Fuel 88 (2009) 1324–1328

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Fuel
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Improvement of bitumen performance with epoxy resin

Meltem Çubuk a, Metin Gürüa *, M. Kürsßat Çubuk b
a
Gazi University, Eng. and Arch. Fac., Chem. Eng. Depart. 06570, Maltepe-Ankara, Turkey
b
Gazi University, Eng. and Arch. Fac., Civil Eng. Depart. 06570, Maltepe-Ankara, Turkey

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

Article history: This paper studies the modification of petroleum bitumen with epoxy resin. Different amounts of epoxy
Received 8 April 2008 were doped into bitumen with 50/70 penetration grade and variations in viscosity as a function of tem-
Received in revised form 16 December 2008 perature and additive concentration were determined. The effects of the epoxy additive were examined
Accepted 17 December 2008
by rheometer, penetration, softening point, DSR (dynamic shear rheometer), DSC (differential scanning
Available online 18 January 2009
calorimeter), RTFOT (rolling thin film oven test), PAV (pressure aging vessel), BBR (bending beam rheom-
eter) and surface tension tests. Adhesion and stability of bitumen aggregate mixtures prepared using ori-
Keywords:
ginal and modified bitumen were compared using Nicholson stripping and Marshall tests. The optimum
Modified bitumen
Epoxy
dosage of the additive yielding the best rheological and performance properties was found to be 2% (w/
Rheology w). Appreciable decrease in the formation of rutting, bleeding, stripping and cracking of modified bitu-
Adhesion men may be obtained through epoxy addition.
Stability Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction mixture by 0.1% (w/w) to prevent stripping [1]. Use of domestic

Bitumen, obtained from petroleum refinery bottoms is a ther-
moplastic containing bituminous materials and finds widespread
use in sealants, binders, waterproof coatings and paving materials
and is preferred for its low cost, inherent cohesive nature, rheolog-
ical properties and thermal resistance. Flexible paving used in the
top layer of the roads is formed from bituminous binders and
aggregates. This layer is exposed to a wide range of temperatures
and great stresses due to seasonal change and heavy truck traffic.
It tends to crack at low temperatures and its cohesive strength de-
creases at elevated temperatures. Problems related to deforma-
tions such as formation of rutting, cracking and stripping are
becoming more severe as traffic loads increase. Performance and
stability improvements of this top paving layer would improve
the quality of roads and appreciable savings would result through
decreased maintenance costs. Since it is the material properties of
bituminous binders and the aggregates that determine the quality
of the paving, improving this quality by various modifications of
bitumen is widely attempted.
Bitumen can be modified through doping with additives such as
surfactants and polymers. Surfactants, both cationic and anionic
are generally used as antistripping agents. Cationic surfactants
are appropriate for electronegative materials such as silex, quartz
and granite. Gürü had reported on the addition of manganese abi-
etate, an anionic surfactant, to electropositive bitumen material
* Corresponding author. Tel.: +90 312 2317400/2555; fax: +90 312 2308434.
E-mail address: mguru@gazi.edu.tr (M. Gürü).
incinerator ash as an aggregate in asphalt concrete was evaluated
by Garrick and Chan, who showed that a mix containing up to
32% (w/w) incinerator ash yielded acceptable parameters on the
Marshall tests. This mix requires a higher than usual asphalt con-
tent and is prone to stripping [2]. Polymers are used as additives
with the intent to improve the performance of binders. Polymers
may be classified into four main groups: thermoplastics, rubbers,
thermosetting plastics and block copolymers.
Maleic anhydride was reported to significantly improve both
the low temperature cracking resistance and the high temperature
cohesive strength of bitumen. In the same study, styrene butadiene
styrene copolymer was found to improve the low temperature
behavior of bitumen, but not its high temperature cohesive
strength and flux resistance [3]. Aged modified bitumen with sty-
rene butadiene styrene also showed an improvement in rheologi-
cal properties [4]. Two penetration grade bitumens can be
modified by styrene butadiene styrene [5]. Very good stability re-
sults were obtained with a blend containing 1% of EVA copolymer
[6]. Improvements were also observed with atactic polypropylene,
ethylene–propylene copolymer and ethylene–propylene rubber
[7]. Amorphous polyalphaolefin, cellulose fiber, polyolefin and sty-
rene butadiene styrene were used as modifiers in asphalt mixtures
[8]. Styrene butadiene styrene addition into the binder can delay
aging. [9]. Promising results were obtained by doping bitumen
with high density polyethylene [10]. Modification of bitumen with
EVA recycled polymer may enhance its service properties by
increasing its viscosity [11]. In a similar study, viscosity of base as-
phalt modified by styrene butadiene styrene and ethylene–vinyl
acetate polymers was investigated and discussed [12].

