Construction and Building Materials 38 (2013) 759–765

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Construction and Building Materials

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Preparation and properties of conventional asphalt modified by physical mixtures

of linear SBS and montmorillonite clay
Martin Jasso a,c,⇑, Dusan Bakos a, Daryl MacLeod b, Ludo Zanzotto c
a
Department of Plastics and Rubber, Institute of Polymer Materials, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9,
812 37 Bratislava, Slovak Republic
b
Husky Energy, 707 8th Ave. SW, Calgary, Alberta, Canada T2P 3G7
c
Department of Civil Engineering, Schulich School of Engineering, University of Calgary, ENF 262, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4

h i g h l i g h t s

" Asphalt blends studied via three factors and five levels of statistical experiment.
" The linear viscoelastic properties were studied at high temperatures.
" Creep characteristics were determined at low-temperatures.
" Findings point to improve properties of paving mixes.

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

Article history: The effect of additions of organically modified clay and a sulfur-based compound on the technological, as
Received 29 May 2012 well as rheological properties of a conventional asphalt that was modified by a linear styrene–butadiene–
Received in revised form 26 August 2012 styrene block copolymer, was studied via three factors and five levels of statistical experiment. Blends
Accepted 21 September 2012
were prepared with conventional physical mixing. The linear viscoelastic properties of asphalt binders
Available online 26 October 2012
were studied in small-amplitude sinusoidal oscillations by a dynamic shear rheometer, and the low-
temperature properties of the tested polymer modified asphalts were determined from their creep char-
Keywords:
acteristics measured in a bending beam rheometer. In particular, it was shown that the organoclay had a
PMA
Organoclay
positive influence on rheological properties of the studied systems, specifically on service temperatures.
Rheology Ó 2012 Elsevier Ltd. All rights reserved.
Superpave

1. Introduction
In recent years, there has been a growing demand for asphalt
binders with improved engineering properties, partially in re-
sponse to the rising numbers of motor vehicles and axle loads on
roads. This all leads to higher stresses on pavements and rapid
deterioration of pavements (i.e., rutting, cracking). Large seasonal
temperature fluctuations require the use of modified asphalt bind-
ers with wide temperature ranges and good performance proper-
ties, particularly in the construction of heavily loaded roads. In
order to prevent rutting and cracking, asphalt binders with addi-
tives of specific properties are frequently produced. One of the
most common methods is the modification of asphalts by various
polymers.
⇑ Corresponding author at: Department of Civil Engineering, Schulich School of
Engineering, University of Calgary, ENF 262, 2500 University Drive NW, Calgary,
Alberta, Canada T2N 1N4. Tel.: +1 403 220 4484; fax: +1 403 282 7026.
E-mail address: martin.jasso@stuba.sk (M. Jasso).
The polymer modifiers of asphalt can belong to either the group
of elastomers [1–3] or the group of plastomers [4,5]. Polymer mod-
ified asphalts (PMAs) are usually blends of asphalt with polymer
added in the range from 2% to 5% by weight. Although there are
a variety of polymers, only a few give satisfactory results and can
be used for the preparation of PMAs. The most commonly used
polymers belong to the group of thermoplastic elastomeric block
copolymers; and, from these, styrene–butadiene–styrene (SBS)
especially seems to be a useful modifier of conventional asphalt
[6,7]. Its structure consists of non-compatible blocks that form a
two-phase system, where the glassy styrenic domains are dis-
persed in the flexible butadienic phase and create a physical elas-
tomeric network. The mixing with asphalt leads to the swelling of
the SBS by the absorption of maltenes and to the formation of a
spatial network, while the SBS microstructure is maintained [8].
Another possible option for modification is the addition of var-
ious nanoparticles, mostly of inorganic origin, into the polymer
matrix to enhance the asphalt’s thermomechanical properties, to
improve the barrier properties (in case of waterproofing asphalts)

