Characterization of Organic Surfactant on Montmorillonite

Nanoclay to Be Used in Bitumen

Gang Liu1; Shaopeng Wu2; Martin van de Ven3; Andre Molenaar4; and Jeroen Besamusca5
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Abstract: In the past decades, montmorillonite nanoclay has been used successfully to strongly improve properties of polymers. Similar
improvements to nanoclay modified bitumen were expected, so the montmorillonite nanoclay was adopted to modify bitumen. To
understand the interaction with bitumen, it was of fundamental importance to know the composition of organic surfactant on montmo-
rillonite nanoclay. Two organically modified montmorillonite 共OMMT兲 nanoclays available in the market were studied to characterize the
composition of the surfactant through X-ray photoelectron spectrometry and simultaneous differential scanning calorimetry and thermo-
gravimetric 共DSC-TG兲 analysis. From the measurements it could be concluded that there was a difference between the surfactants. One
surfactant was composed of two states of nitrogen: quaternary ammonium and probably amine or nitrile. The other surfactant only
contained quaternary ammonium. In general, C u C bonds could be detected very well for the two surfactants and there were no other
functional groups, such as carboxylic, hydroxyl, ketone, etc. However, it was unclear if the surfactants had C v C bonds. DSC-TG
analysis indicated that the two OMMTs showed very different thermal behavior, but at temperatures below 200° C no problems were
expected.
DOI: 10.1061/共ASCE兲MT.1943-5533.0000013
CE Database subject headings: Asphalts; Organic matter; Nanotechnology; Clays; Material properties; Polymer.
Author keywords: Montmorillonite; Organic surfactant; Bitumen; XPS; DSC-TG.

Introduction
Montmorillonite 共MMT兲 is a very soft phyllosilicate mineral with
a 2:1 type layer structure, i.e., it has two tetrahedral sheets sand-
wiching a central octahedral sheet 共Pusch and Yong 2006兲. In the
past decades MMT has been successfully introduced into polymer
systems to form polymer-clay nanocomposites 共PCN兲 in which
silicate layers of nanoclay were randomly and homogeneously
dispersed at molecular level in the polymer matrix 共Okada and
Usuki 2006; Koo 2006; Giannelis 1996; Pinnavaia and Beall
2006; Kato et al. 1997兲. Due to the addition of the nanoclay, a
number of properties of PCN, such as the mechanical, thermal,
gas barrier properties, etc., are superior to those of pristine poly-
mers and/or conventional composites. In order to make the nano-
1
Ph.D. Student, Key Laboratory of Silicate Materials Science and En-
gineering of Ministry of Education, Wuhan Univ. of Technology, Wuhan
430070, China; and, Faculty of Civil Engineering and Geo Sciences,
Delft Univ. of Technology, Delft 2600 GA, The Netherlands.
2
Professor, Key Laboratory of Silicate Materials Science and Engi-
neering of Ministry of Education, Wuhan Univ. of Technology, Wuhan,
430070, China.
3
Associate Professor, Faculty of Civil Engineering and Geo Sciences,
Delft Univ. of Technology, Delft 2600 GA, The Netherlands 共correspond-
ing author兲. E-mail: m.f.c.vandeven@tudelft.nl
4
Professor, Faculty of Civil Engineering and Geo Sciences, Delft
Univ. of Technology, Delft 2600 GA, The Netherlands.
5
Senior Scientist, Dept. of Bitumen, Kuwait Petroleum Research and
Technology, The Netherlands.
Note. This manuscript was submitted on May 15, 2009; approved on
December 10, 2009; published online on February 6, 2010. Discussion
period open until January 1, 2011; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Materials in
Civil Engineering, Vol. 22, No. 8, August 1, 2010. ©ASCE, ISSN 0899-
1561/2010/8-794–799/$25.00.
clay more compatible with the polymer, some surfactants, such as
quaternary ammonium salt surfactants, are usually used to modify
the nanoclay in which organic cations will replace the interlayer
hydrated Na+ and K+. In this way, the normally hydrophilic sili-
cate surface becomes organophilic 共Giannelis 1996兲. Moreover,
the organic cations may contain various functional groups that
react with the polymer to improve adhesion between the inorganic
phase and the matrix. Meanwhile, they can increase the basal
spacing of silicate plates which makes polymer molecules conve-
niently enter the gallery space 共Alexandre and Dubois 2000兲.
Bitumen is widely used in road construction as a binder. Due
to traffic loads and environmental factors, bitumen properties can
change during service life. Bitumen will age due to diffusion of
oxygen and ultraviolet radiation 共hardening兲. Repeated loading
will result in decreasing strength because of fatigue. Water can
influence the adhesion between the bitumen and the aggregate.
All these influences could lead to early failure 共Rostler and White
1962; Petersen 1984; Halstead 1985兲. Some polymers, especially
styrene-butadiene-styrene 共SBS兲, were used as modifiers to im-
prove the properties of bitumen 共Morgen and Mulder 1995; Lu
and Isacsson 1997兲. Recently, some efforts were made by a few
researchers to detect the potential of MMT nanoclay in the modi-
fication of bitumen. Organic MMT 共OMMT兲 nanoclays, nanofill
and cloisite, were adopted to modify bitumen and properties of
modified bitumens, and corresponding asphalt mixes were tested
at the Delft University of Technology 共Gile 2006兲. Two MMTs,
one organic and another inorganic, were also adopted in the modi-
fication of bitumen and a comparison was made between the
rheological properties 共Yu and Xuan 2007兲. Research results in-
dicated that the addition of nanoclay might improve the properties
of bitumen with respect to stiffness, rutting, aging etc.
To characterize the relationship between the nanoclay and bi-
tumen more unambiguously, a joint research on the nanoclay

