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The Utilization of Multiple-Walled Carbon Nanotubes in Polymer Modified

Bitumen

Article in Materials · April 2017

DOI: 10.3390/ma10040416

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 materials
Article
The Utilization of Multiple-Walled Carbon
Nanotubes in Polymer Modified Bitumen
Benan Shu, Shaopeng Wu, Ling Pang * and Barugahare Javilla
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology,
Wuhan 430070, China; Shuba@whut.edu.cn (B.S.); wusp@whut.edu.cn (S.W.); makorogo@whut.edu.cn (B.J.)
* Correspondence: lingpang@whut.edu.cn

Academic Editor: Marco Morreale

Received: 25 February 2017; Accepted: 12 April 2017; Published: 15 April 2017

Abstract: SBS (styrene-butadiene-styrene block copolymer) modified bitumen is one of most widely
used polymer modified bitumens in China. It is also not satisfactory when subjected to extreme
conditions. Multiple-walled carbon nanotubes, as a type of advanced nanomaterial, are investigated
extensively because of their strong adsorption capacity. Little research has been done about
MWCNTs/SBS modified bitumen, and in view of this, the performance and modification mechanism
of MWCNTs/SBS modified bitumen was investigated in this paper. Conventional bitumen tests,
Brookfield viscosity, bending beam rheometer, and dynamic shear rheometer tests showed improved
performance at high and low temperature. The optimum MWCNTs content was determined as 1.0%.
FT-IR, bitumen four components, and thermal analysis tests were conducted and revealed that the
addition of MWCNTs led to a decrease in the content of light components. In addition, the rate
of decomposition and volatilization of saturates and aromatics was reduced and better thermal
stability of bitumen was found. Fluorescence microscopy tests showed that MWCNTs improved the
dispersion of SBS and storage stability of the binder. Finally a schematic was proposed to explain
how MWCNTs improved the performance of SBS modified bitumen through their strong adsorption
property created by π–π intermolecular forces.

Keywords: MWCNTs; SBS modified bitumen; rheological properties; modification mechanism

1. Introduction
The total mileage of bitumen highways in China reached 117,000 kilometers in 2016, and it is
expected that there will be a rapid increase in the next few years. Highways are expected to have high
temperature rutting resistance and low temperature crack resistance, and in view of this, modified
bitumen such as SBS modified bitumen has shown a better rutting and cracking resistance compared
to unmodified bitumen. The main problems identified with modifiers such as SBS have been its poor
dispersion and compatibility with bitumen, and this is known to affect the rheological properties of
bitumen [1].
In recent years, nanomaterials have been widely used to improve the rheological properties
of bitumen, and to that effect, researchers have doped different nanoparticles [2,3]. Two specific
types of nanomaterials, namely nano-metal oxides and nano-inorganic materials, have been widely
investigated. Nano-metal oxides including nano-TiO2 , nano-SiO2 , and nano-ZnO could improve the
rutting resistance of bitumen, but had little effect on its low temperature cracking resistance [4,5].
Nano-inorganic materials including nano-clay and nano-CNTs exhibited some special properties in
bitumen because of their specific properties and structures. For example, nano-clay had a positive
interaction effect with bitumen and polymer, because of the high compatibility between the clay and
polymer which led to a better dispersion of the polymer in the bitumen. Nano-OMMT improved the

Materials 2017, 10, 416; doi:10.3390/ma10040416 www.mdpi.com/journal/materials

Materials 2017, 10, 416 2 of 16

thermal oxidative aging resistance of bitumen because of its specific layered structure which effectively
blocked oxygen penetration in bitumen and thus improved thermal oxidative aging [6].
Carbon nanotubes (CNTs) are seamless nanotube structures containing monolayer or multilayer
graphite sheets revolving at specific helix angles around the same axis. Each layer wall is
a cylindrical surface composed of a hexagonal network plane made of sp2 hybrid carbon
atoms [7]. Because of the overlap of P orbitals, the highly disjointed π-bond could exist at the outer
layer of the CNTs. The non-covalent interaction between multi-wall carbon nanotubes (MWCNTs) and
other macromolecules with conjugated properties such as aromatics and styrene exist because of the
highly disjointed π-bond [8–10].
Amin et al. [11] used multi-wall carbon nanotubes (MWCNTs) as an additive to bitumen and
it enhanced the high temperature performance of bitumen. Yang et al. [12] reported that single-wall
carbon nanotubes (SWCNTs) as an additive to bitumen improved its penetration, softening point,
ductility, and flash point properties. In bitumen mixtures, an optimum percentage of 0.05% of
SWCNTs improved the Marshall stability and rigidity flow. Faramarzi [13] also investigated the
effect of MWCNTs in bitumen and reported an increase of rutting factor G ∗ / sin δ. The study of
Santagata et al. [14] showed that susceptibility to oxidative aging of bitumen was reduced with the
addition of carbon nanotubes. Aging was expected to further improve with the long-term performance
of bituminous mixtures.
SBS is widely used to improve the properties of bitumen such as rutting resistance, but it has
been reported that the polystyrene in SBS was incompatible with bitumen. The attraction between
polystyrene molecules resulted in the formation of insoluble agglomerates, and thus the swelling
potential of SBS was limited [15]. Due to the highly disjointed π-bond of MWCNTs, a π–π interaction
with polystyrene of SBS was expected, which would improve its compatibility with bitumen, and thus
result in an improved rheological performance. For that reason, this paper conducted a series of
experiments to determine the effect and mechanism of MWCNTs on SBS modified bitumen.

2. Experiments

2.1. Materials
90A bitumen was supplied by KOCH Bitumen Co., Ltd. (Wuhan, China). SBS was bought from
Dongguan Huahong Engineering Plastic Co., Ltd. (Dongguan, China). The type of SBS is Linear/161B.
MWCNTs were bought from Suzhou Hengqiu Graphene Technology Co., Ltd. (Suzhou, China).
The properties and micro-morphology of the MWCNTs are shown in Table 1 and Figure 1, respectively.
From the SEM images it is seen that MWCNTs intertwined with each other because of their extremely
large surface area, and so it was essential to use a high-speed shearing mixer to make them disaggregate
in bitumen during the preparation of the MWCNTs/SBS modified bitumen. In order to determine the
specific surface area of MWCNTs, the Specific surface area test (BET test) was conducted and the result
was 213.6872 m2 /g.

Table 1. Physical properties of multi-wall carbon nanotubes (MWCNTs) supplied by the manufacturer.

Internal Outside Surface

Purity Length Density Preparation Method
Diameter Diameter Area
>95/%
3–5 nm 8–10 nm 3–12 µm >200 m2 /g 0.1 g/cm3 Chemical vapor deposition
(by weight)
Materials 2017, 10, 416 3 of 16
Materials 2017, 10, 416 3 of 16