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.09.043
760 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765
and possibly other properties. The success of the addition of inor-
ganic particles to polymers depends on the character of the nano-
particles, the organic modifier, the polymeric matrix and the
processing technology.
Layered silicates are commonly used for the preparation of
nanocomposites. Polymer nanocomposites (PNCs) can be divided
into intercalated and exfoliated PNCs. Intercalated PNCs are cre-
ated by the incorporation of polymer chains into the layered sili-
cate structure that occurs in a crystallographically regular
fashion, regardless of the silicate-to-polymer ratio. Exfoliated PNCs
are formed by dispersive mixing, where the individual silicate lay-
ers are separated in a continuous polymer matrix by an average
distance, which totally depends on the layered silicate loading [9].
Layered silicates with a 2:1 crystallographic structure consist of
two-dimensional layers, where the central atom of the octahedron
layer of aluminum or magnesium is associated with two external
tetrahedral layers coordinated by silicon atoms [10]. The layer
thickness is about 1 nm, and the lateral dimensions of the layers
are in the range of 300 Å to several microns, depending on the type
of silicates.
For the preparation of PNCs, two properties of the layered sili-
cates are important. The first is the ability of the silicate particles
to disperse at the level of layers, and the second is the ability to
modify their surface by ion-exchange reactions with organic and
inorganic cations. These two characteristics are related to the de-
gree of dispersion of the layered silicate in the polymer matrix
and depend on the cation in the interlayer.
Layered silicates that are miscible with a less polar polymer ma-
trix should be converted to make an organophilic polymer interca-
lation. In general, it is feasible using ion-exchange reactions with
cationic agents, including primary, secondary, tertiary and quater-
nary alkyl-phosphate or alkyl-ammonium cations. These cations
reduce the surface energy of the inorganic host and improve the
surface wet-ability of polymer aggregates, which results in greater
interlayer distances. Moreover, alkyl-phosphate or alkyl-
ammonium cations can provide functional groups that can react
with the polymer matrix and, in some cases, initiate polymeriza-
tion of the monomers to improve the adhesion between an
inorganic compound and a polymer matrix [11,12]. For the prepa-
ration of PNCs, four different techniques are used [13–16], namely
in situ polymerization, the template technique, melt intercalation
and intercalation of polymer from solution.
The use of ternary asphalt/polymer/clay system is an unex-
plored direction with respect to asphalt modification, and our
interest was the study of the properties of such individual systems
prior to the practical design of pavements. For the purpose of as-
phalt modification, the last two methods (i.e., melt intercalation
and intercalation of polymer from solution) seem to be useful. In
the intercalation of polymer from solution, solvents that are able
to swell silicates and dissolve polymer are used. In this way, lay-
ered silicates with weak interlayer forces are easily dispersed;
and, polymer chains are able to replace the solvent in the interlayer
of silicate. Similarly, it may constitute solvent for polymer, with
one main difference that asphalt remains in the system as a carrier
of properties.
In the melt intercalation method, one can either gradually add
polymer and clay into a high shear mixer containing the asphalt di-
rectly or first prepare a polymer/clay nanocomposite by melt com-
pounding and then mixing the nanocomposite with asphalt. The
latter method is, of course, more time consuming and expensive,
thus less suitable for technological utilization.
Recently, much attention has been devoted to inorganic nanof-
illers, which are able (in a relatively small amount) to improve the
properties of polymer matrices, as well as asphalt. Polacco et al.
[17] monitored the effect of adding clays as the third component
to PMAs. These authors studied binary mixtures of asphalt and clay
and also polymer and clay. They then prepared a tertiary mixture
by adding clays and polymer into asphalt, either alone or in the
form of a master batch. In both cases, they obtained intercalated
nanocomposites with comparable interlayer distances and glass
transition temperatures. Their results showed that the mixing
method significantly impacted the final rheological properties of
the prepared materials.
The effects of two types of nanoclay (CloisiteÒ and NanofilÒ) on
the rheological properties of PMA blends were studied by Jahromi
and Khodaii [18]. Asphalt blends were prepared by the melt inter-
calation process. The dispersion of clay at the nanoscopic level was
observed with X-ray diffraction (XRD). It was also shown that
Nanofil particles were smaller in size than Cloisite particles. On
the other hand, rheological tests have shown clay’s significant
effect on the internal structure of asphalt blends, which was
reflected in changes in the rheological properties. The asphalt
blends of the studied system showed higher elasticity, lower dissi-
pation of mechanical energy and good compatibility. According to
these authors, intercalation of layers of nanoclay depends mainly
on asphalt molecules.
Yu et al. [19] studied the effect of nanoclay (montmorillonite)
on the properties of asphalt modified by an SBS copolymer pre-
pared by melt blending with different amounts of sodium mont-
morillonite (Na-MMT) and organophilic montmorillonite
(OMMT). It was found that the addition of Na-MMT and OMMT in-
creased the viscosity of the SBS-modified asphalt. In addition, the
nanoclay/SBS-modified asphalt gained a higher complex modulus
and lower phase angle, implying a stiffer and more elastic asphalt.
Therefore, the nanoclay-modified asphalt was determined to have
better rutting resistance than the original or SBS-modified asphalt.
Based on the XRD results, it was found that Na-MMT-modified as-
phalt may form an intercalated structure, whereas the OMMT-
modified asphalt may form an exfoliated structure.
You et al. [20] investigated the influence of larger amounts of
nanoclays as modifiers on the mechanical properties of asphalt
binders. Nanoclays, at 2% and 4% by weight, were blended with as-
phalt at a high temperature to exfoliate the nanoclay within the as-
phalt. It was found that the nanoclays used in this study increased
the complex shear modulus (|G|) and viscosity of the prepared
asphalts binders. The direct tension test also indicated better
low-temperature cracking resistance. Finally, it is worth noting
that the blending procedure was crucial in achieving a good distri-
bution of nanoclay in asphalt.
The addition of two different organoclays as the third compo-
nent of PMAs was tested by Sureshkumar et al. [21]. Mixtures were
prepared by adding organoclay and ethylene–vinyl acetate (EVA)
into asphalt, either individually or as a masterbatch. According to
the chemical structure of the clays used in this work, it was shown
that the organoclays had a higher affinity to asphalt than to the
polymer; thus, the mechanically mixed clays should preferably
be intercalated into the asphalt molecules. On the other hand, in
the case of PMA, there were spotted interactions between the
organoclay and the polymer, which could persist during the mixing
phase. Master batches of the polymer/clay had higher polarity than
pure polymers, due to the content of clay. This higher polarity was
reflected in improved compatibility with asphalt. Clay also acted as
a surfactant. Its presence can lead to increased interaction between
the incompatible phases. The authors argued that, generally, the
higher the affinity between polymer and clay, the better the homo-
geneity of the prepared mixture.
Liu et al. monitored the impact of organoclay on the properties
of asphalt [22]. Asphalt binders were prepared using a high-shear