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J. Mater. Civ. Eng. 2010.22:794-799.


OMMT
Intensity
OMMT in bitumen
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0 2 4 6
2θ [°]
Fig. 1. XRD curves for one OMMT before and after mixing with
bitumen
modified bitumen is being performed between the Delft Univer-
sity of Technology and the Wuhan University of Technology. In
that research, at least six types of organic surfactant modified
MMTs are used in the modification of bitumen with different
grades. Some interesting results are shown in Figs. 1 and 2. The
X-ray diffraction 共XRD兲 spectra in Fig. 1 show that the interlayer
spacing of OMMT in the bitumen increases compared to its origi-
nal interlayer spacing 共Liu et al. 2010兲. This means that the nano-
clay and bitumen interact at nanometer level. An aging index 共AI兲
for the base bitumen and modified bitumen are shown in Fig. 2.
The AI of the binder is defined here as the ratio of the complex
shear modulus 共at 0.1 rad/s兲 after and before the rolling thin film
oven aging. As indicated in Fig. 2, the AI for the modified bitu-
men is significantly lower at all testing temperatures compared to
the base. A possible reason could be the gas barrier property of
the nanoclay, but concerns are also that the changed viscosity due
to the addition of the nanoclay could have played a role.
3.0
Ageing index after RTFOT at 0.1 rad/s
2.5
2.0
1.5
1.0
0.5
-10 10
Temperature [°C]
Fig. 2. Comparison of the AI 共ratio shear modulus兲 between the base
and modified bitumen
The research results also indicated that different MMT types
had a different influence on the modification of bitumen, which
was believed to be strongly related to the type of surfactant on the
MMT. So it is of fundamental importance to know the composi-
tion of the organic surfactant. In this paper the results are reported
of a study in which X-ray photoelectron spectrometry 共XPS兲 and
simultaneous differential scanning calorimetry and thermogravi-
metric 共DSC-TG兲 analyses were used to characterize the organic
surfactant cations in two nanoclays.
Experimental
Materials
8 10 12
Two types of organic surfactant modified MMT, OMMT-1 and
OMMT-2, were studied. They are available in the market and
provided by different nanoclay companies.
XPS
XPS is a spectroscopic technique that measures the elemental
composition, empirical formula, chemical state, and electronic
state of the elements that exist within a material 共Carleya 2001兲.
XPS spectra are obtained by irradiating a material with a beam of
X rays while simultaneously measuring the kinetic energy 共KE兲
and number of electrons that escape from the top 1 to 10 nm of
the materials being analyzed.
Because the energy of a particular X-ray wavelength equals a
known quantity, the electron binding energy 共BE兲 of each of the
emitted electrons can be determined using an equation as follows:
Ebinding = Ephoton − Ekinetic − ⌽ 共1兲
where Ebinding = energy of the electron emitted from one electron
configuration within the atom; Ephoton = energy of the X-ray pho-
tons being used; Ekinetic = KE of the emitted electron as measured
by the instrument; and ⌽ = work function of the spectrometer 共not
the material兲.
Each element produces a characteristic set of XPS peaks at
corresponding BE values that directly identify the existence of the
element on the surface of the material being analyzed. A charac-
teristic peak shift will occur when the chemical state of the ele-
ment is changed, which is used to speculate about the existence of
a related element.
Some details of the XPS equipment used are shown below.
• Equipment type: XSAM800, Kratos Ltd.;
• Vacuum condition: 2 ⫻ 10−7 Pa;
• Resolution: 0.9 eV/104 counts per second 共CPS兲;
• Wide scanning range: 0–1,000 eV;
• Fine scanning range for N1s: 395–415 eV; and
• Fine scanning range for C1s: 279–299 eV.
Base bitumen
OMMT modified bitumen DSC and Thermogravimetry
TG analysis is based on the continuous recording of relative mass
changes of a sample of material as a function of a combination of
temperature with time and the addition of pressure and gas com-
position. DSC is used to observe the small energy changes that
30 50 70 occur during physical and chemical processes 共Rjeb et al. 2005兲.
To characterize the thermal stability and decomposition of or-
ganically modified montmorillonite, simultaneous DSC-TG
analysis was adopted and conducted with a thermal analyzer
equipment NETZSCH STA 449 C using an atmospheric air
JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / AUGUST 2010 / 795
J. Mater. Civ. Eng. 2010.22:794-799.
 19000 CPS 5500
Analyser Mode: FRR C (1s)
CPS O C-C,
Resolution: Medium C-R
Magnification: High
Energy Range: X 1 C
Exciting Source: Mg
Region 01: Wide
B.E. 1000.00-0.00eV
100mS per 0.25 eV
Across Scan for 1 time
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Si
COOH, COH,
COOR COR
Al CO3
N