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.12.024
 M. Çubuk et al. / Fuel 88 (2009) 1324–1328 1325

Table 1 surface energy tests. Adhesion and stability properties of bitumen

Chemical and physical properties of the bitumen with 50/70 penetration. aggregate mixtures are studied with the Nicholson stripping test
Property Data and the Marshall test and compared to those of unmodified
Penetration, 25 °C, 100 g, 5 s, 0.1 mm 62 bitumen.
Solubility in trichloroethylene (%) 99.7
Softening point (°C) 49.2
Flash point (°C) 260+ 2. Materials and methods
Viscosity, 135 °C (Pa s) 0.280
Asphaltene (w/w)% 20.75 50/70 penetration grade bitumen widely used as pavement
Aromatics (w/w)% 53.72
material was obtained from Aliağa Petroleum Refinery and used
Saturated hydrocarbons (w/w)% 6.55
Resin (w/w)% 18.98 throughout the study. Properties of the bitumen used in all exper-
iments are given in Table 1.
Properties and chemical open formula of the BPA type epoxy
resin used in all experiments as the modifying agent are given in
Table 2
Table 2 and Fig. 1.
Properties of epoxy resin.
The experimental set-up consisted of an open reactor, oil bath
Status of physical Liquid with a thermostat and a mixer. Modified bitumen was obtained
Equivalent weight of epoxy (g/eq) 184–190 by placing it in an oil bath preheated to 150 °C in an oven. Epoxy
Viscosity (cps/25 °C) 12,000–15,000 was added to the hot bitumen at ratios varying between 1% (w/
Colour (Gardner) 1 max.
w) and 6% (w/w) and mixed for 1 h. This sample was then main-
Flash point (°C) 150 "
Hdrolyzable Chlorine (ppm) 1000 "
tained at 150 ± 2 °C in an oven for 1 h and at 20 ± 1 °C for 1 day. Ef-
Density (25 °C) 1,16 fects of epoxy dosages on the viscosity of modified bitumen were
measured according to the ASTM D 4402 standard at 19 ± 1 of
shear rate by means of a Brookfield DV-III Rheometer. Transition
Waste polymer and rubber material may also be used as modi- glass temperature tests of bitumens were done with a Perkin–El-
fying agents in bituminous materials. The modification of bitumen mer DSC. Experiments were carried out at the heating rate of
with four different types of waste polymers, namely EVA, EVA/ 50 °C/min under the running of nitrogen gas. Conventional tests
LDPE blend, crumb tire rubber and ABS has been investigated such as penetration (ASTM D 5), softening points (ASTM D 36)
[13]. Rheological characteristics of ground tire rubber-modified and rolling thin film oven tests (ASTM D 2872) were carried out
bitumen were determined and compared with unmodified and on bitumens with and without epoxy by Krebs Elec. & MFG, Sur
polymer modified (SBS) bitumens [14]. In a similar study, flexible Berlin RKA2 and CS 325-A (James Cox.&Sons Inc.), respectively.
bituminous material was obtained through the modification of Surface energies of samples were automatically determined using
bitumen with tire rubber waste [15]. contact angle method by means of KRUSS DSA 100 apparatus. Pres-
The purpose of the present study is to investigate the effects of sure aging vessel tests was carried out using a Buttler PAV appara-
epoxy addition on the rheology of modified bitumen through vis- tus (AASHTO PP1). A Thermoelectric BBR (Canon Instrument
cosity, penetration, softening point, DSR, DSC, RTFOT, PAV, BBR, Company) (AASHTO TP1) and a CVO 100 ADS DSR Rheometer

Fig. 1. Chemical open formula of BPA type epoxy resin.