mixer, with an organoclay content of 4 wt.%. The rheological char-
acteristics and changes due to the aging of the asphalt were mea-
sured by a dynamic shear rheometer (DSR), and the degree of
dispersion of organoclay in the asphalt was measured by XRD
 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765
and computed tomography (CT) scans. The presence of organically
modified montmorillonite in the asphalt significantly affected the
rheological properties and resistance to aging, due to the good
compatibility between the montmorillonite and the asphalt. The
authors attributed the improved resistance to aging to the organo-
clay particles, which could create an oxygen barrier, thus basically
preventing the penetration of gas molecules. Another reason may
be the reduced volatility of the oil components of asphalt.
2. Experimental
Conventional asphalt prepared by vacuum distillation of crude oil with a 200/300
Penetration grade was used as a base for the preparation of polymer/organoclay mod-
ified asphalts. This base asphalt was modified by a medium molar mass linear SBS
block copolymer with a styrene content of 31 wt.%. The second modifier was Cloisite
CA20 organoclay from Southern Clay Products Inc. The CA20 was prepared from a so-
dium montmorillonite with a cation exchange capacity of 0.926 meq/g of
Me2(HT)2NCl (dimethyldihydrogenated-tallow ammonium chloride), where hydro-
genated tallow is a composition of alkyls on C18 at 65%, C16 at 30% and C14 at 5%. The
third component was ‘‘Additive A’’, a sulfur-based compound.
2.1. Preparation of materials
The PMAs were prepared using a high-shear mixer. The components of the
PMAs were mixed until no separate parts of polymer were observed. The parts of
the mixtures were gradually dispersed in asphalt at temperatures above 180 °C.
After mixing, the prepared binders were left to stabilize and were finally stored
in a freezer before further testing.
2.2. Characterization of materials
2.2.1. Penetration
Penetration is an empirical test that provides a general overlook of consistency
of asphalt binders. This test was performed according to the ASTM T5 standard.
2.2.2. Kinematic viscosity
The viscosities of the prepared samples were measured at 135 °C using a Brook-
field viscometer DV-III Ultra, equipped with an SC4-31spindle. According to the
AASHTO T316 specification, the maximum viscosity at this temperature must not
exceed 3000 MPa s.
2.2.3. Aging
The effects of paving mix production were studied by using artificial aging of
the binders in the rolling thin film oven (RTFO), according to AASHTO T240. Aging
in a pressure-aging vessel (PAV) was performed on the binders after the RTFO. The
PAV aging was used for the simulation of long-term asphalt aging in a pavement
during its service life.
2.2.4. Dynamic rheological properties
The linear viscoelastic properties of asphalt binders are usually studied in small
amplitude oscillations. These were performed in a DSR, according to AASHTO T315.
The asphalt and mixtures were tested at high and intermediate temperatures and at
the constant frequency of 10 rad/s. The data of the magnitudes of the G and the
associated phase angle (d) were collected in the DSR. The tested binders have to sat-
isfy the conditions described in the AASHTO T315-09 specification, which are
shown in Table 1. The parameter |G|/sin d estimates the maximum rutting resis-
tance of the binder, and the parameter |G|sin d is related to fatigue cracking [23].
The complex modulus, G(x), was determined in a Malvern Instruments’ CVOR
rheometer. The geometry was of the plate–plate type. Original (unaged) and RTFO-
aged samples were studied with plates that were 25 mm in diameter with a gap of
1 mm. PAV-aged samples were tested at intermediate temperatures with 8 mm
plates and a gap of 2 mm. The detailed conditions are given in Table 1.
Experimental data were automatically processed by software into the magni-
tude of the |G| and the d, as well as the temperature (the maximum service temper-
ature for the original and RTFO-aged samples, and the intermediate service
temperature for the PAV-aged samples) at which the samples must meet the con-
ditions in Table 1.
Table 1
Conditions for high (original and RTFO-aged binders) and intermediate (PAV-aged
binders) temperatures according to the AASHTO specification.
Binder Shear strain (%) Condition
Original 12 |G|/sin d P 1.0 kPa
RTFO – aged 10 |G|/sin d P 2.2 kPa
PAV – aged 1.0 |G|sin d 6 5000 kPa
761
2.2.5. Creep tests with a bending beam rheometer (BBR)
According to the Strategic Highway Research Program (SHRP), the low-tempera-
ture properties of asphalt binders are determined from their creep characteristics,
which are measured in a bending beam rheometer (BBR) according to AASHTO
T313. Rectangular beams of asphalt binder (125  12.5  6.25 mm) were cooled in
a liquid bath, and the deflection was monitored with time and used for calculation
of the stiffness as a function of time. The stiffness (S) and the slope (m) of the stiffness
curve (log S – log t) were then used as the low-temperature characteristics of binders.
3. Results and discussion
The influence of variable contents of organoclay on the physical
and rheological properties and the high-temperature storage sta-
bility of asphalt binders were studied in [19]. According to these
authors, the storage stability of these modified asphalts decreased
with an increasing content of organoclay. It was found that
asphalts modified by organoclay were stable when the content of
clay was lower than 3 wt.%, there by suggesting the maximum con-
tent of organically modified clay in PMAs.
In the present study, the influence of changing the concentra-
tion of individual components on the rheological properties of as-
phalt modified by SBS and the above-mentioned organoclays was
studied. From a statistical point of view, three factors and five
levels of experiments were realized. The three factors were the
content of the SBS (ranging from 2 to 5 wt.%), the content of Addi-
tive A (ranging from 0.01 to 0.12 wt.%) and the content of organo-
clay (ranging from 0.89 to 3 wt.%). These three factors at the five
levels of the planned experiment were used for the processing
and statistical evaluation of the measured values [24]. The coded
values of the experiments are given in Table 2, where the coded
levels have been converted into real values for all factors. The com-
positions of PMA blends correspond to levels of the planned exper-
iment with the introduction of real amounts of SBS, Additive A and
organoclay, see Table 3.
A detailed analysis of the impact of the individual factors was
done via the quality-quantitative evaluation of the statistical signif-
icance of the effects, as represented by the respective coefficients of
regression [24]. The used regression equations are of the form:
Y ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b11 x1 x1 þ b12 x1 x2 þ b13 x1 x3 þ b22 x2 x2
þ b23 x2 x3 þ b33 x3 x3
where Y is the evaluated parameter; b0, b1, b2, b3, b11, b12, b13, b22,
b23 and b33 are the coefficients of regression; and, x0, x1, x2, x3, x11,
x12, x13, x22, x23 and x33 are the factors of the coded levels.
3.1. Mechanical properties
The aim of these experiments was the acquisition of more exact
information about a spotted system of PMA binders, which can
help in the understanding and, subsequently, setting of the param-
eters of modification, in order to obtain the best properties of PMA
binders.
The values of the measured characteristics are shown in Table 4.
The influence of SBS (x1), Additive A (x2) and organoclay (x3) on the
penetration, as measured according to ASTM T5, is shown in Fig. 1.
From this figure, it is evident that only two factors have an effect
on the penetration of PMA mixtures. The most significant impact
on the penetration was the SBS, where sharp decreasing values
Table 2
Table of coded values of the planned experiment.
Factor (coded level) 1.682 1 0 1 1.682
x1 0.02084 0.02751 0.03729 0.04708 0.05374
x2 0.00010 0.00032 0.00065 0.00098 0.00120
x3 0.00899 0.01351 0.02014 0.02678 0.03130
762 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765