0 298 294 290 286 282 278

1000 900 800 700 600 500 400 300 200 100 0 Binding Energy (eV)
Binding energy (eV)

Fig. 5. Example of high energy resolution XPS spectrum for carbon

Fig. 3. Wide scan survey spectrum for OMMT-1
at different states

stream of 10 mL/min, while heating from room temperature to
800° C at a linear temperature increase of 10° C / min.
Results and Discussion
XPS
Figs. 3 and 4 show a wide scan survey spectrum for the OMMT-1
and the OMMT-2, respectively. The x axis represents each el-
ement’s characteristic BE of the electron emitted from one elec-
tron configuration within an atom, and the y axis reflects detected
photoelectron CPS, i.e., intensity. According to the captured sur-
face element signal corresponding to related characteristic peaks,
carbon, nitrogen, oxygen, silicon, and aluminum were detected
for both nanoclays. This indicates that the elements on the surface
of both nanoclays are similar.
High energy resolution XPS spectrum was used to determine
the chemical state of the element being detected. An example of
the high energy resolution XPS spectrum for carbon is given in
Fig. 5 共Briggs 1998兲. In this example, an envelope curve of car-
bon was obtained. Due to the existence of different functional
groups, the characteristic peak of carbon would shift toward
higher BE, from the typical alkyl carbon peak at around 285 eV.
Through professional spectrum analysis software, other character-
istic peaks representing the different chemical state of carbon in
the related functional group can also be obtained.
It was expected to observe the difference between organic sur-
factant cations in both nanoclays. So the spectrum analysis fo-
cused on the elements carbon and nitrogen. High energy
resolution XPS spectra of these two elements are shown in Figs. 6
and 7, respectively. In Fig. 6, it was found that both carbon spec-
trums are single, symmetrical, and similar, with the peaks at 284.8
and 285.0 eV, respectively. So based on the element analysis re-

17000 16000
CPS Analyser Mode: FRR CPS Analyser Mode: FRR
O OMMT-1
Resolution: Medium Resolution: Medium
285.0 eV
C Magnification: High
Magnification: High
Energy Range: X 1 OMMT-2
Energy Range: X 1
Exciting Source: Mg 248.8 eV
Exciting Source: Mg
Region 01: C1S
Region 01: Wide
B.E. 299.00-279.00 eV
B.E. 1000.00-0.00eV ChargeShift: 4.100 eV
100mS per 0.25 eV 500mS per 0.10 eV
Across Scan for 1 time Across Scan for 3 times

Si

Al
N

2000
295 290 285 280 275
0
Binding Energy (eV)
1000 900 800 700 600 500 400 300 200 100 0
Binding energy (eV)
Fig. 6. High energy resolution XPS spectrum for carbon in OMMT-1
Fig. 4. Wide scan survey spectrum for OMMT-2 and OMMT-2

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J. Mater. Civ. Eng. 2010.22:794-799.

