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Polymer modified bitumen

Article  in  Materials Research Innovations · March 2012

DOI: 10.1179/1433075X11Y.0000000021

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REVIEW
Polymer modified bitumen
V. O. Bulatović*1, V. Rek1 and K. J. Marković2
Standard methods of characterisation of bitumen (BIT) and polymer modified bitumen (PMB) do
not provide sufficient information. We propose to rely on determination of rheological properties
which are much more informative. Along theses lines, we have determined rheology before and
after the rolling thin film oven test. The materials studied were BIT, BITzlinear (L), styrene–
butadiene–styrene (SBS), block copolymer, BITzradial (R) and SBS copolymer. The rheological
properties of the modified binders are characterised using a dynamic shear rheometer, over wide
ranges of temperatures at a fixed traffic frequency of 10 rad s21. The SBS block copolymers
increase the elasticity of the BIT at high temperatures and contribute to a better flexibility at low
temperatures. Polymer modified bitumens have higher resistance to permanent deformation. After
aging, the hardening of BIT and PMBs occurred and the elastic response decreases as a
consequence of degradation. The determined rheological properties are in agreement with the
results of conventional tests.
Keywords: Polymer modified bitumen, Rheological properties, DSR, SBS-L, SBS-R, Thermooxidative degradation

Introduction
Bitumen (BIT) is used in road industry as a binder for
asphalt. Roads must withstand changes in temperature
in the range of .80uC and handle heavy loads without
cracking at low temperatures, and also must provide
resistance to the occurrence of permanent deformation
of asphalt mixtures at high temperatures.1 Today’s
climate in addition to the increases demands that are
placed on the BIT as a binder affect the configuration
and geometry of the vehicle tire. As BIT has not the
temperature resistance for high and low temperatures, it
softens in summer and cracks in winter.2 In order to
produce BIT with improved properties, i.e. wider
temperature range in use as well as better rheological
properties, polymers are used. Polymers with high
viscoelasticity, higher creep and recovery under the
traffic frequency, enhance BIT resistance to permanent
deformation. Polymer modified bitumens (PMBs) are
generally considered to provide a prolonged life or
enhanced pavement performance of BITs.2–6 In Europe
BIT and PMBs are still defined on conventional tests
such as penetration, ring and ball temperature. It is not
enough to carry out conventional BIT tests to give an
insight into rheological properties.7 The USA adopted
rheological specifications at the end of the Strategic
Highway Research Program (SHRP) in the early 1990s,
well known as the performance grade.7–9 The perfor-
mance grade classification includes two methods: one
characterising the binder in the high temperature range,
1
Faculty of Chemical Engineering and Technology, University of Zagreb,
Marulićev trg 19, 10000 Zagreb, Croatia
2
Institute of Civil Engineering Croatia d.d, J. Rakuše 1, 10 000 Zagreb,
Croatia
*Corresponding author, email vocelic@fkit.hr
the other is for low temperature range. The idea behind
this criterion is that too fluid a binder leads a risk of
permanent deformation, and that too rigid a binder
leads a risk of cracking for the pavement. Within the
SHRP, the permanent deformation of BIT and PMB is
correlated to viscoelastic functions, shear complex
modulus, G* and phase angle d with the equation G*/
sin d.10 Therefore, BITs with a high complex modulus
and a high degree of elasticity produced pavements with
a low tendency for permanent deformation. The most
commonly used method of rheological testing of BIT
and PMB, included in SHRP is the dynamical mechan-
ical method using the oscillatory type testing with
dynamic shear rheometers (DSRs).4,11,12 Polymers with
the higher glass transition compared with BIT, thermo-
plastic, enhance BIT resistance to high temperatures,
while polymers with the lower glass transition, elasto-
mers, enhance BIT resistance to low temperatures.
Bitumen modified with thermoplastic elastomers and
styrenic block copolymers due to their ability to
combine both elastic and thermoplastic properties has
better temperature resistance to high and low tempera-
tures than BIT.
One of the most important modifiers in the styrenic
block copolymers is styrene-butadiene-styrene (SBS)
block copolymer.2–6,11,12 The structure of SBS copoly-
mers consists of SBS three block chains, having a two-
phase morphology of spherical glassy polystyrene block
domains within a matrix of rubber polybutadiene.12,13
The formation of a PMB is based on the dissolution and/
or fine dispersion of polymer in BIT and on the
compatibility of the polymer–BIT blend.
The elastomeric phase of the SBS copolymer swells in
the maltene phase of BIT and a continuous polymer
network is formed through the PMB, which influences
the viscoelastic properties of PMB.12–15