Table 3
Conditions for the planned experiment.

Number of Coded levels Real levels SBS content Additive A content Clay content
blends (wt.%) (wt.%) (wt.%)
x1 x2 x3 x1 x2 x3
1 1 1 1 0.02751 0.00032 0.01351 2.64 0.032 1.33
2 1 1 1 0.04708 0.00032 0.01351 4.44 0.032 1.33
3 1 1 1 0.02751 0.00098 0.01351 2.64 0.097 1.33
4 1 1 1 0.04708 0.00098 0.01351 4.44 0.097 1.33
5 1 1 1 0.02751 0.00032 0.02678 2.64 0.032 2.61
6 1 1 1 0.04708 0.00032 0.02678 4.44 0.032 2.61
7 1 1 1 0.02751 0.00098 0.02678 2.64 0.097 2.61
8 1 1 1 0.04708 0.00098 0.02678 4.44 0.097 2.61
9 1.682 0 0 0.02084 0.00065 0.02014 2.00 0.065 1.97
10 1.682 0 0 0.05374 0.00065 0.02014 5.00 0.065 1.97
11 0 1.682 0 0.03729 0.00010 0.02014 3.52 0.010 1.97
12 0 1.682 0 0.03729 0.00120 0.02014 3.52 0.120 1.97
13 0 0 1.682 0.03729 0.00065 0.00899 3.52 0.065 0.90
14 0 0 1.682 0.03729 0.00065 0.03130 3.52 0.065 3.00
15 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97
16 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97
17 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97
18 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97
19 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97
20 0 0 0 0.03729 0.00065 0.02014 3.52 0.065 1.97