Materials 2017, 10, 416 3 of 16

(a) (b)
Figure 1. SEM images of MWCNTs (1 μm scale bar) at different magnification. (a) ×20,000; (b)
Figure 1. SEM images of MWCNTs (1 µm scale bar) at different magnification. (a) ×20,000; (b) ×10,000.
×10,000.
(a) (b)
2.2. Preparation of MWCNTs/SBS
2.2. Preparation
Figure 1. SEM images of Modified
of MWCNTs/SBS Bitumen
Modified
MWCNTs (1Bitumen
μm scale
bar) at different magnification. (a) ×20,000; (b)
×10,000.
(1) SBS (determined by weight) was added to 90A virgin asphalt which was at a temperature
3.5% SBS (determined by weight) was added to 90A virgin asphalt which was at a temperature
(1) 3.5%
of 160 °C. The mixture was stirred using a high‐speed shearing mixer at 5000 rpm for one hour.
◦ C.
of 160 The mixture
2.2. Preparation was stirred
of MWCNTs/SBS using
Modified a high-speed shearing mixer at 5000 rpm for one hour.
Bitumen
(2) The temperature of the SBS modified bitumen was maintained at 160 °C by heating using an
(2) The(1)temperature
3.5%
oil of the SBS
SBS (determined
bath. modified
by weight) bitumen
was added to 90Awas maintained
virgin asphalt which 160 at◦ C
at was by heating using
a temperature
an(3)
oil bath.
of 160 °C. The
MWCNTs weremixture
steadilywas stirred
added intousing a high‐speed
the bitumen for 30shearing mixer
min with at 5000 rpm
a high‐speed for one hour.
shearing mixer
(3) (2) The temperature
running at 5000 of
rpm. the SBS modified bitumen was maintained
MWCNTs were steadily added into the bitumen for 30 min with a high-speed shearing at 160 °C by heating using an mixer
(3) oil bath.the high‐speed shearing mixer at 5000 rpm was applied for 30 min to disaggregate and
Finally,
running at 5000 rpm.
(3) disperse
MWCNTsthe were steadily added
agglomerated into the into
MWCNTs bitumen
the for 30 minmatrix.
bitumen with a high‐speed
High‐speedshearing
shearingmixer
and
(4) Finally,intelligent
the high-speed
running 5000 rpm.shearing
at temperature mixer at 5000 rpm was applied for 30 min to disaggregate
control device was showed in Figure 2. In addition, the normal
and(3)disperse
properties the
Finally, the agglomerated
ofhigh‐speed
90A bitumen andMWCNTs
shearingSBSmixer into
at 5000
modified thewas
rpm
bitumen bitumen
applied
were matrix.
for 30
showed in min High-speed
Table shearing
to2.disaggregate and and
disperse
intelligent the agglomerated
temperature MWCNTs
control device wasinto the bitumen
showed in Figure matrix. High‐speedthe
2. In addition, shearing
normalandproperties
of 90A intelligent
bitumen and temperature control bitumen
SBS modified device was wereshowed
showed in Figure
in Table 2. In
2. addition, the normal
properties of 90A bitumen and SBS modified bitumen were showed in Table 2.

Figure 2. High‐speed shearing and intelligent temperature control device. Part 1: Electronic
temperature controller: Controls the temperature of bitumen intelligently by connecting with the
temperature probe and the electrical resistance furnace. Part 2: Electrical resistance furnace: Heats
Figure 2.Figure 2. High‐speed
High-speed shearing shearing and intelligent
and intelligent temperature
temperature controlcontrol
device.device.
Part 1:Part 1: Electronic
Electronic temperature
temperature controller: Controls the temperature of bitumen intelligently by connecting with the
controller: Controls the temperature of bitumen intelligently by connecting with the temperature
temperature probe and the electrical resistance furnace. Part 2: Electrical resistance furnace: Heats
probe and the electrical resistance furnace. Part 2: Electrical resistance furnace: Heats bitumen
intelligently by connecting with the electronic temperature controller. Part 3: Oil bath: Heats bitumen
uniformly. Part 4: High speed shearing machine: Provides high-speed shearing and shearing rate
control. Part A: Temperature probe: Detects the temperature of bitumen.
Materials 2017, 10, 416 4 of 16

Table 2. Properties of virgin binder and SBS modified asphalt.

Physical Properties 90A SBS Modified Bitumen

Penetration (25 ◦ C, 0.1 mm) 84.7 72.8
Softening point (◦ C) 47.8 52.0
Ductility (5 cm/min, 5 ◦ C, 1 mm) / 521
Viscosity (135 ◦ C, pa·s) 0.47 0.69
90A is an abbreviation of bitumen with 80/100 pen grade. The content of MWCNTs (namely x%) involved in this
paper was mass percentage relative to the binder.

2.3. Instrument and Performance Tests

2.3.1. Conventional Bitumen Tests

The three conventional bitumen indexes were conducted to make comparisons between the
SBS modified bitumen and the MWCNTs/SBS modified bitumen. A penetration tester (SYD-2801F,
Shangyi, Shanghai, China), softening point tester (SYD-2806F, Shangyi, Shanghai, China), and ductility
tester (LYY-7D, ZGHTKY, Cangzhou, China) were used in this paper. They were used to perform the
penetration test (0.1 mm at 25 ◦ C, 100 g, 5 s), softening point test, and ductility test (5 cm/min, 5 ◦ C),
which were done in accordance with JTG E20-2011 [16].

2.3.2. Brookfield Viscosity

The Brookfield rotational viscometer (THERMOSEL, BROOKFIELD, Stoughton, MA, USA)
test was conducted to determine the viscosity temperature susceptibility of the SBS modified bitumen
and MWCNTs/SBS modified bitumen at four different temperatures of 120 ◦ C, 135 ◦ C, 150 ◦ C and
165 ◦ C, in accordance with JTG E20-2011 [16].

2.3.3. Dynamic Shear Rheometer (DSR) Tests

A dynamic shear rheometer (DSR) of model MCR101 and manufactured by Anton Paar
(Vienna, Austria) was used. A temperature sweep test was conducted using the DSR under strain-controlled
mode with a constant frequency of 10 rad/s according to specifications [17]. A temperature sweep from
30 to 80 ◦ C with a temperature increment of 2 ◦ C per minute was designed to investigate the high
temperature property of MWCNTs/SBS modified bitumen. Plates with 25 mm diameter and 1 mm
gap were used. The performance indicators recorded by DSR were the complex shear modulus (G*)
and phase angle (δ).

2.3.4. Bending Beam Rheometer (BBR) Tests

In order to obtain the different low temperature performances between the SBS modified bitumen
and SBS/MWCNTs, the BBR (TE-BBR, Cannon, New York, NY, USA) test was used to measure the
stiffness and m value in accordance to specifications [16]. According to the standard [18], SBS modified
bitumen was tested for several temperatures and finally −16 ◦ C was determined as the critical
temperature to evaluate the low temperature property of MWCNTs/SBS modified bitumen.

2.3.5. Modification Mechanism Characterization

In order to compare the modification difference between the SBS modified bitumen and
MWCNTs/SBS modified bitumen, bitumen’s four components test was conducted in accordance
with specifications [16]. In addition, thermal analysis and FTIR tests were also conducted to investigate
the modification mechanism.
The thermal analysis test with a working temperature range of 100–700 ◦ C was conducted.
A TGA/DSC simultaneous thermal analyzer STA449c/3/G manufactured by NETZSCH (Selb, Germany)
was used in this paper. The heating rate was controlled at 20 ◦ C/min with a maximum temperature of
Materials 2017, 10, 416 5 of 16