ß W. S. Maney & Son Ltd. 2012

Received 30 May 2011; accepted 17 September 2011
DOI 10.1179/1433075X11Y.0000000021 Materials Research Innovations 2012 VOL 16 NO 1 1
 Bulatović et al. Polymer modified bitumen

Bitumen aging is one of the principal factors causing
the deterioration of asphalt pavements. BIT is aging
during production, application and their service life.3
Aging is a very complex process in BIT and the com-
plexity increases when polymer bitumens are involved.
In BIT aging oxidation and physical hardening are
present.13
The factors affecting BIT and PMB aging in-
clude characteristics of BIT and composition of BIT
and PMB, polymer content, structure and phase
interactions.4 The same factors influence the rheological
properties and temperature range in use.
In this paper, the influence of the content and
structures of SBS copolymers, as a BIT polymer
modifier on the rheological properties of PMBs in a
set range of temperatures under defined traffic frequen-
cies with a DSR, was researched. The rheological
properties of unaged PMBs and PMBs after artificial
termooxidative aging in the rolling thin film oven test
(RTFOT) were determined. Two SBSs were used: one
with a linear structure (SBS-L), and the other with a
radial structure (SBS-R).
Experimental
Materials
The investigations are carried out with the 70/100
penetration grade base BIT. The source of BIT is INA
Refinery Croatia, Rijeka, Croatia.
Two SBS block copolymers are used in this study: one is a
linear SBS (SBS-L), commercial grade Kraton D 1101, with a
content of 31 wt-% polystyrene and the other is a branched
block copolymer (SBS-R), commercial grade Kraton D 1184,
with a content of 30 wt-% polystyrene, fabricated by the Shell
Chemicals Company, Wesseling, Germany.
Five SBS-L PMBs and five SBS-R PMBs are
produced with various contents of polymer (Table 1).
Sample preparation
All the PMBs were prepared using a Silverson L4R
mixer of 1500 min21. First, the base BIT is thoroughly
heated (160uC) and stirred for y2 h to obtain homo-
geneity and is then poured into 1 L aluminium cans. The
cans of BIT were then heated to 180–185uC and stirred
for 10 min before adding the polymer. A given part of
SBS was then added slowly into the BIT under high
speed stirring for 4 h until the blend became essentially
homogenous. A constant temperature was kept while the
mixing process continued.
After completion, the blends were removed from the
aluminium cans and divided into small containers,
covered with aluminium foil and stored for testing at
ambient temperature.
Measurements
Conventional tests
The base BIT and PMBs were subjected to the following
conventional BIT tests according to standards: the
penetration test (HRN EN1426), the ring and ball
technique to determine the softening point temperature
(HRN EN1427), the elastic recovery test (HRN EN13398)
and the Fraass breaking point test (HRN EN12593/01).
The results of these are listed in Table 2.
Furthermore, the penetration index (PI) was calcu-
lated from the penetration test and the softening point
was determined from the ring and ball test to predict
temperature susceptibility. A classical approach to the
PI calculation is given in ‘Shell bitumen handbook’,
which is shown by the following equation

Table 1 Composition of samples PI~1952{500|log (pen25 ){

Sample 20SP=50|log (pen25 ){SP{120 (1)

where pen25 is the penetration at 25uC and SP is the
SBS-L SBS-R BIT 70/ SBS content/
mark mark 100 wt-% wt-%
softening point temperature of PMB.16

2L 2R 98 2 Rheological measurements
3L 3R 97 3 Rheological properties, i.e. viscoelastic parameters such
4L 4R 96 4 as the complex modulus G*, the complex viscosity g*,
5L 5R 95 5 and the phase angle d, were determined with a DSR,
7L 7R 93 7
MCR 301, Anton Paar, using the Peltier temperature