of penetration were recorded with an increasing content of SBS in
the mixture. A similar effect was seen also for the organoclay,
where an increasing content of organoclay led to slightly decreas-
ing values of penetration. The value of penetration of the standard
asphalt was 247 dmm. The presence of all three factors resulted in
a decrease of the values of penetration to about 50%.
On the other hand, increasing amounts of Additive A in the mix-
ture caused a slight increase in the value of penetration, but it was
not statistically significant. This is clearly seen from Tables 5 and
6, which show calculated regression coefficients for mechanical
and rheological properties. The statistically significant coefficients
are labelled in bold.
Testing of asphalts binders according to the Superpave specifi-
cation is the main motivation of this work. It simulates the three
critical stages of a binder’s life. The first stage is represented by
the tests carried out on the original asphalts with the goal to
evaluate the abilities of the binder in transportation, storage and
handling. For this purpose, the viscosity was measured at 135 °C,
according to AASHTO T316, for all grades, with the limitation that
the maximum viscosity at this temperature must not exceed
3000 MPa s. It can be clearly seen in Fig. 2 that this characteristic
was significantly affected by all factors. Increased loading of the
SBS and organoclay in the asphalt binder led to sharp increases
in viscosity, whereas only slightly increased values of viscosity
can be observed for increased contents of Additive A.
There were also interactions between factors, of which the most
significant were the interactions between the SBS and the organo-
clay, where increasing contents of the SBS and clay shifted the vis-
cosity to higher values. The highest measured viscosity of the
prepared PMAs was 2206 MPa s, which represents a viscosity that
is ten times higher than standard asphalt (i.e., without modifiers).
3.2. Rheological properties
For the characterization of the viscoelastic properties of the as-
phalt binders, their dynamic material functions were determined

Table 4
Summary of measured values of mechanical and rheological properties according to the planned experiment.

