a slight increase in CR values. Among the studied acidic aggre- U:S:$4.96=kg (U:S:$2.25=lb) of nanoclays (Sherman 2004), the
gates, with and without nanoclays, basalt is the most compatible cost of per metric ton of equivalent PG 70-28 and PG 76-28 binders
with a CR value ranging from 2.04 to 3.15 (good), next is granite is U.S. $622 and U.S. $712, respectively. Thus, the cost per ton of
with a CR value ranging from 1.86 to 2.25 (good), next is sandstone nanoclay modified binders is expected to be in the range from
(CR value ranges from 0.61 to 0.9), and next is gravel (CR ranges 2233% less than that of polymer modified binders.

© ASCE 04014261-7 J. Mater. Civ. Eng.

J. Mater. Civ. Eng.

 Conclusions and Recommendations
In the research reported in this paper, varying dosages of two types
of nanoclay [(1) 2 and 4% Cloisite 15 A, and (2) 2, 4, and 6% of
Cloisite 11B] were blended with a local PG 64-22OK binder. The
state of exfoliation of different dosages of the two selected nano-
clays was examined using SEM and SAXD techniques. Findings of
this paper suggest that the binder has to be blended with the nano-
clay so that it is fully exfoliated. Based on the SAXD data, two of
the tested samples [(1) 4% Cloisite 11B, and (2) 6% Cloisite 11B]
showed a fully exfoliated microstructure. The moisture resistance
of the nanoclay-modified binders was evaluated through a SFE
technique. The work of cohesion increased when the base asphalt
Downloaded from ascelibrary.org by North Carolina State University on 05/14/15. Copyright ASCE. For personal use only; all rights reserved.
binder was modified with either of the previously mentioned nano-
clays. Preliminary test results of the research reported in this paper
also suggest that 4% Cloisite 15 A and 6% Cloisite 11B are
the dosages that show the highest adhesive energy, between aggre-
gate and binder systems. However, the compatibility of aggregate
and binder systems reduces when nanoclay is blended with the neat
binder, indicating poorer moisture resistance of nanoclay-modified
binders compared to the base binder. Among the different aggre-
gates, in general, basalt is the most compatible and gravel is the
least compatible aggregate with nanoclay-modified binders. When
compared to size of nanoclays, Cloisite 15 A being smaller than
Cloisite 11B, no particular tend in the compatibility ratio values
is observed for the tested aggregate-binder systems. To alleviate
the compatibility issue, antistripping agents may be evaluated in
a future study. Furthermore, nanoclay-modified binders are ex-
pected to be 22–33% less expensive than polymer-modified bind-
ers. Findings of this paper also imply additional research is needed
in this area before nanoclay-modified binders can be effectively
used for road construction.
Acknowledgments
The writers would like to express their sincere appreciation to
the University of Oklahoma (UO) Research Council and UO
College of Engineering for providing financial support for the re-
search reported in this paper. Thanks to Dr. Zhanping You, from
Michigan Technological University for assistance in blending
nanoclay with asphalt binder. Special thanks to Dr. Brian P. Grady
for assistance in the SAXD experiments. Also, the writers are
thankful to Mr. Jackson Autrey, from the University of Oklahoma,
for assistance with laboratory testing.
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