Table 2 Conventional properties of modified BIT

%SBS content

Property 2 4

Before RTFOT 0 SBS-L 3 SBS-R 5 7

Penetration 25uC/dmm 74 57 64 51 50 49 51 46 45 41 42
Ring and ball temperature/uC 48 53 55 76 86 83 94 88 99 90 103
PI 20.83 20.17 0,60 3.83 3.10 4.65 6.06 5.12 6.22 5.05 6.48
Fraass breaking point/uC 212 214 228 214 214 215 225 220 212 .231 231
Elastic recovery 25uC/% … 47 71 93 93 95 97 96 97 97 97
After RTFOT
Penetration 25uC/dmm 35 31 34 28 29 28 30 27 28 29 33
Ring and ball temperature/uC 58 64 67 78 81 85 87 89 92 92 103
Change of mass/% 20.20 20.23 20.20 20.24 20.30 20.30 20.20 20.23 20.01 20.23 20.01
Retained penetration/% 47 54 53 56 58 57 59 59 61 71 77
Fraass breaking point/uC 213 211 212 215 211 218 218 221 229 230 232
Elastic recovery 25uC/% … 54 75 79 78 78 82 80 85 85 90

Materials Research Innovations 2012 VOL 16 NO 1 2

 Bulatović et al. Polymer modified bitumen

control system. A dynamic rheometer is a type of testing The complex shear viscosity g* (Pa s) is defined as18
equipment which applies sinusoidal, oscillatory loading t
on a material sample. The tests are conducted over a g ~ : (12)
c
range of temperatures and loading frequencies in order :
to provide a complete characterisation of the viscoelastic where c is the shear rate function, the time derivative of
properties of the binder. The sinusoidally varying shear the sinusoidal strain (or deformation) function c(t).
stress can be expressed as17,18 The DSR tests were performed under controlled strain
loading conditions using temperature sweep tests. The
t(t)~t0 sinð$tzdÞ (2) temperature sweep was applied in the range 25 to 80uC
at a fixed traffic frequency of 10 rad s21 (y85 km h21)
and the resulting strain as
and variable strain. Preliminary tests were carried out at
c(t)~c0 sin $t (3) different temperatures in order to determine the strain
range in which the BIT remains in the linear viscoelastic
where t0 is the stress amplitude (Pa), c0 is the strain range (LVN).19 In this range, the stress response is
amplitude, v is the angular frequency (rad s21), t is the directly proportional to the strain value and the complex
time (s), and d is the phase angle of the measured modulus is independent of the strain level.19 In the terms
material response (u). for defining the LVN range, the chosen strain value is
The angular frequency v, also known as the where the complex modulus does not differ by .5%
rotational frequency, is defined as from its initial value.19,20 The temperature sweep tests
for low temperatures between 25 and 30uC were carried
$~2pf (4)
out with a parallel plate testing geometry of 8 mm
where f is the frequency (Hz). diameter and a 2 mm gap, and for the medium and
The sinusoidally varying stress and strain can also be higher temperatures, the tests were carried out with a
represented by the following complex notation as parallel plate testing geometry of 25 mm diameter and a
1 mm gap. The sample was put onto the lower plate of
c ~c0 ei$t (5) the DSR and was heated to flow. Then, the top plate was
lowered to come into contact with the sample, and the
t ~t0 ei($tzd) (6) sample was trimmed. Before the temperature sweep test,
all the samples were tempered at 80uC for 10 min and
The complex shear modulus G* is then defined as then the measurements started.21
t t0 id To provide a more profound insight into the
G ~ ~ e (7) rheological properties, the critical temperature with-
c c0
out permanent deformation (rutting) was determined
With equation (7) also being written as according to the SHRP.9 The critical temperature is
    both the temperature at which G*/sin d is equal to or less
t0 t0
G ~ cos dzi sin d~G’ziG’’ (8) than 1 kPa at a frequency of 10 rad s21 (the strain is the
c0 c0 constant 10%) before aging and that at which G*/sin d is
where G* is the complex shear modulus (Pa), G9 is the equal to or less than 2?2 kPa (the strain value is 12%)
storage modulus (Pa) related to the energy stored and G0 after aging.9 The critical temperature was determined
is the loss modulus (Pa) related to the energy lost at automatically by the DSR software.
deformation.
Aging procedure
The in-phase component of G*, or the real part of the
complex shear modulus, is defined as Accelerated thermooxidative aging of base BIT and
PMBs was performed using the RTFOT, according to
G’~G  cos d (9) ASTM D2872. The RTFOT procedure simulated the
short term aging of BIT and PMBs. The BIT and PMBs
and the out-of-phase component, or the imaginary part were exposed to elevated temperatures to simulate the
of the complex shear modulus as conditions during the production, mixing and lying of
G’’~G  sin d (10) asphalt mixes. Samples of a specific weight were placed
into glass containers heated to 163uC for y15 min and
It can be shown that G9 is the ratio of the stress, in phase then were placed into a rotating oven at 163uC for
with the strain to the strain, whereas G0 is the ratio of 85 min with the air on, and with the flowrate of
the stress, 90u out of phase with the strain to the strain. 4 L min21. All measurements were performed before
These two components (G9 and G0) are related to the and after the simulated aging in the laboratory, i.e.
complex shear modulus and to each other through the before and after the RTFOT.
phase angle d, which indicates the viscoelastic character
of the materials and defined as Results and discussion
G’’ The results of rheological behaviour of the base BIT and
tan d~ (11) the PMBs modified with SBS-L and SBS-R in depen-
G’
dence on temperature are presented in Figs. 1–6.
If d50u, the material is entirely elastic, and if d590u, Changes in G*, g* and d in the temperature range
completely viscous. Between these two extremes the from 25 to 80uC under the traffic frequency of
material behaviour can be considered to be viscoelastic 10 rad s21 are noted.
in nature with a combination of viscous and elastic As the temperature increases, the G* of the base BIT
responses.15,17 and PMBs decreases (Figs. 1 and 3). The decrease is