Number Penetration Viscosity Maximum service Maximum service Intermediate service Low service
of blends @25 °C @135 °C temperature of original temperature of RTFO- temperature of PAV-aged temperature of PAV-
(dmm) (MPa s) mixtures (°C) aged mixtures (°C) mixtures (°C) aged mixtures (°C)
Standarda 247 209 54 52 13 26
1 131 633.4 67.7 65.6 12.1 27
2 107.7 1199.3 76.6 72.3 7.1 23
3 132.7 703.8 69.5 65.4 11.1 27
4 104.7 1443.3 79.8 74.4 9 28
5 126 825.8 71.5 67 10.3 26
6 88 1645.3 78 74.1 7.4 23
7 130 873.8 71.1 71.1 10.6 26
8 96 2206 84.5 76.8 9.7 28
9 140.7 593.9 66.6 62.7 12.1 26
10 92.3 1742 80.1 80.5 5.1 29
11 111.3 958.3 70.7 68.7 12.8 24
12 115.7 1247.3 78.8 70.9 10.1 27
13 125 874.3 73.8 69.4 10.4 27
14 109.7 1360 79.7 71.5 9.3 27
15 119 1042.7 76.5 70.3 11.5 27
16 113.7 1093.7 76.4 70.7 10.5 26
17 115 1080.7 75.3 70.2 10.7 27
18 115.7 1123 75.6 70.7 10.3 27
19 111 1108 76.2 70.2 10.4 27
20 111.3 1111.7 76.4 70.4 9.8 27
a
Standard sample of asphalt without modifiers.
 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765 763

increasing contents of SBS, Additive A and organoclay in the mix-

Fig. 1. Dependency of the penetration of asphalt mixtures on the levels of the
planned experiment.
in a DSR. All tests carried out in the DSR were performed according
to AASHTO T315. The complex shear modulus (|G|) and its compo-
nents were of particular interest. The |G| is a measure of the total
resistance of a material to the deformation when exposed to re-
peated pulses of shear stress. The phase angle (d) is an indicator
of the relative amounts of the recoverable and non-recoverable
deformations. Asphalt at high technological temperatures is vis-
cous and, at low service temperatures, is an elastic material. At
intermediate temperatures, asphalt shows true viscoelastic behav-
ior with ability to accumulate deformations. This can lead to rut-
ting and further deterioration of pavements.
In this regard, the parameter |G|/sin d was suggested. It indi-
cates the rutting potential, especially in conventional asphalt
binders. According to the Superpave specification [25], the asphalt
binder must meet the condition that |G|/sin d is greater than or
equal to 1 kPa for the original asphalt binder and greater than
or equal to 2.20 kPa for RTFO-aged asphalt binders. For better char-
acterization of fatigue cracking at intermediate temperatures, the
binders must fulfill the condition of a maximum value of
5000 kPa for the parameter |G|sin d. In this case, low values of both
|G| and d are considered desirable for better fatigue cracking
resistance.
In Fig. 3, the influences of the contents of SBS, Additive A and
organoclay on the maximum service temperature, which were ob-
tained from (|G|/sin d), can be observed as the last characteristic of
the original modified asphalt. From the results, we can conclude
that the maximum service temperature of the original asphalt
binders was again significantly affected by all three factors: with
ture, the levels of maximum service temperature increased. The
largest share of the increase in temperature was caused by the
maximum content of SBS.
From our statistical evaluation, we can also observe the interac-
tion between Additive A and SBS, which probably led to the forma-
tion of a highly entangled three-dimensional network structure in
PMAs [26] and caused an increase in the values of the monitored
parameter. Another possible explanation maybe that the presence
of organoclay strengthened the network of the internal structure
formed in the PMA. The maximum service temperature of the ori-
ginal asphalt blend was achieved at 84.5 °C.
From the results shown in Fig. 4, one can claim that the maxi-
mum service temperatures of asphalt binders exposed to RTFO
aging were affected by all three factors in the case of the original
modified asphalt. The most significant contribution to the growth
of maximum service temperature values was again the amount
of SBS. The impact was four times higher than the impact of
organoclay and Additive A, where the values of the maximum ser-
vice temperature increased with increased content of each factor.
In comparison, in the original and RTFO-aged blends, the maxi-
mum service temperature worsened after RTFO-aging was re-
corded, moving in intervals from 2 to 8 °C.
One can suppose that this effect of decreasing maximum service
temperatures after RTFO aging of the studied blends was caused by
spotted interactions between the SBS and the organoclay and the
SBS and Additive A, i.e., by thermo-oxidative degradation of the or-
ganic part of the organoclay as well as that of the entire system.
Another possible explanation of the worsening of this property
maybe an insufficient dispergation of the organoclay into the
asphalt, which may lead to agglomeration and, thus, less resistance
to thermo-oxidative degradation. According to [27,28], the resis-
tance to the aging of PMA that have been modified by nanofillers
may be improved, due to the creation of a barrier of intercalated
and exfoliated structures to oxygen. Based on this work, it can be
indicated that, with enhancement of the aging resistance, the exfo-
liated structure is more effective than the intercalated structure.
The maximum service temperature of the RTFO-aged asphalt blend
was achieved at a value of 80.5 °C.
After RTFO aging, samples were exposed to simulated long-term
aging (estimated 5–10 years of service life) through the PAV. These
samples were tested at intermediate service temperatures (i.e.,
where the intermediate service temperature meets the condition
of |G|sin d 6 5000 kPa), as well as at low service temperatures.
The intermediate service temperature characteristic is portrayed
in Fig. 5, where we can see that, with increased content of SBS in
the mixture, the intermediate service temperatures at which the