 3400
CPS Analyser Mode: FRR Fitting
OMMT-1 Envelope curve
Resolution: Medium curve
402.5 eV
Magnification: High
Energy Range: X 1 Quaternary-N,
Exciting Source: Mg OMMT-2 401.687 eV
Region 04: N1S 401.5 eV
B.E. 415.00-395.00 eV
ChargeShift: 4.100 eV 399.800 eV
500mS per 0.10eV
Across Scan for 12 times
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2700
411 409 407 405 403 401 399 397 395 393 391
411 409 407 405 403 401 399 397 395 393 391
Binding Energy (eV)
Binding Energy (eV)
Fig. 7. High energy resolution XPS spectrum for nitrogen in
OMMT-1 and OMMT-2 Fig. 8. Processing of high energy resolution XPS spectrum for nitro-
gen in OMMT-2

sults and the example shown in Fig. 5, it can be concluded that
some organic functional groups, such as carboxylic, hydroxyl,
ketone, etc., do not exist in the carbon chains of two organic
cations in both nanoclays. The chemical state of carbon in the
OMMT-1 and the OMMT-2 mainly exists in the form of C u C.
However, because the photoelectron binding energies of carbon in
the form of C u C and C v C are very close, it is impossible to
decide the existence of C v C through the XPS.
The comparison of the nitrogen spectra for the OMMT-1 and
the OMMT-2 is shown in Fig. 7. It was found that there is a
significant difference in the position and configuration of the ni-
trogen peaks. The nitrogen spectrum for the OMMT-1 is almost
symmetrical with a peak at 402.5 eV, which means that just one
chemical state of nitrogen exists. Compared with the spectrum for
the OMMT-1, the nitrogen spectrum peak for the OMMT-2 shifts
to the position at 401.5 eV and shows a clear asymmetric curve.
The photoelectron BE of nitrogen in the form of quaternary am-
monium is within the range of 401.5 to 402.5 eV 共Briggs 1998兲. It
can be concluded that both nanoclays contain quaternary ammo-
nium cation, the most common surfactant cation used in the modi-
fication of the MMT. However due to the asymmetry of the
nitrogen XPS spectrum for the OMMT-2, it is also supposed that
TG and DSC
The thermal behavior of two nanoclays was examined by simul-
taneous DSC-TG analysis. TG and DTG 共derivative thermo-
gravimetry兲 curves of two nanoclays are shown in Figs. 9 and 10.
Thermal decomposition of the OMMT is considered in three re-
gions at the studied temperature range. As shown in TG curves,
initial mass loss is dominated by the volatilization of absorbed
water below 200° C 共Region I兲. Subsequently, the decomposition
of organic surfactant cations in the OMMT takes place from 200
to 500° C 共Region II兲. Dehydroxylation of the layered silicate
occurs from 500 to 700° C 共Region III兲 共Huskic et al. 2008兲. It is
meaningless to observe the thermal behavior of the OMMT at the
elevated temperature over 700° C. Because the conventional ser-
vice environment of nanoclay modified bitumen is just below
100 ° C. However, the Region II for the decomposition of organic
substance is meaningful, for the thermal behavior in this region
has some implications for the thermal stability during the manu-
0.1
TG curve for OMMT-1
100
0.05
DTG curve for OMMT-1
Derivation of mass loss [%/min]

other chemical states of nitrogen are possible. So the nitrogen 0

XPS spectrum may contain other unresolved peaks. With the pro- 90
Mass loss [%]

fessional spectrum analysis software XPSpeak4.1, two peaks Free water

-0.05
were obtained at 401.687 and 399.8 eV, and their fitting curves
are combined close to the envelope as shown in Fig. 8. The pho- 80 -0.1
toelectron BE of nitrogen in the form of amine, amide, nitrile, Dehydroxylation

carbamide, etc., is in the range of 399 to 400 eV 共Briggs 1998兲. -0.15

However, the above analysis of the carbon spectrum indicates that 70
the ketone 共RCOR⬘兲 does not exist in the carbon chains. So the -0.2
existence of amides 共RCONH2兲 and carbamide 关CO共NH2兲2兴 is not Decomposition of organic matter
realistic. In order to detect the accurate molecular structure of the 60 -0.25
organic surfactant cations, nuclear magnetic resonance 共NMR兲 is 0 200 400 600 800 1000
necessary in a next study. It could detect the existence of C v C Temperature [ºC]

bonds and a more accurate estimate the molecular structure of the

organic surfactant. Fig. 9. TG and DTG curves for OMMT-1

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J. Mater. Civ. Eng. 2010.22:794-799.