4.0

3.5

3.0
Viscosity (Pa.s)

2.5

2.0

1.5

1.0

0.5

0.0
0 1 2 3 4 5 6
Epoxy Resin (%)
90 °C 120 °C 150 °C
100 °C 130 °C 160 °C
110 °C 140 °C 170 °C

Fig. 2. Variation of bitumen viscosity as a function of epoxy concentration

1326 M. Çubuk et al. / Fuel 88 (2009) 1324–1328

(Bohlin Instrument) (AASHTO TP5) apparatus were used for as-
phalt rod strength and dynamic shear stress tests. In order to
determine the adhesion properties of asphalt-aggregate mixtures,
the Nicholson stripping test was carried out on the non-compacted
mixtures with and without epoxy. At the end of the test, the non-
stripped aggregate surface related to total aggregate surface has
been given as the data of resistance to stripping. Additionally, Mar-
shall Stability test (ASTM D 1559) were applied on the compacted
mixtures with and without epoxy. Behavior of modified bitumen
and asphalt-aggregate systems with varying epoxy concentrations
and temperatures were determined.
3. Results and discussions
Viscosity was the first parameter to be investigated for bitumen
as a function of additive concentration and temperature, due to its
importance in processing, aging and service. Viscosity was mea-
sured with epoxy concentrations of 0–6% by weight. As is evident
from Fig. 2, viscosity increased exponentially at below the 110 °C
with increasing epoxy concentration up to 2% (w/w), due to the in-
creased cohesion of bitumen at low epoxy concentrations. How-
ever, at higher concentrations, a noticeable decrease, due to the
domination of epoxy was observed. Above 110 °C, the effect of
the additive on bitumen viscosity decreases with increasing tem-
perature. On the other hand, viscosities of bitumen with and with-
out epoxy decreased exponentially as a function of temperature, as
can be seen in Fig. 3. This is the expected result of the Newtonian
property of bitumen. The viscosity increase at environmental tem-
peratures obtained through (2–3)%wt epoxy addition will prevent
rutting arising from heavy truck traffic. Expected bitumen–poly-
mer reactivity is to form the cross linking structure and leads to
the increasing of bitumen viscosity. At higher temperatures, dop-
ing does not increase viscosity due to the poor cross linking bonds.
Therefore, doping does not pose a problem at asphalt plant pro-
cessing temperatures. The epoxy addition ratio (2%) which corre-
sponds to the maximum viscosity below 110 °C, was chosen as a
constant parameter for the experiments that followed. Styrene
butadiene styrene doping was also used to increase the viscosity
of modified bitumen. [16].
After the logarithmic viscosity change with temperature was
plotted for each epoxy concentration, the change of lnl as a func-
tion of 1/T was drawn, as shown in Fig. 4. The forward activation

4.5

4.0

3.5
Viscosity (Pa.s)

3.0

2.5

2.0

1.5

1.0

0.5

0.0
90 100 110 120 130 140 150 160 170
Temperature ( °C)
Pure bitumen 0% Epoxy resin1% Epoxy resin 2%
Epoxy resin 3% Epoxy resin 4% Epoxy resin 5%
Epoxy resin 6%

Fig. 3. Variation of bitumen viscosity as a function of temperature.

2.0

1.5

1.0

0.5

0.0
y = 7.2947x - 19.148
lnμ

2.26 2.31 2.36 2.41 2.46 2.51 2.56 2.61 2.66 2.71 2.76
-0.5
y = 7.9038x - 20.494
-1.0 y = 7.5482x - 19.401

-1.5 y = 7.54x - 19.443

y = 6.9998x - 18.25
-2.0
y = 6.7673x - 17.684
-2.5
y = 6.6081x - 17.321
-3.0
[1/T(K)]∗10
3