The thermal analysis test with a working temperature range of 100–700 °C was conducted. A
TGA/DSC
Materials 2017, simultaneous
10, 416 thermal analyzer STA449c/3/G manufactured by NETZSCH (Selb, 5 of 16
Germany) was used in this paper. The heating rate was controlled at 20 °C/min with a maximum
temperature of 700 °C. At the same time, high‐purity nitrogen ambient gas was applied at a flow
700 ◦of
rate C. 500
At the same time,
mL/min. During high-purity
the pyrolysisnitrogen ambient
process, the gas was applied
organic volatileatsubstances
a flow rateofofthe 500polymers
mL/min.
During the pyrolysis process, the organic volatile substances of the
were decomposed to low molecular weight products. The relationship between the mass of thepolymers were decomposed to test
low
molecular
sample andweight
the products.
temperature The relationship
can be obtainedbetween the mass
from of the test
the TGA sample
tests, and andthe the temperature
decomposition
can be obtained from the TGA tests, and the decomposition temperature
temperature of different components can also be obtained from the DTG and DSC curves. of different components can
also be obtained from the DTG and DSC curves.
The FT‐IR test was conducted to investigate the modification mechanism with wavelengths
Thefrom
ranging FT-IR400 testtowas
4000 conducted
cm−1, using to investigate
an infraredthe modification
spectrum mechanism
instrument Nexus with wavelengths
manufactured by
ranging from 400 to 4000 cm −1 , using an infrared spectrum instrument Nexus manufactured by
Thermo Nicolet Corporation (MA, USA). The FT‐IR test can detect functional groups in an
Thermo Nicolet
organism whichCorporation
can be used(MA, USA). Thewhether
to determine FT-IR test can detectreaction
a chemical functional groups
occurs in an organism
by comparing the
which can be
differences in used to determine
functional groups. whether a chemical reaction occurs by comparing the differences in
functional groups.
The concentration change of different components (saturates, aromatics, resins, and
The concentration
asphaltenes) in bitumen changewasofstudied
differentbycomponents
the thin (saturates, aromatics, resins,
layer chromatography and asphaltenes)
detection (TLC‐FID) in
bitumen was studied by the thin layer chromatography detection (TLC-FID)
method. The four components analyzer Iatroscan MK‐6 manufactured by IATRON (Japan) was method. The four components
analyzer
used. Iatroscan
Bitumen wasMK-6
dissolvedmanufactured by IATRON
in dichloromethane (Japan)and
solution, wasthenused.N‐heptane,
Bitumen was dissolved in
toluene/heptane
dichloromethane
(80:20, v/v), toluene/ethanol then N-heptane,
solution, and(55:45, v/v) weretoluene/heptane
used as the first,(80:20,
second,v/v), toluene/ethanol
and third extension (55:45, v/v)
solvent,
were used as the first, second, and third extension solvent, respectively, to isolate
respectively, to isolate saturates, aromatics, and resins successively. Organic ions are generated by saturates, aromatics,
andhigh
the resins successively.
temperature of Organic
the hydrogenions are generated
flame, and FID bycan
the detect
high temperature of the hydrogen
the current intensity generatedflame,
by
and organic
the FID can detect
ions. theThecurrent
larger intensity generated
the current by thethe
intensity, organic
moreions. The larger
content the current
of bitumen intensity,
components
the more content
corresponds to thisof area
bitumen
on thecomponents corresponds to this area on the chromatography.
chromatography.
The fluorescence
The fluorescencemicroscopy
microscopytest testwas
was used
used to detect
to detect fluorescence
fluorescence materials
materials in theinbinder
the binder
such
such as SBS. The specimens included the SBS modified bitumen,
as SBS. The specimens included the SBS modified bitumen, 1.0% MWCNTs/SBS modified bitumen, 1.0% MWCNTs/SBS modified
bitumen,
and thoseand those obtained
obtained by the by the segregation
segregation experiment.
experiment. The The segregation
segregation test,
test, ininaccordance
accordance withwith
◦ C to analyze the
specifications [16],[16], was
was conducted
conductedby byheating
heatingtubes
tubesfilled
filledwith
with binder
binder forfor
48 48
h ath 160
at 160 °C to analyze
difference
the differencebetween
betweenthe the
upper 1/3 1/3
upper partpart
of the bitumen
of the bitumen andandthethe
bottom
bottom 1/31/3
part
partof the bitumen.
of the bitumen.
For all
allthe
thetests listed
tests above,
listed above,threethree
replicates were performed
replicates were performedfor the different contents of
for the different MWCNTs
contents of
for the same
MWCNTs fortesting
the sameconditions.
testing conditions.

2.3.6. Experimental
2.3.6. Experimental Program
Program Outline
Outline
The experimental
The experimentalprogram
programoutline
outlineis is shown
shown in in Figure
Figure 3. Firstly,
3. Firstly, 90A90A virgin
virgin bitumen,
bitumen, SBS, SBS,
and
and MWCNTs were mixed to produce MWCNTs/SBS modified bitumen by
MWCNTs were mixed to produce MWCNTs/SBS modified bitumen by high‐speed shearing. high-speed shearing.
Secondly, the
Secondly, the performance tests and
performance tests and modification
modification mechanism
mechanism tests
tests were
were conducted.
conducted. Finally,
Finally, aa novel
novel
conjecture was
conjecture was proposed
proposed based
based on
on the
the performance
performance and
and modification
modification mechanism
mechanism analysis.
analysis.

Figure
Figure 3.
3. Experimental
Experimental program
program outline.
outline.
Materials 2017, 10, 416 6 of 16

3. Results and Discussion

Materials 2017, 10, 416 6 of 16

3.1. Performance Analysis

3. Results and Discussion

3.1.1. Conventional
3.1. PerformanceTest Analysis
Analysis

Figure 4 shows theTest

3.1.1. Conventional effect of the MWCNTs additive on the penetration and softening point of
Analysis
original bitumen. The penetration reflects the softening and hardening degrees of bitumen at moderate
Figure 4 shows the effect of the MWCNTs additive on the penetration and softening point of
conditions. The smaller the penetration value, the harder the bitumen. It was observed that the
original bitumen. The penetration reflects the softening and hardening degrees of bitumen at
addition of MWCNTs
moderate to theThe
conditions. SBS modified
smaller bitumen had
the penetration a significant
value, the harder effect on the Itpenetration
the bitumen. was observed resistance.
Penetration significantly
that the addition ofdecreased
MWCNTs with to thetheSBSaddition
modifiedofbitumen
MWCNTs hadup a to 1%. After
significant then,
effect on athe
moderate
decreasepenetration resistance.
was observed. Penetration
This impliedsignificantly decreased with
that the MWCNTs couldthesignificantly
addition of MWCNTs
improve upthe
to 1%.
hardening
degree After
of thethen,
SBSamodified
moderate decrease
bitumen. was observed. This implied that the MWCNTs could significantly
improve the hardening degree of the SBS modified bitumen.
The softening point test is commonly used as a standard test for describing an approximate limit
The softening point test is commonly used as a standard test for describing an approximate
between viscous and visco-elastic bitumen behavior, and it reflects the deformation resistance degree
limit between viscous and visco‐elastic bitumen behavior, and it reflects the deformation resistance
of bitumen
degreeat of
high temperature
bitumen [19]. When
at high temperature theWhen
[19]. softening point value
the softening point is higher,
value the modified
is higher, the modifiedbitumen is
considered to have
bitumen a stronger
is considered elastic
to have characteristic
a stronger against bitumen
elastic characteristic againstflow. Seenflow.
bitumen in Figure
Seen in4,Figure
the softening
4, the
point had softening point
a moderate had a with
increase moderate
the increase
additionwith the addition
of 0.5% MWCNTs of 0.5%andMWCNTs
a sharpand a sharpwith the
increase
increase with the addition of 1.0% MWCNTs. When more than 1.0%
addition of 1.0% MWCNTs. When more than 1.0% of MWCNTs were added, the softening point of MWCNTs were added, the value
softening point value fluctuated and no significant change was observed. It was generally
fluctuated and no significant change was observed. It was generally concluded that MWCNTs made the
concluded that MWCNTs made the SBS modified bitumen more stable against flowing when
SBS modified
subjectedbitumen more stable against
to high temperatures, flowing
which meant when
that the subjected to
MWCNTs/SBS high temperatures,
modified which meant
bitumen had a better
that thehigh
MWCNTs/SBS modified
temperature rutting bitumen had a better high temperature rutting resistance.
resistance.