 0.03 7
TG curve for OMMT-2
100 OMMT-1
DTG curve for OMMT-2
0 6
OMMT-2

Derivation of mass loss [%/min]

90 -0.03
Free water
Mass loss [%]

Enthalpy [mW/mg]
4
-0.06
Dehydroxylation
80
3
-0.09
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2
70
-0.12
Decomposition of organic matter
1

60 -0.15
0 200 400 600 800 1000 0
Temperature [ºC]

-1
Fig. 10. TG and DTG curves for OMMT-2
0 200 400 600 800 1000
Temperature [ºC]

facture of the nanoclay modified bitumen, and the possible utili- Fig. 11. DSC curves for OMMT-1 and OMMT-2
zation of the OMMT as a flame retardant for the bitumen.
From the DTG curves it seems that the evaporation rate of
water for both nanoclays reaches the maximum between 40 and organic surfactant cation in the OMMT-1 shows a better thermal
60° C. Although the OMMT is conventionally considered organo- stability than the organic surfactant in the OMMT-2.
philic because of the addition of organic cations, water absorption
still occurs on the exterior of the aggregates and along the hydro-
philic layer edges, and depends on environmental conditions, Conclusions
such as relative humidity 共Xie et al. 2001兲. TG curves indicate
that a small amount of water of approximately 1% by weight is Some properties of two bitumen nanoclay modifiers, OMMT-1
contained in the OMMTs used in this study. Note that the polarity and OMMT-2, were studied. First of all, the X-ray photoelectron
of water would negatively influence the interaction between the spectroscopy was adopted to characterize the composition of the
nanoclay and bitumen. Therefore certain drying treatment for the organic surfactant cations in the nanoclay. It could be concluded
OMMT before the nanocomposite synthesis is necessary to ensure that the surfactants were not the same. The surfactant in the
the reproducibility of an experimental result. OMMT-1 only contained quaternary ammonium. The other sur-
As shown in DTG curves between 200 and 500° C, organic factant in the OMMT-2 showed two states of nitrogen: quaternary
substances in the OMMT-1 and the OMMT-2 exhibit different ammonium and probably amine or nitrile. In general, C u C
decomposition fashion. There are two overlapping DTG peaks for bonds could be detected very well for the two surfactants, and
the OMMT-2, however, only a sharp one for the OMMT-1 in this there were no other functional groups, such as carboxylic, hy-
region. This results from different decomposition mechanisms be- droxyl, ketone, etc. However, it was unclear if the surfactants had
tween organic substances in the OMMT-1 and the OMMT-2, re- C v C bonds. DSC-TG analysis was used to determine the ther-
spectively. In general, thermal decomposition of organic mal stability of the OMMTs. Production of modified bitumen nor-
molecules occurs at the site with the smallest bond dissociation mally occurs at temperatures in excess of 150° C. Although the
energy 共Xie et al. 2001兲. The bond energies within organic cations surfactants in the two nanoclays showed different thermal behav-
decreased in the order of 400–415 kJ/mol for C u H, 390 kJ/mol ior, at temperatures below 200° C, no problems are expected.
for N u H, 345–355 kJ/mol for C u C, and 290–315 kJ/mol for Based on the results other techniques, such as NMR, are recom-
C u N 共March 1992兲. On the basis of the high energy resolution mended to further analyze the composition of the surfactants, and
XPS spectrum for nitrogen in the OMMT-2, the change of the its impact on the interaction of the nanoclay with the bitumen
chemical state of the nitrogen could influence the C u N bond must also be studied further.
energy and cause a different decomposition process compared to
that of the OMMT-1. From the TG curve in Region II, it can be
calculated that the content of organic matter is 21.8 and 16.9% by Acknowledgments
weight for the OMMT-1 and the OMMT-2, respectively.
The OMMTs are characterized by the exothermic DSC peak in The writers appreciate the cooperation between the Delft Univer-
Fig. 11. The first endothermic peak on the DSC curves is assigned sity of Technology, the Wuhan University of Technology, and
to the evaporation of the water. Corresponding to the DTG Kuwait Petroleum Research and Technology.
curves, there are also two exothermic peaks on the OMMT-2 DSC
curve and one on the OMMT-1 DSC curve in Region II. Exother-
mic peaks generally involve some oxidation reactions with vola- References
tile oxidation products, such as CO2, H2O, and N2. The
temperature at the first exothermic peak in the OMMT-2 DSC Alexandre, M., and Dubois, P. 共2000兲. “Polymer-layered silicate nano-
curve is lower than that in the OMMT-1. This indicates that the composites: Preparation, properties and uses of a new class of mate-