Materials Research Innovations 2012 VOL 16 NO 1 3


1 Complex modulus as function of temperature for BIT
70/100 and SBS-L PMB
2 Complex viscosity as function of temperature for BIT
70/100 and SBS-L PMB
3 Phase angle as function of temperature for BIT 70/100
and SBS-L PMB
smaller for the PMBs modified with SBS-L (Fig. 1). The
G* and g* values of PMBs are higher than those of the
base BIT and increase with the polymer content (Figs. 2
and 4). It means that the polymer gives stiffness to the
BIT and act as the filler.4 However, sometime filler can
decrease g* which is connected with the influence of
molecular structure on rheology.22 The formation of
elastic plateau is noted on the G*/T and g*/T curves
of PMBs with higher polymer contents.15 It indicates the
development of dominant polymer network.11 The
plateaus are more expressed on the curves of PMBs
modified with SBS-R (Figs. 4 and 5). It is due to various
interactions between SBS-R and BIT. At lower tem-
peratures in the range of 25 to 10uC, the PMB values of
G* and g* are the same as the pure BIT values. As the
Bulatović et al. Polymer modified bitumen
4 Complex modulus as function of temperature for BIT
70/100 and SBS-R PMB
5 Complex viscosity as function of temperature for BIT
70/100 and SBS-R PMB
6 Phase angle as function of temperature for BIT 70/100
and SBS-R PMB
temperature increases, the increase in G* and g* values
of PMBs is more expressed in comparison with the same
BIT values. This increase is more expressed in the PMB
with the higher polymer content.
The changes in the phase angle d related with changes
in temperature (Figs. 3 and 6) are more expressed than
those in G* in the same temperature range. The base BIT
shows predominantly viscous behaviour with increasing
temperature and the phase angle approaches 90u. The d/
T curves of PMBs (Figs. 3 and 6) are shifted to lower d
values. The PMBs with higher SBS contents have lower
d values and the formation of plateau on the d/T curve is
noted. This is in agreement with the plateau formation
on the G*/T curves of PMBs and indicates the formation
Materials Research Innovations 2012 VOL 16 NO 1 4
 Bulatović et al. Polymer modified bitumen

7 Complex modulus as function of temperature for BIT 10 Complex modulus as function of temperature for BIT
70/100 and SBS-L PMB after RTFOT 70/100 and SBS-R PMB after RTFOT

8 Complex viscosity as function of temperature for BIT 11 Complex viscosity as function of temperature for BIT
70/100 and SBS-L PMB after RTFOT 70/100 and SBS-R PMB after RTFOT

9 Phase angle as function of temperature for BIT 70/100 12 Phase angle as function of temperature for BIT 70/100
and SBS-L PMB after RTFOT and SBS-R PMB after RTFOT