Figure 4. Penetration and Softening point of bitumen with different content of MWCNTs.
Figure 4. Penetration and Softening point of bitumen with different content of MWCNTs.
Figure 5 shows the results of the ductility test. There was a small amplitude increase or
decrease
Figure compared
5 shows to the original
the results bitumen at
of the ductility 0.5%,
test. 1.0%,
There 1.5%,
was and 2.0%
a small MWCNTs.
amplitude A general
increase or decrease
fluctuation of ductility was observed for MWCNTs addition up to 2.0%.
compared to the original bitumen at 0.5%, 1.0%, 1.5% and 2.0% MWCNTs. A general With the addition of 3.0%
fluctuation
MWCNTs, there was a significant decrease in ductility. One possible reason was that when the
of ductility was observed for MWCNTs addition up to 2.0%. With the addition of 3.0% MWCNTs,
content of MWCNTs was less than 2.0%, there was a complex interaction between the MWCNTs
there was
andathe
significant decrease
SBS modified in ductility.
bitumen One possible
which reflected no severereason was
regularity that when
against theHowever
ductility. content of MWCNTs
with
was less than 2.0%, there was a complex interaction between the MWCNTs and
the addition of 3.0% MWCNTs, the agglomeration of MWCNTs became a stress concentration area the SBS modified
bitumen which
which reflected
accelerated the no severe
fracture regularity
process againstagainst
when subjected ductility. However
tensile with
stress at low the addition of 3.0%
temperature.
MWCNTs, the agglomeration of MWCNTs became a stress concentration area which accelerated the
fracture process when subjected against tensile stress at low temperature.
Materials 2017, 10, 416 7 of 16
Materials 2017, 10, 416 7 of 16

Figure 5. Ductility of bitumen with different content of MWCNTs.

3.1.2. Brookfield Viscosity Test Analysis

Figure 6 shows the results of the Brookfield viscosity test. The Brookfield viscosity test reflects
the frictional resistance which comes from the relative motion between two fluid layers in the
bitumen. The higher the viscosity,
Figure theofbetter
5. Ductility bitumen the
with frictional resistance
different content of bitumen against flowing,
of MWCNTs.
Figure 5. Ductility of bitumen with different content of MWCNTs.
and this reflects a better high temperature rutting resistance property. The VTS (Viscosity
3.1.2. Brookfield
temperature Viscosityvalue
susceptibility) Test Analysis
was used to evaluate the temperature susceptibility of bitumen.
3.1.2. Brookfield Viscosity Test Analysis
The higherFigure
the VTS, the more susceptible
6 shows the results of the Brookfield the bitumenviscosityis to changes
test. in viscosity
The Brookfield when
viscosity testsubjected
reflects to
high temperature
the frictional
Figure [20].results
6 shows resistance
the Fromwhichthethe
of testing
comes results
from
Brookfield the (Figure 6),
relativetest.
viscosity itThe
motion was noted two
between
Brookfield thatviscosity
withlayers
fluid thetest
addition
the ofthe
inreflects
bitumen.
MWCNTs,
frictional theThe
resistance higher the
viscosity
which value
comesviscosity,
has
from athe
the better
stable the frictional
increase
relative resistance
frombetween
motion 0% to 2%, of bitumen
two but
fluidwithagainst
eachin
layers flowing,
subsequent
the bitumen.
and ofthis reflects a better high temperature arutting resistance property. The VTSwhich (Viscosity
Theaddition
higher the higher
viscosity, percentages
the better the of MWCNTs, viscosity
frictional resistance increase
of bitumen was observed
against flowing, and this wasreflects
the
temperature susceptibility) value was used to evaluate the temperature susceptibility of bitumen.
highest
a better The at 120
highhigher °C.
temperature At 135 °C,
rutting the viscosities recorded were all within an acceptable range of
the VTS, the more resistance
susceptible property.
the bitumenThe is toVTS (Viscosity
changes temperature
in viscosity susceptibility)
when subjected to
Superpave
value was used specifications
to evaluate recommended for mixing [21]. When 3.0% MWCNTs was added, the
high temperature [20]. the
From temperature susceptibility
the testing results (Figure 6),ofit bitumen.
was notedThe that higher
with thethe VTS, the
addition of more
viscosity
susceptible value
MWCNTs, had
the bitumen a significant
is to changes
the viscosity increase.
value hasinaviscosity whenfrom
stable increase subjected
0% to to high
2%, but temperature [20]. From the
with each subsequent
testing Figure
addition
results 7 shows
of higher
(Figure thepercentages
6),Log‐Log
it was noted Viscosity
that(cp)
of MWCNTs, with vs. Log Temperature
a viscosity
the increaseofwas
addition (R) with different
observed
MWCNTs, which contents
was
the viscosity of
the value
MWCNTs.
highest Table
at 1203 °C.
shows At the °C,
135 VTSthevalues of the
viscosities original
recorded wereandallmodified
within anbitumen
acceptablealong
range with
of the
has a stable increase from 0% to 2%, but with each subsequent addition of higher percentages of
coefficient of determination
Superpave specifications (R 2). It can be for
recommended seenmixing
that the[21].VTSWhen values
3.0%decreased
MWCNTs with the increase
was added, the of
MWCNTs, a viscosity increase was observed which was the highest at 120 ◦ C. At 135 ◦ C, the viscosities
viscosity
MWCNTs, value hadlower
indicating a significant increase.susceptibility of the bitumen. In view of this, MWCNTs as
temperature
recorded were all within
Figure 7 shows anthe
acceptable
Log‐Log range of(cp)Superpave specifications recommended for mixing [21].
an additive could improve the highViscosity
temperaturevs.rutting Log Temperature
resistance(R) of with
SBS different
modifiedcontents
bitumen of and
When 3.0% MWCNTs
MWCNTs. Tablewas added, thethe
3susceptibility.
shows VTSviscosity
values ofvalue had a and
the original significant
modifiedincrease.
bitumen along with the
decrease temperature
coefficient of determination (R2). It can be seen that the VTS values decreased with the increase of
MWCNTs, indicating lower temperature susceptibility of the bitumen. In view of this, MWCNTs as
an additive could improve the high temperature rutting resistance of SBS modified bitumen and
decrease temperature susceptibility.

Figure 6. Viscosity versus temperature of bitumen with different content of MWCNTs.

Figure 6. Viscosity versus temperature of bitumen with different content of MWCNTs.
Figure 6. Viscosity versus temperature of bitumen with different content of MWCNTs.
Figure 7 shows the Log-Log Viscosity (cp) vs. Log Temperature (R) with different contents
of MWCNTs. Table 3 shows the VTS values of the original and modified bitumen along with the
coefficient of determination (R2 ). It can be seen that the VTS values decreased with the increase of
MWCNTs, indicating lower temperature susceptibility of the bitumen. In view of this, MWCNTs as
an additive could improve the high temperature rutting resistance of SBS modified bitumen and
decrease temperature susceptibility.
Materials 2017, 10, 416 8 of 16
Materials 2017, 10, 416 8 of 16

Figure 7. Log‐Log V. (cp) versus Log T. (R) with different content of MWCNTs.
Figure 7. Log-Log V. (cp) versus Log T. (R) with different content of MWCNTs.

Table 3. Viscosity temperature susceptibility (VTS) of MWCNTs/SBS modified bitumen.