798 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / AUGUST 2010

J. Mater. Civ. Eng. 2010.22:794-799.

 rials.” Mater. Sci. Eng., 28, 1–63.
Briggs, D. 共1998兲. Surface analysis of polymers by XPS and static SIMS,
Cambridge University Press, West Nyack, N.Y.
Carleya, A. F. 共2001兲. Surface analysis: X-ray photoelectron spectros-
copy, Elsevier, Oxford, U.K.
Giannelis, E. 共1996兲. “Polymer layered silicate nanocomposites.” Adv.
Mater., 8, 29–35.
Gile, D. B. 共2006兲. “Effects of nanoclay modification on rheology of
bitumen and on performance of asphalt mixtures.” MS thesis, the
Delft Univ. of Technology, The Netherlands.
Halstead, W. J. 共1985兲. “Relation of asphalt chemistry to physical prop-
Downloaded from ascelibrary.org by UEM - Universidade Estadual De Maringa on 05/12/14. Copyright ASCE. For personal use only; all rights reserved.
erties and specification.” Proc. Assoc. Asphalt Paving Technol., 54,
91–117.
Huskic, M., et al. 共2008兲. “Modification of montmorillonite by quaternary
polyesters.” J. Non-Cryst. Solids, 354, 3326–3331.
Kato, M., et al. 共1997兲. “Synthesis of polypropylene oligomer-clay inter-
calation compounds.” J. Appl. Polym. Sci., 66, 1781–1785.
Koo, H. J. 共2006兲. Polymer nanocomposites: Processing, characteriza-
tion, and applications, McGraw-Hill, New York.
Liu, G., et al. 共2010兲. “Influence of sodium and organo-montmorillonites
on the properties of bitumen.” Appl. Clay Sci., in press.
Lu, X., and Isacsson, U. 共1997兲. “Rheological characterization of styrene-
butadiene-styrene copolymer modified bitumens.” Constr. Build.
JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / AUGUST 2010 / 799
J. Mater. Civ. Eng. 2010.22:794-799.
Mater., 11, 23–32.
March, J. 共1992兲. Advanced organic chemistry: Reactions mechanisms
and structure, 4th Ed., Wiley, New York.
Morgen, P., and Mulder, A. 共1995兲. The shell bitumen industrial hand-
book, Shell Bitumen, Surrey, England.
Okada, A., and Usuki, A. 共2006兲. “Twenty years of polymer-clay nano-
composites.” Macromol. Mater. Eng., 291, 1449–1476.
Petersen, J. C. 共1984兲. “Chemical composition of asphalt as related to
asphalt durability: State of the art.” Transport Research Record. 999,
Transportation Research Board, Washington, D.C.
Pinnavaia, T. J., and Beall, G. W. 共2006兲. Polymer-clay nanocomposites,
Wiley, Chichester, U.K.
Pusch, R., and Yong, N. R. 共2006兲. Microstructure of smectite clays and
engineering performance, Taylor & Francis, London.
Rjeb, M., et al. 共2005兲. “TG and DSC studies of natural and artificial
aging of polypropylene.” Physica A, 358, 212–217.
Rostler, F. S., and White, R. M. 共1962兲. “Composition and changes in
composition of highway asphalts, 85–100 penetration grade.” Elec-
tron. J. Assoc. Asphalt Paving Technol., 31, 35–89.
Xie, W., et al. 共2001兲. “Thermal degradation chemistry of alkyl quater-
nary ammonium montmorillonite.” Chem. Mater., 13, 2979–2990.
Yu, J. Y., and Xuan, Z. 共2007兲. “Preparation and properties of montmo-
rillonite modified asphalts.” Mater. Sci. Eng., A, 447, 233–238.