% 0 Epoksi % 2 Epoksi % 4 Epoksi

% 6 Epoksi
% 1 Epoksi % 3 Epoksi % 5 Epoksi

Fig. 4. Variation of bitumen lnl data as a function of 1/T for each concentration.
 M. Çubuk et al. / Fuel 88 (2009) 1324–1328 1327

energy of viscosity change was determined from the slope of the
logarithmic line for each concentration using the Arrhenius Eq. (1).
m ¼ AeEa=RT
As can be seen from Table 3, activation energy (Ea) of bitumen
decreases below 110 °C with increase in epoxy concentration up
to 2% (w/w). It is known that crystallization and cross linking of
modified bitumen increases, resulting in a hardened structure
due to decreasing activation energy [7].
In order to investigate the effects of epoxy resin curing period
on the variation of viscosity, viscosities of modified bitumen with
Table 3
Intersection and activation energy data of bitumen.
Epoxy additive (%) A (Pa s)
0 4,832  109
1 1,257  109
2 3,752  109
3 3,597  109
4 1,186  108
5 2,089  108
6 3,003  108
90°C 110°C 130°C 150°C
100°C 120°C 140°C 160°C
5.0
4.5
4.0
2% (w/w) and 3% (w/w) epoxy additive were measured as a func-
tion of time up to 28 days. As shown in Fig. 5, below 110 °C viscos-
ity change of modified bitumen with 2% epoxy reaches the
ð1Þ maximum value on the fourteenth day and then starts to decrease.
This curve flattens at higher temperatures and the maximum is no
longer present. Viscosity variation after the second day remains
steadily above 140 °C. For the 3% epoxy mixtures, viscosity change
of modified bitumen below 110 °C reaches the maximum value on
the 21st day, and then starts to decrease. This shows that the cur-
ing period increases with increasing of epoxy concentration.
Penetration and softening point tests were applied to the origi-
nal and to the 2% epoxy modified bitumen. Modification decreased
penetration from 62 to 54. Softening point increased from 49.2 °C
to 52.2 °C. Transition glass temperature of modified bitumen with
2% epoxy increased from 22.50 °C to 13.85 °C. Decrease in pen-
etration, increase in softening point and transition glass tempera-
Ea (kJ mol1) tures are thought to arise from a hardening in modified bitumen.
60,648 In a similar study, polyolefin and EVA additives decreased the pen-
65,712 etration and increased the softening point of bitumen [17,18].
62,756
Increasing of the softening point was reported to lead to a decrease
62,688
58,196 in rutting [19].
56,263 In order to determine the effect of doping on stripping durabil-
54,940 ity of asphalt-aggregate, surface energy of bitumen with and with-
out epoxy were measured and 30.90 and 32.00 mN/m were
observed. Percent stripping with and without epoxy were found
to be (0–5)% and (50–55)% in the Nicholson stripping test. It is pos-
170°C
1300
Marshall Stability (kg)

3.5 1200
Vscosity (Pa.s)

3.0
1100
2.5
2.0
1000
1.5
1.0 900
0.5
800
0.0
0 7 14 21 28 2.5 3 3.5 4 4.5 5

Time (Day) Bitumen %

Pure bitumen Epoxy Resin 2%
Fig. 5. Variation of viscosity as a function of curing period for modified bitumen
with 2% epoxy. Fig. 6. Variation of Marshall Stability values as a function of bitumen percent.

Table 4
Superpave test results of original and modified bitumen.