Table 3. Viscosity temperature susceptibility (VTS) of MWCNTs/SBS modified bitumen.
Content of MWCNTs/% 0 0.5 1.0 1.5 2.0 3.0
Content of MWCNTs/%
VTS 0
−3.3642 0.5
−2.8098 1.0
−2.8135 1.5
−2.7363 2.0
−2.783 3.0
−2.4001
VTSR2 −3.3642
0.9765 −2.8098
0.9997 −2.8135
0.9994 −2.7363
0.9992 −
0.9987
2.783 −0.9961
2.4001
R2 0.9765 0.9997 0.9994 0.9992 0.9987 0.9961
3.1.3. DSR Analysis
3.1.3. DSR Analysis
Figures 8–10 show the result of the dynamic shear rheometer test. The complex shear modulus
describes
Figuresthe8–10
stiffness
showdegree of the
the result of bitumen,
the dynamic andshear
the higher the modulus,
rheometer test. Thethe stronger
complex shearthemodulus
property
to resist the
describes deformation,
stiffness degree namely
of thethe better and
bitumen, rutting resistance
the higher of bitumen
the modulus, pavement
the stronger at high
the property
temperature.
to From Figure
resist deformation, namely 8, the complex shearresistance
better rutting modulusof had a slight
bitumen increase at
pavement with
highthetemperature.
addition of
0% toFigure
From 2.0% MWCNTs.
8, the complexWhenshear 3.0% modulus
MWCNTshad was added,increase
a slight a significant
with increase
the addition of 25%of 0% on average
to 2.0%
was observed
MWCNTs. When within the temperature
3.0% MWCNTs was added, range from 30 increase
a significant to 50 °C. The on
of 25% phase angle
average was reflects
observed the
proportion
within between therange
the temperature elastic
fromcomponent ◦
30 to 50 and viscous
C. The phasecomponents.
angle reflectsThe thesmaller
proportion the between
phase angle, the
the higher
elastic the elasticity
component recovery
and viscous when the The
components. bitumen
smaller pavements
the phaseare subjected
angle, the higherto traffic at high
the elasticity
temperatures
recovery when[22,23]. With the
the bitumen additionare
pavements of subjected
MWCNTsto(Figure 9),high
traffic at theretemperatures
was a decrease fromWith
[22,23]. 40 tothe50
°C whichofwas
addition attributed
MWCNTs to the9),formation
(Figure there wasofa adecrease
noticeablefrom elastic 50 ◦ C which
40 tonetwork at thiswastemperature
attributed by the
to the
SBS. Whenofthe
formation temperature
a noticeable wasnetwork
elastic higher than 50 temperature
at this °C, the network wasSBS.
by the destroyed
When the andtemperature
the phase angle was
increased
higher thanwith ◦
50 higher temperature.
C, the network When theand
was destroyed temperature
the phase was anglehigher thanwith
increased 50 °C, with temperature.
higher the addition
of MWCNTs,
When the phasewas
the temperature angle had athan
higher 50 ◦ C, with
decreasing trendthein addition
general which
of MWCNTs,meant that the the
phasecontent
angleofhadthe
viscous components decreased and the content of the elastic components
a decreasing trend in general which meant that the content of the viscous components decreased and increased. The binder
containing
the content of1.0%
theand 1.5%
elastic MWCNTsincreased.
components did not have The obvious regularity,1.0%
binder containing which andmay1.5%beMWCNTs
attributeddid to
the have
not complex interaction
obvious between
regularity, which the maybitumen, SBS, to
be attributed andtheMWCNTs. When adding
complex interaction between3.0%the MWCNTs,
bitumen,
the variation
SBS, and MWCNTs. range When
of the adding
phase angle with the rise
3.0% MWCNTs, the of temperature
variation range of is far
the less
phase than forwith
angle the original
the rise
SBS
of modified asphalt.
temperature is far lessItthan
couldforbe theseen that SBS
original MWCNTsmodified as asphalt.
an additive improved
It could be seenthe that deformation
MWCNTs
∗
recovery
as ability
an additive of bitumen.
improved / sin versus
the deformation temperature
recovery ability ofof the bitumen
bitumen. G ∗ / sin
with different
δ versus content of
temperature
MWCNTs
of the bitumenwas with
calculated andcontent
different is shown in Figure 10.
of MWCNTs was It calculated
can be seenand thatisthe
shownrutting factor 10.
in Figure increased
It can
to seen
be a different
that theextent with
rutting the addition
factor increasedoftoMWCNTsa differentwhich
extentindicated
with the that MWCNTs
addition as an additive
of MWCNTs which
improvedthat
indicated the MWCNTs
high temperature ruttingimproved
as an additive resistancethe ofhigh
the SBS modifiedrutting
temperature bitumen. Overall,ofthe
resistance the DSR
SBS
test implies
modified that the
bitumen. MWCNTs
Overall, the DSR improved the high
test implies thattemperature
the MWCNTs performance
improved the of high
the SBS modified
temperature
bitumen.
performance of the SBS modified bitumen.
Materials 2017, 10, 416 9 of 16
Materials 2017, 10, 416 9 of 16
Materials 2017, 10, 416 9 of 16
Materials 2017, 10, 416 9 of 16

Figure 8. G* versus temperature of bitumen with different content of MWCNTs.

Figure G*G*
8. 8.
Figure versus
versustemperature
temperature of
of bitumen withdifferent
bitumen with differentcontent
contentofof MWCNTs.
MWCNTs.
Figure 8. G* versus temperature of bitumen with different content of MWCNTs.

Figure 9. Phase angle versus temperature curve of bitumen with different content of MWCNTs.
Figure 9. Phase
9. Phase angle
angle versustemperature
versus temperature curve of bitumen
bitumenwith
withdifferent content of of
MWCNTs.
Figure
Figure 9. Phase angle versus temperature curve
curve of
of bitumen with different
different content
content MWCNTs.
of MWCNTs.

Figure 10. ∗ / sin versus temperature of bitumen with different content of MWCNTs.
Figure 10. ∗∗/ sin versus temperature of bitumen with different content of MWCNTs.
Figure
Figure / sinδ versus
10.10.G ∗ / sin versustemperature
temperatureof
of bitumen
bitumen with
withdifferent
differentcontent
contentofof
MWCNTs.
MWCNTs.
Materials 2017, 10, 416 10 of 16
Materials 2017, 10, 416 10 of 16