Table 3 Critical temperature according to SHRP

Temperature where G*/sin d51 kPa before RTFOT and G*/sin d52.2 kPa after RTFOT/uC

%SBS content SBS-L SBS-R

0.0 64.0
2.0 70.0 64.0
3.0 76.0 70.0
4.0 82.0 76.0
5.0 88.0 88.0
7.0 94.0 106.0

Materials Research Innovations 2012 VOL 16 NO 1 5


of polymer network as a consequence of the swelling of
SBS in the maltene phase in BIT.14 Lower d and plateau
formation mean that PMBs have better elastic beha-
viour. At the low and higher temperatures the BIT with
radial SBSs (Fig. 6) has a reduced phase angle and a
more pronounced plateau region than the BIT modified
with the same content of SBS-L (Fig. 3). This increase in
elastic response of the PMBs at higher temperatures can
be attributed to the viscosity of the base BIT being low
enough to allow the elastic network of the polymer to
influence the mechanical properties of the modified
BIT.4 This is evident for the PMBs with higher polymer
contents and is more expressed in the PMB modified
with SBS-R. This may be assigned to different compat-
ibilities of SBS-L and SBS-R with BIT.
The changes in rheological properties, i.e. in G* and
g*, and in d are noted after aging under RTFOT
conditions (Figs. 7–12). After aging, the d values of BIT
on the d/T curve (Figs. 9 and 12) are evidently lower as
well as the d values of PMBs with lower contents of SBS-
L and SBS-R. In PMBs with higher SBS contents (5 and
7%), the decrease in d is smaller after aging for both
polymers and the elastic plateaus are destroyed to a
lesser degree. Polymer modified bitumens aged with
SBS-R as a modifier exhibit fewer changes in d after
aging. At higher temperatures d values of PMBs increase
after aging; this results in less elastic behaviour. Bitumen
and PMBs show the increase in G* after aging (Figs. 7
and 10). It means that chemical processes which include
degradation reactions as well as secondary processes of
cross-linking take place during the aging of BIT and
PMBs. As a consequences of aging, the viscosity g* of
BIT and PMBs increases (Figs. 8 and 11) and the elastic
response decreases (Figs. 9 and 12). In the degradation
processes, the polymer network is affected.23–26
The critical SHRP temperature values for permanent
deformation, when the value of G*/sin d>1 kPa before
aging, and the value of G*/sin d>2?2 kPa after aging,
are presented in Table 3. The critical temperatures of
PMBs are higher than that of the base BIT. Polymer
modified bitumens with higher polymer contents have
higher critical temperatures, which means better tem-
perature resistance to permanent deformation.
Better rheological properties and resistance to tem-
perature can be also noted in conventional tests, such as
the penetration test, the ring and ball temperature test,
and the elastic recovery test (Table 2). The addition of
polymers SBS-L and SBS-R decreases the BIT penetra-
tion and increases its ring and ball temperature and
elastic recovery. The ring and ball temperature increases
with the polymer content and this is more pronounced in
PMB modified with SBS-R.
Aged BIT and PMBs have lower values of penetration
and elastic recovery (Table 2) and higher ring and ball
temperature. It indicates that hardening occurs during
aging, as a consequence of secondary reaction of
degradation.13,26 Elastic recovery decrease is smaller in
the SBS-R modified BIT. These changes are in agree-
ment with the changes in rheological properties of BIT
and PMBs after aging.
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Bulatović et al. Polymer modified bitumen
Conclusions
The rheological properties of road BIT are improved by
means of SBS-L and SBS-R polymer modification as
proven by both conventional and rheological parameters
G*, g* and d obtained by DSR measurements. With the
addition of SBS, G* and g* are increased as well as the
elastic response. These increases are more pronounced
with changes in the temperature and the higher polymer
content. Styrene–butadiene–styrene with a radial struc-
ture shows a great degree of polymer modification.
After aging, the hardening of BIT and PMBs occurred
and the elastic response decreases as a consequence of
degradation. These changes are less pronounced in
PMBs with a higher polymer content and PMBs
modified with SBS-R.
Acknowledgement
The financial support of the Ministry of Science,
Education and Sports of the Republic of Croatia (grant
no. 125-125-2971-2578) is acknowledged.
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