Table 5
Regression coefficients of mechanical and rheological properties of modified asphalts.

Parameter Penetration @25 °C Viscosity @135 °C Maximum service Maximum service Intermediate service Low service
(dmm) (MPa s) temperature of original temperature of RTFO- temperature of PAV-aged temperature of PAV-
mixtures (°C) aged mixtures (°C) mixtures (°C) aged mixtures (°C)
bi bic bi bic bi bic bi bic bi bic bi bic
b0 114.328 3.138 1090.045 30.225 75.982 0.521 70.410 0.243 10.542 0.588 -26.82 0.428
b1 14.992 2.082 394.696 20.058 4.527 0.346 4.280 0.161 1.660 0.390 0.077 0.284
b2 1.326 103.226 1.811 0.908 0.076 1.102
b3 4.528 174.929 1.569 1.086 0.231 0.147
b12 0.087 2.720 85.788 26.202 1.038 0.451 0.113 0.211 0.613 0.510 1.250 0.371
b13 2.588 105.788 0.088 0.363 0.413 0.250
b23 1.663 36.788 0.137 0.612 0.213 0.000
b11 0.496 2.028 39.708 19.536 0.929 0.337 0.463 0.157 0.741 0.380 0.112 0.277
b22 0.565 16.625 0.433 0.174 0.267 0.596
b33 0.797 21.710 0.275 0.056 0.299 0.065

Note: Coefficients labelled in bold are statistically significant at a significance level of 95%.
764 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765

Table 6
Statistical parameters.

Statistical Penetration Viscosity Maximum service Maximum service Intermediate service Low service temperature
parameter @25 °C @135 °C temperature of original temperature of RTFO-aged temperature of PAV-aged of PAV-aged mixtures
(dmm) (MPa s) mixtures (°C) mixtures (°C) mixtures (°C) (°C)
FS1 125.48 1078.72 484.09 1722.9 40.72 33.91
FS2 1.75 37.76 17.07 24.70 8.09 18.55
SLF 0.42 15.03 8.97 53.89 4.60 10.335
SE 1 1 1 1 1 1

Note: FS1 – Fisher–Snedecor criteria for confidence testing of the linear part of the regression equation; FS2 – Fisher–Snedecor criteria for confidence testing of the nonlinear
part of the regression equation; SLF – standard deviation of the lack of fit error source; SE – standard deviation of experimental error source.