3.1.4. BBR Analysis

3.1.4. In
BBR Analysis
order to evaluate the low temperature crack resistance performance of the bitumen, bending
beam In rheometer (BBR) the
order to evaluate tests
lowwere conducted.
temperature crackSHRP showed
resistance that the ofBBR
performance test had bending
the bitumen, a better
correlation
beam with (BBR)
rheometer low temperature crack resistance
tests were conducted. SHRP compared
showed that to the
the BBR
ductility test.a Parameter
test had “m” of
better correlation
the BBR test was related to stress relaxation [24]. As m increased,
with low temperature crack resistance compared to the ductility test. Parameter “m” of the BBR the stress relaxation property
improved.
test In other
was related words,
to stress when subjected
relaxation [24]. Astomlow temperatures,
increased, the stress SBSrelaxation
modified property
bitumen improved.
containing
MWCNTs
In is expected
other words, to have a to
when subjected better
low stress relation behavior.
temperatures, SBS modified S reflected
bitumen thecontaining
degree of brittleness.
MWCNTs
isThe highertothe
expected haveS value, the
a better lower
stress the cracking
relation behavior. resistance
S reflected at the
lowdegree
temperature. According
of brittleness. to the
The higher
standard
the S value,[17],
theSBS
lowermodified bitumenresistance
the cracking was tested at at
lowseveral temperatures.
temperature. Whentothe
According thetemperature fell
standard [17],
to −16
SBS °C, the bitumen
modified stiffness of thetested
was SBS modified
at several bitumen was larger
temperatures. When thanthe300temperature
MPa, so finally −16−°C
fell to ◦ C,
16 was
determined
the stiffness ofas thethe
SBS critical
modifiedtemperature
bitumen wasto evaluate
larger than 300 theMPa, finally −16 ◦ Cproperty
lowso temperature of the
was determined
MWCNTs/SBS
as modified to
the critical temperature bitumen.
evaluateFromthe lowFigure 11, it can
temperature be seen
property that
of the with the addition
MWCNTs/SBS modified of
MWCNTs, the m value generally had an increasing trend, while S slowly
bitumen. From Figure 11, it can be seen that with the addition of MWCNTs, the m value generally had decreased with the
addition
an of 0trend,
increasing to 1.5%
whileofS slowly
MWCNTs. The stiffness
decreased was lessofthan
with the addition 300 MPa
0 to 1.5% when 0.5%
of MWCNTs. to 2.0%
The stiffness
MWCNTs
was less thanwas 300added.
MPa whenWhen0.5%moretothan2.0%1.5% MWCNTs
MWCNTs was was
added. added,
When S had
more a sharp increase
than 1.5% which
MWCNTs
may result from the agglomeration of MWCNTs, improving the stiffness
was added, S had a sharp increase which may result from the agglomeration of MWCNTs, improving of the binder. Overall, the
addition
the of MWCNTs
stiffness of the binder. improved
Overall, thethelow temperature
addition of MWCNTs crack resistance
improvedofthe SBS
low modified bitumen
temperature crackat
concentrations
resistance of SBSless than 2.0%.
modified bitumen In ataddition, it also less
concentrations reflected that the
than 2.0%. ductilityit was
In addition, not the most
also reflected that
appropriate
the ductility was evaluation tool of
not the most the low evaluation
appropriate temperature performance
tool of bitumen,performance
of the low temperature especially forof
evaluating
bitumen, MWCNTs/SBS
especially modified
for evaluating bitumen.
MWCNTs/SBS modified bitumen.

Figure11.
Figure 11.Creep
Creepstiffness
stiffnessand
andmmfrom
from60
60s satat−−16
16 ◦°C.
C.

3.2. Modification Mechanism

3.2. Modification Mechanism
3.2.1. Far
3.2.1. Far Infrared
InfraredSpectrum
SpectrumAnalysis
Analysis
Fromthe
From theFT-IR
FT‐IR testtest (Figure
(Figure 12), 12), no chemical
no new new chemical functional
functional groupsgroups were with
were formed formed with the
the addition
addition
of MWCNTs, of MWCNTs,
and all theand all theconcentrations
different different concentrations
of MWCNTs ofshowed
MWCNTs showed
a similar a similar
trend. trend.
This meant
This meant that the MWCNTs did not chemically react with bitumen, or that the interaction
that the MWCNTs did not chemically react with bitumen, or that the interaction was so weak that the was so
weak test
FT-IR thatcould
the FT‐IR test could
not detect not detect it directly.
it directly.
Materials 2017, 10, 416 11 of 16
Materials 2017, 10, 416 11 of 16

Figure
Figure 12.12. FT‐IRofoforiginal
FT-IR original and
and 1.0%
1.0%MWCNTs
MWCNTsmodified
modifiedbitumen.
bitumen.

3.2.2. Bitumen Four Components Analysis

3.2.2. Bitumen Four Components Analysis
Table 4 shows the bitumen four components test. It was seen that with the addition of
Table 4 shows
MWCNTs, the bitumen
the contents four components
of saturates and aromatics test.decreased.
It was seenOnthat
the with
other the addition
hand, of MWCNTs,
the contents of
the contents of saturates and aromatics decreased. On the other hand, the contents
resins and asphaltenes increased. One possible reason for this is that the MWCNTs have a strong of resins and
asphaltenes increased.
adsorption One organic
capacity with possiblemolecules
reason for this is that
containing the MWCNTs
benzene rings, suchhave
as thea aromatics
strong adsorption
and
polystyrene
capacity of SBS,molecules
with organic through π–π intermolecular
containing benzene forces.
rings,Insuch
suchasa the
case, SBS would
aromatics andhave better
polystyrene of
SBS, compatibility
through π–πwith bitumen which
intermolecular meantInthat
forces. suchmore saturates
a case, SBSwere
would absorbed in the network
have better of SBS with
compatibility
and then
bitumen whicha stronger structure
meant that morewas formed.
saturates Saturates
were absorbedwhichinfiltered into theofnetwork
the network SBS and ofthen
SBS could
a stronger
not be washed out by the solvent used in the bitumen four components test [25]. As a result, the
structure was formed. Saturates which filtered into the network of SBS could not be washed out
percentage of light components decreased and the percentage of heavy portions such as resins and
by the solvent used in the bitumen four components test [25]. As a result, the percentage of light
asphaltenes increased, respectively, which gave an increased viscosity and softening point of the
components
bitumen.decreased
The resultandwasthe percentagewith
in agreement of heavy portions such
the Brookfield as resins
viscosity and asphaltenes
and softening increased,
point test. At
respectively, which gave an increased viscosity and softening point of the bitumen.
concentrations higher than 2.0%, the agglomeration of MWCNTs played a major role in the bitumen The result was in
agreement with the Brookfield
and agglomerated MWCNTsviscosity and softening
lose this specific propertypoint test.the
and thus Atpercentage
concentrations higher than
of the bitumen four 2.0%,
the agglomeration
components didofnot MWCNTs
change. played a major role in the bitumen and agglomerated MWCNTs lose
this specific property and thus the percentage of the bitumen four components did not change.
Table 4. Proportion of MWCNTs/SBS bitumen four components.
Table 4. Proportion of MWCNTs/SBS bitumen of
The Content four components.
Components/%
The Percentage of MWCNTs/%
Saturation Aromatic Resin Asphaltene
The Content of Components/%
The Percentage0 of MWCNTs/% 17.27 45.22 32.65 4.86
0.5 Saturation
15.99 Aromatic
44.52 Resin
34.12 Asphaltene
5.37
1.00 14.50
17.27 42.19
45.22 37.85
32.65 5.46
4.86
0.5
1.5 15.99
14.11 44.52
42.18 34.12
38.08 5.37
5.63
1.0 14.50 42.19 37.85 5.46
2.0 14.04 42.29 38.17 5.50
1.5 14.11 42.18 38.08 5.63
3.0
2.0 14.32
14.04 42.01
42.29 37.74
38.17 5.93
5.50
3.0 14.32 42.01 37.74 5.93
3.2.3. Thermal Analysis
3.2.3. Thermal Analysis
The thermal analysis test was conducted to investigate the thermal decomposition pattern of
the test samples. Thermal Gravimetric analysis (TG) and Derivative Thermogravimetry analysis
The thermal analysis test was conducted to investigate the thermal decomposition pattern of the
(DTG) were performed to analyze the thermal stability and decomposition of different phases.
test samples.
ParametersThermal Gravimetric
Ted, Tm, and analysis
Mf were used (TG) and
to evaluate Derivative
the thermal Thermogravimetry
stability of the materials, inanalysis
which Ted(DTG)
wereisperformed to analyze the thermal stability and decomposition of different phases.
the epitaxial decomposing temperature, Tm is the temperature corresponding to the maximum Parameters
Ted , Tm , and Mf were used to evaluate the thermal stability of the materials, in which Ted is the
epitaxial decomposing temperature, Tm is the temperature corresponding to the maximum mass
loss rate, and Mf is the final residue mass ratio [26–29]. The DTG curve was used to distinguish the
different components in bitumen. Figure 13a shows that the SBS modified bitumen with 0% and 0.5% of
Materials 2017, 10, 416 12 of 16
Materials 2017, 10, 416 12 of 16
mass loss rate, and Mf is the final residue mass ratio [26–29]. The DTG curve was used to
distinguish the different components in bitumen. Figure 13a shows that the SBS modified bitumen
MWCNTs
with 0% and decomposed at an earlier
0.5% of MWCNTs time. An improvement
decomposed was observed
at an earlier time. at a MWCNTs
An improvement concentration
was observed at a
of 1.0%, and after then, only a slight improvement was observed.
MWCNTs concentration of 1.0%, and after then, only a slight improvement was observed.
Compared
Compared to to the
the DTG
DTG curves,
curves,ititwas
wasobserved
observedthat
thatthere
therewaswasa aslight
slightstep step before
before TmTnamely
m namely in
in
area 1 (the curve part obviously lower than other content MWCNTs/SBS modified bitumen bitumen
area 1 (the curve part obviously lower than other content MWCNTs/SBS modified between
between ◦ C and 400 ◦ C) in Figure 13b. The DTG from 300 to 400 ◦ C was mainly attributed
300400°C)
300°C and in Figure 13b. The DTG from 300 to 400 °C was mainly attributed to the
to the decomposition
decomposition and volatilization
and volatilization of saturates
of saturates and aromatics
and aromatics [30]. A [30].
similar A similar
step alsostep alsoin
exists exists in
Figure
Figure 13b, namely 2 (the curve part slightly higher than area 1 between 300 ◦ C and 400 ◦ C), but was
13b, namely 2 (the curve part slightly higher than area 1 between 300°C and 400°C), but was
slightly
slightly higher
higherwhich
whichindicated
indicatedthat the
that thedecomposition
decomposition raterate
of the lightlight
of the components
components decreased. At 1.0%
decreased. At
concentration, the DTG curve became smooth and did not show
1.0% concentration, the DTG curve became smooth and did not show the steps. the steps.
Table
Table 55 shows
shows thethe parameters
parameters TTed , Tm , and M for the six different concentrations of MWCNTs.
ed, Tm, and Mff for the six different concentrations of MWCNTs.
It
It was
was generally
generally observed
observed thatthat with
with the
the addition
addition of
of MWCNTs,
MWCNTs,the theTTeded,, TTmm,, and
and M Mff increased
increased which
which
meant
meant that the MWCNTs improved the thermal stability of the SBS modified bitumen. This
that the MWCNTs improved the thermal stability of the SBS modified bitumen. This better
better
performance should be attributed to the stronger network structure which
performance should be attributed to the stronger network structure which prevented the prevented the decomposition
and volatilization
decomposition andofvolatilization
light components.of lightAs a result, theAs
components. value of DTG
a result, the regarding
value of DTG the saturates
regardingand
the
aromatics decreased. Thermal analysis confirmed the testing results of
saturates and aromatics decreased. Thermal analysis confirmed the testing results of the the bitumen four components
bitumen
test
fouranalysis.
components test analysis.