Bitumen Status of Bitumen Applied test Result Limits of specification

Pure bitumen Original Viscosity, 135 °C 0.280 Pa s 3 Pa s
20 rpm, 18,6 SR
DSR (G*/sind) 0.99817 kPa 1 kPa
10 rad/s, 64 °C (min.)
RTFOT is executed DSR (G*/sind) 2.3915 kPa 2.2 kPa
10 rad/s, 64 °C (min.)
PAV is executed DSR (G*  sind) 4099 kPa 5000 kPa
10 rad/s, 25 °C (max.)
BBR 60 sn, S 148 MPa 300 MPa (max.)
12 °C m 0.318 0.300 (min.)
Modified bitumen with 2% epoxy resin addition Original Viscosity, 135 °C 0.435 Pa s 3 Pa s
20 rpm, 18.6 SR
DSR (G*/sind) 1.2223 kPa 1 kPa
10 rad/s, 64 °C (min.)
RTFOT is executed DSR (G*/sind) 3.08655 kPa 2.2 kPa
10 rad/s, 64 °C (min.)
PAV is executed DSR (G*  sind) 3010 kPa 5000 kPa
10 rad/s, 25 °C (max.)
BBR 60 s, S 218 MPa 300 MPa (max.)
12 °C m 0.388 0.300 (min.)
1328
20
Pouring values (1/100")
15
10
5
2.5 3 3.5 4 4.5
Bitumen %
Pure bitumen Epoxy Resin 2%
Fig. 7. Variation of pouring values as a function of bitumen percent.
sible to conclude that doping increases the adhesion of the asphalt-
aggregate system and stripping is prevented through doping with
2% (w/w) epoxy resin. Strength of the asphalt concrete increases
and water penetration is blocked. Gürü had also recommended
manganese abietate as an antistripping agent [1].
Test results and requirement limits of RTFOT, PAV, DSR and BBR
are given in Table 3. Test results of modified bitumen remained
within the requirement limits. G*/sind values of bitumen have to
be higher than 1 and 2.2 kPa to resist rutting. G*/sind values of
bitumen given in Table 4 show that epoxy addition to bitumen de-
creases rutting. G*sind value as a fatigue cracking factor of aged
bitumen was limited at a maximum 5000 kPa. It is seen that 2%
(w/w) epoxy addition to bitumen offers the best outcome in
decreasing fatigue cracking. Creep hardness in the BBR test was
limited at a maximum of 300 MPa in the superpave requirement.
Creep hardness values of bitumen with and without additive
stayed in the required limits. M values which indicate creep hard-
ness as a function of time were required to be higher than 0.300.
Our results were consistently above this value. Superpave tests
indicate a decrease in rutting in modified bitumen by 22%, and in
modified aged bitumen by 29%. The decrease in fatigue cracking
is 27%.
The results for Marshall Stability and pouring of original and
modified bitumen are presented in Figs. 6 and 7, respectively. Var-
iation of Marshall Stability as a function of percent bitumen for ori-
ginal and modified bitumen with 2% (w/w) epoxy is presented in
Fig. 6. Addition of 3% epoxy into the bitumen increased the stability
from 1044 to 1199. Maximum Marshall Stability was found at 3%
bitumen ratio and decreased with further increase in bitumen. Sta-
bility of the mixture depends on the internal friction and cohesion
between aggregates and the binder. Addition of epoxy increases
the stability by increasing cohesion and shear stress. Previous re-
search had indicated that the stability of polymer modified bitumi-
nous sample was higher than the stability of the original
bituminous sample [8,20]. As seen from Fig. 7, generally pouring
values of epoxy modified bitumen are less than those of the origi-
nal bitumen. Elastic to plastic behavior transition point is also ele-
vated with the addition of epoxy. The minimum pouring value has
been recorded at 3% bitumen and increased with increasing
amount of bitumen. Therefore, preparation of superpave with 2%
(w/w) epoxy addition will resist to the formation of rutting, col-
lapse, fatigue cracking, thermal cracking and creep hardness under
the heavy traffic.
M. Çubuk et al. / Fuel 88 (2009) 1324–1328
4. Conclusion
Viscosity, softening point, transition glass temperature and sta-
bility increase and heat sensitivity, surface energy, penetration and
stripping decrease when bitumen is modified with the addition of
2% epoxy. Therefore, modified bitumen can be recommended for
use in hot climates, humid regions, in roads with heavy traffic
loads, at road curves and at bus stations to prevent rutting, bleed-
ing, cracking, stripping and aging. Low cost and lower operating
5
and maintenance requirements offer additional advantages for
superpave applications. Waste epoxy powder could be substituted
for epoxy resin for further economy and environmental advantage.
Acknowledgement
This study was supported by DPT (the State Planning Organiza-
tion of Turkey) under project number 2001K120590. The authors
are grateful to the DPT for financial support and Gazi University
for the provision of laboratory facilities.
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