Fig. 2. Dependency of the viscosity of asphalt mixtures on the levels of the planned Fig. 4. Dependency of the maximum service temperature of the RTFO-aged asphalt
experiment. mixtures on the levels of the planned experiment.

Fig. 5. Dependency of the intermediate service temperature of the PAV-aged

Fig. 3. Dependency of the maximum service temperature of the original asphalt
asphalt mixtures on the levels of the planned experiment.
mixtures on the levels of the planned experiment.

3.3. Low-temperature cracking

tested samples met the Superpave specification requirement (|G|-
sin d 6 5000 kPa) were linearly decreasing with an increasing con-
tent of Additive A and simultaneously passing through a maximum
depending on the content of SBS.
The effect of individual Additive A and individual organoclay
additions have been proven as statistically irrelevant; however, it
is worth mentioning that an interaction between Additive A and
the SBS was statistically significant, and that an increasing content
of Additive A led to lower values of this temperature. The lowest
value of intermediate service temperature parameter, according
to planned experiment, was achieved at the value of 5.1 °C, while
the value of the intermediate service temperature parameter for
the standard asphalt sample was 13 °C, indicating an improvement
of this parameter by 8 °C.
Thermal cracking is observed at low temperatures, when an as-
phalt binder shows a tendency to shrink, leading to the increase of
tensile stresses in pavements. The low-temperature performance
was tested according to AASHTO T313. The measured values,
which are shown in Fig. 6, were also investigated by an analysis
of variance (ANOVA). One can establish that only Additive A statis-
tically affected the low service temperature. Increasing the content
of Additive A led to decreasing values for the low service temper-
ature, up to a concentration of 0.065 wt.%. Another addition of
Additive A caused increasing values of this property.
It is worth mentioning that there were interactions between
factors x1 and x2, i.e., SBS and Additive A. While the increase
of SBS caused worsening of the low service temperature, its
 M. Jasso et al. / Construction and Building Materials 38 (2013) 759–765
Fig. 6. Dependency of the low service temperature of the PAV-aged asphalt
mixtures on the levels of the planned experiment.
interaction with Additive A led to a sharp shift of this property to
lower (i.e., better) values. Experimental values ranged from 23
to 29 °C, which represents a temperature difference of 3 °C in
comparison with the standard sample.
4. Conclusions
The impact of adding organically modified clay and Additive A
on the technological, as well as rheological, properties of a conven-
tional asphalt modified by a linear SBS block copolymer were stud-
ied via three factors and five levels of statistical experiments. From
the experimental point of view, the method was used to acquire
useful and comprehensive information. The blends were prepared
by conventional physical mixing, and the mechanical and rheolog-
ical properties were studied.
The viscosity of prepared blends increased and the penetration
decreased, depending on the increasing content of the components
in the asphalt blends.
The maximum service temperature of the original asphalt bind-
ers was affected by all three factors. With increased content of
individual components in the mixtures, there were increases in
the maximum service temperatures. One can claim that improve-
ment of the maximum service temperature can result from the for-
mation of a highly entangled three-dimensional network structure
in polymer modified asphalts.
The worsening of the maximum service temperatures of the as-
phalt binders that were exposed to RTFO aging was also monitored.
This worsening or decreasing of the maximum service tempera-
tures was caused by spotted interactions between the SBS and
the organoclay and the SBS and Additive A, i.e., by thermo-
oxidation degradation or insufficient dispergation of organoclays
into asphalt binders.
The |G|sin d of less than or equal to 5000 kPa at intermediate
service temperatures were statistically affected by Additive A and
SBS. Increasing the content of these components and their interac-
tions led to lower values of the fatigue-cracking temperature.
Similarly, in the case of low service temperatures, increasing
contents of Additive A led to decreasing values for the low service
temperature. In spite of the fact that increased content of SBS
caused worsening of the low service temperature, interaction of
the SBS with Additive A led to a sharp shift of this property to lower
values.
765
These findings point to possibility of using quaternary PMAs for
the preparation of paving mixes; however, additional research in
this area is necessary.
Acknowledgements
The authors would like to acknowledge Husky Energy Inc. for its
financial support of this work. We would like to thank Mr. R. Wirth
and Mrs. E. Vargova, for their help with the preparation of the
PMAs, and Dr. J. Stastna, for valuable discussions on the rheological
properties of PMAs.
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