(a) (b)
Figure 13 Thermal analysis of bitumen with different content of MWCNTs: (a) TG versus
Figure 13. Thermal analysis of bitumen with different content of MWCNTs: (a) TG versus temperature;
temperature,
(b) (b)temperature.
DTG versus DTG versus temperature.

Table 5. The Ted (epitaxial decomposition temperature), the Tm (temperature of the fastest
Table 5. The Ted (epitaxial decomposition temperature), the Tm (temperature of the fastest decomposition
decomposition rate), and the Mf (final residual mass) of MWCNTs/SBS modified bitumen.
rate), and the Mf (final residual mass) of MWCNTs/SBS modified bitumen.
The Percentage of MWCNTs/% Ted/°C Tm/°C Mf/%
The Percentage of MWCNTs/% Ted /◦ C T /◦ C M /%
0 364.5 m 451.4 f 14.23
0 364.5
0.5 374.1 451.4
451.4 14.23
14.78
0.5 374.1 451.4 14.78
1.0
1.0 390.9
390.9 453.7
453.7 15.92
15.92
1.5
1.5 393.9
393.9 453.3
453.3 16.52
16.52
2.0 397.9 459.2 13.61
2.0
3.0
397.9
397.1
459.2
457.6
13.61
18.30
3.0 397.1 457.6 18.30
3.2.4. Fluorescence Microscopy Test
3.2.4. Fluorescence Microscopy Test
The fluorescence microscopy test was conducted to analyze the dispersion and storage stability
The fluorescence microscopy test was conducted to analyze the dispersion and storage stability
of PmB. SBS produces fluorescence under UV irradiation which can be used to detect the traces of
of PmB. SBS produces fluorescence under UV irradiation which can be used to detect the traces of
SBS. From the performance tests, we concluded that 1.0% MWCNTs was the optimum content, so SBS
SBS. From the performance tests, we concluded that 1.0% MWCNTs was the optimum content, so
modified bitumen and 1.0% MWCNTs/SBS modified bitumen was tested to determine the difference.
SBS modified bitumen and 1.0% MWCNTs/SBS modified bitumen was tested to determine the
From Figure 14a,b, the existent morphology of SBS changed from floccule to granule and SBS has
difference. From Figure 14a,b, the existent morphology of SBS changed from floccule to granule and
a better dispersion in Figure 14b. The flocculent structure is one stage of SBS agglomeration. Figure 14c
Materials 2017, 10, 416 13 of 16
Materials 2017, 10, 416 13 of 16
SBS has a better dispersion in Figure 14b. The flocculent structure is one stage of SBS
agglomeration. Figure 14c shows that a large number of SBS grains agglomerated and became clear
shows
ribbonsthat
anda there
large number
were moreof SBS grains
slight and agglomerated
vague ribbonsand became14e.
in Figure clear
In ribbons
addition,andthethere wereofmore
content SBS
slight and vague ribbons in Figure 14e. In addition, the content of SBS in Figure
in Figure 14d is less than that in Figure 14f. Overall, Figure 14a,b shows that the MWCNTs 14d is less than that
in Figure 14f.
improved the Overall, Figure
dispersion 14a,binshows
of SBS that the MWCNTs
the bitumen, and Figureimproved the dispersion
14e–f indicate that the of MWCNTs
SBS in the
bitumen, and Figure 14e–f indicate that the MWCNTs improved the storage stability of
improved the storage stability of the SBS modified bitumen. There may be a complex interaction the SBS modified
bitumen. There may be a complex interaction between the bitumen, SBS, and MWCNTs
between the bitumen, SBS, and MWCNTs which resisted the agglomeration of SBS and promoted which resisted
the
the agglomeration
dispersion andofdissolution
SBS and promoted
of the SBStheindispersion
bitumen. and dissolution of the SBS in bitumen.

(a) (b)

(c) (d)

(e) (f)
Figure 14.
Figure 14. Fluorescence
Fluorescence microscopy
microscopy from
from ××100:
100: (a) SBS modified
(a) SBS modified bitumen;
bitumen; (b)
(b) 1.0%
1.0% MWCNTs/SBS
MWCNTs/SBS
modified bitumen; (c) the upper 1/3 part of the tube filled with SBS modified bitumen;
modified bitumen; (c) the upper 1/3 part of the tube filled with SBS modified bitumen; (d) the bottom (d) the
bottom
1/3 part1/3 parttube
of the of the tube
filled filled
with SBSwith SBS modified
modified bitumen; bitumen; (e) the
(e) the upper 1/3upper
part of1/3 tubeoffilled
thepart the tube
withfilled
1.0%
with 1.0% MWCNTs/SBS modified bitumen; (f) the bottom 1/3 part of the
MWCNTs/SBS modified bitumen; (f) the bottom 1/3 part of the tube filled with 1.0% MWCNTs/SBS tube filled with 1.0%
MWCNTs/SBS
modified bitumen.modified bitumen.
Materials 2017, 10, 416 14 of 16
Materials 2017, 10, 416 14 of 16

A
A strong
strong π–π
π–π interaction
interaction between
between thethe aromatic
aromatic molecules
molecules andand MWCNTs
MWCNTs was was noted
noted from
from the
the
study,
study, and
and the
the adsorption
adsorption of of carbon
carbon nanotubes
nanotubes on on the
the saturated
saturated molecules
moleculeswas wasmuchmuchlesslessthan
thanthat
that
of
of the
the organic
organic molecules
molecules containing
containingbenzene
benzenerings
rings[31–33].
[31–33].InIn view
view of
of this,
this, aa conjecture
conjecture about
about the
the
specific
specificinteraction
interactionbetween
betweenMWCNTs MWCNTsand andSBS
SBSmodified
modified bitumen
bitumenwaswasproposed
proposed to explain whywhy
to explain the
MWCNTs
the MWCNTs improved the performance
improved the performance of theofSBS
themodified
SBS modifiedbitumen: One end
bitumen: One of end
the MWCNTs
of the MWCNTscould
have
couldformed a non‐covalent
have formed complex
a non-covalent with the
complex polystyrene
with of the of
the polystyrene SBS
thethrough π–π conjugates,
SBS through and
π–π conjugates,
the
andother part part
the other could alsoalso
could have a π–π
have a π–π conjugate
conjugateaction
actionwith
witharomatics.
aromatics.This Thisimplied
impliedthatthat the
the
MWCNTs
MWCNTs could could make
make SBS SBS have
have aa better
better compatibility
compatibility with
with bitumen
bitumen andand then
then more
more saturates
saturates and
and
aromatics
aromatics would be befiltered
filteredintointo
thethe
SBSSBS network
network structure.
structure. As a aresult,
As a result, strongera stronger
network network
structure
structure
consistingconsisting of SBS,
of SBS, light light components
components of bitumen,of bitumen,
and MWCNTs and MWCNTs
was formed waswhich
formed whichthe
yielded yielded
better
the
highbetter high temperature
temperature ruttingand
rutting resistance resistance and lowcrack
low temperature temperature
resistancecrack resistance
of bitumen. Thisofexplanation
bitumen.
This explanationwith
is in agreement is intheagreement
performance with theand
tests performance
the mechanism tests and
and structure
the mechanism
analysis.and structure
According to
analysis.
the aboveAccording to the
explanation, theabove explanation,
schematic in Figurethe15 schematic
was proposed.in Figure 15 was proposed.

Figure 15. Schematic of MWCNTs/SBS modified bitumen.

Figure 15. Schematic of MWCNTs/SBS modified bitumen.

4. Conclusions
4. Conclusions
In this paper, experiments were conducted according to two different approaches: one was to
In this paper, experiments were conducted according to two different approaches: one was to
investigate the effect of adding MWCNTs on the properties of SBS modified bitumen at high and
investigate the effect of adding MWCNTs on the properties of SBS modified bitumen at high and
low temperatures, and the other was to explain the modification mechanism according to the
low temperatures, and the other was to explain the modification mechanism according to the specific
specific structure and properties of MWCNTs, as well their the interaction with SBS bitumen. Five
structure and properties of MWCNTs, as well their the interaction with SBS bitumen. Five different
different percentages (0.5%, 1.0%, 1.5%, 2.0%, and 3.0%) of MWCNTs were blended with SBS
percentages (0.5%, 1.0%, 1.5%, 2.0% and 3.0%) of MWCNTs were blended with SBS modified bitumen.
modified bitumen. the following conclusions can be drawn:
the following conclusions can be drawn:
1. MWCNTs as an additive had a positive effect on the performances of the SBS modified
1. bitumen.
MWCNTs Theasoptimum
an additive had a positive
concentration effect on the
of MWCNTs in performances
SBS modified of the SBSwas
bitumen modified bitumen.
determined as
The optimum concentration of MWCNTs in SBS modified bitumen was determined as 1.0%.
1.0%.
2.2. TheTheBrookfield
Brookfieldrotational
rotationalviscosity
viscositytest
testshowed
showedthat thatthe
theMWCNTs
MWCNTsas asananadditive
additiveimproved
improvedthe the
hightemperature
high temperaturesusceptibility
susceptibilityofofthe theSBS
SBSbitumen.
bitumen.The TheDSR
DSRtest
testshowed
showedthat thatMWCNTs
MWCNTscould could
improve the high temperature property of the SBS modified bitumen and
improve the high temperature property of the SBS modified bitumen and the BBR test indicated the BBR test indicated
that
that MWCNTsimproved
MWCNTs improvedthe thelow
lowtemperature
temperaturecrackcrackresistance.
resistance.
3. The IR test revealed that there is no new chemical
3. The IR test revealed that there is no new chemical functional groups functional groups formed
formed by by
thethe addition
addition of
of MWCNTs.
MWCNTs. The The bitumen
bitumen fourfour components
components testtest showed
showed that
that MWCNTs
MWCNTs asasananadditive
additivetotoSBS
SBS
modifiedbitumen
modified bitumenresult
resultininchanges
changesininthe thecontent
contentofofeach
eachcomponent.
component.The Thethermal
thermalanalysis
analysistest
test
confirmed that the MWCNTs improved the thermal stability of the SBS
confirmed that the MWCNTs improved the thermal stability of the SBS modified bitumen and modified bitumen and
thethelight
lightcomponents
componentsdecomposed
decomposedatataaslower slowerrate.
rate.InInaddition,
addition,the
thefluorescence
fluorescence microscopy
microscopy
test showed that the MWCNTs improved the dispersion and storage stability of SBS in
bitumen. A schematic was proposed by the strong adsorption property due to π–π interaction
Materials 2017, 10, 416 15 of 16

test showed that the MWCNTs improved the dispersion and storage stability of SBS in bitumen.
A schematic was proposed by the strong adsorption property due to π–π interaction between
MWCNTs and organic molecules that containing benzene rings, to explain why MWCNTs had
a positive effect on the SBS modified bitumen. It was suggested that MWCNTs act like a ‘bridge’;
one of its ends had a π–π conjugated complex with the polystyrene of SBS, and the other side
had a π–π conjugate interaction with the aromatic molecules. There was a better compatibility of
polystyrene and for that reason, more saturates and aromatics filtered into the network structure
of SBS and then a stronger network structure consisting of SBS, light components of bitumen,
and MWCNTs in the MWCNT/SBS modified bitumen was formed. The improved high and
low temperature performance was attributed to the stronger network structure. Further study is
needed to directly confirm the existence of π–π interactions between the polystyrene of SBS and
the MWCNTs in bitumen.

These conclusions are only limited to the materials used in this study and they may be different
for other materials.

Acknowledgments: This research was supported by the National Key Scientific Apparatus Development Program
from the Ministry of Science and Technology of China (No. 2013YQ16050102) and the National Basic Research
Program of China (973 Program No. 2014CB932104).
Author Contributions: Conceived and designed the experiments: Benan Shu, Ling Pang, Shaopeng Wu,
and Barugahare Makorogo Performed the experiments: Benan Shu Analyzed the data: Benan Shu, Ling
Pang, Shaopeng Wu, and Barugahare Makorogo Attributed reagents/materials/analysis tools: Ling Pang and
Shaopeng Wu Wrote the paper: Benan Shu and Ling Pang.
Conflicts of Interest: There are no conflicts of interest regarding the publication of this paper.

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