SCIENTIFIC REPORTS

Materials and Structures/Matriaux et Constructions, Vol. 30, December 1997, pp 618-626

Compatibility and storage stability of styrene-butadienestyrene copolymer modified bitumens

X. Lu and U. Isacsson
Division of Highway Engineering, Royal Institute of Technology, S-100 44 Stockholm, Sweden

Paper received: August 20, 1996; Paper accepted: October 24, 1996

A B S T R A C T

R S U M

The compatibility and storage stability of styrenebutadiene-styrene copolymer (SBS) modified bitumens
were studied using f luorescence microscopy and
dynamic mechanical analysis. Chemical characteristics of
base bitumens and SBS polymers were determined by
means of thin layer and gel permeation chromatography,
respectively. The results showed that the morphology
and phase separation of the modified binders varied with
the characteristics of bitumens and polymers and were
influenced by polymer content. At a given polymer content, the modified binders produced from bitumens
with a higher content of aromatics exhibited better compatibility and higher storage stability. An increase in
asphaltenes was observed to adversely affect storage stability. When mixing a small amount of polymer with
bitumen, the modified binder showed dispersed polymer
particles. At relatively high polymer content, depending
on the base bitumens used, a continuous SBS phase was
observed. On the other hand, the storage stability of
modified binders decreased with increasing SBS content.
Compared with branched SBS polymer, linear SBS displayed a finer dispersion in modified binder, and consequently, a lower phase separation was observed during
hot storage. The degree of SBS dispersion in bitumen
influenced storage stability and the rheological properties of modified binders; however, no definite relationships among them could be established.

La compatibilit et la stabilit au stockage des bitumes modifis par des copolymres styrne-butadine-styrne (SBS) ont t
tudies au moyen de la microscopie fluorescence et de lanalyse
rhologique dynamique. Les caractristiques chimiques des bitumes
de base ont t dtermines par chromatographie en couche mince
alors que celles des polymres SBS lont t par chromatographie
permation de gel. Les rsultats ont montr que la morphologie et
la sparation de phases des liants modifis variaient selon les caractristiques des bitumes et des polymres et quelles taient influences par le contenu en polymres. Pour une teneur en polymres
donne, les liants modifis base de bitumes ayant un fort taux
daromatiques ont montr une meilleure compatibilit et une plus
grande stabilit au stockage. Il a t observ quune augmentation
de la teneur en asphaltnes dgradait la stabilit au stockage. Pour
des teneurs en polymre faibles, lobservation des liants modifis
montre des particules de polymre disperses dans la phase bitume.
des teneurs relativement importantes en polymre, mais
variables selon le bitume de base utilis, on observe une phase
polymre continue. Par contre, la stabilit au stockage des liants
modifis diminue lorsque la teneur en SBS augmente. En comparaison avec un polymre SBS de type radial (ramifi), le polymre
SBS de type linaire donne des dispersions plus fines qui se traduisent par une moindre tendance la sparation de phases lors du
stockage chaud. Le degr de dispersion du polymre SBS dans le
bitume influence la fois la stabilit au stockage et les proprits
rhologiques des liants modifis. On na cependant pas pu tablir
de relations prcises entre ces proprits.


1. INTRODUCTION
For at least three decades, polymer modified bitumens (PMBs) have been used in road technology with
the intention of reducing road deterioration such as rutting, cracking and stripping. PMBs are obtained by
incorporation of polymers in bitumens using mechanical
mixing or chemical reaction. When mixing is used, the

compatibility due to differences in molecular weight,

polarity and structure of the base bitumen and the polymer may be a critical part of the system. In order to
achieve the optimum properties of PMBs, suitable compatibility between bitumen and polymer is required.
Low compatibility may result in poor storage stability,
which in turn leads to separation of polymeric and bituminous phases and inconsistent binder quality. The use

Editorial note
Mr. Ulf Isacsson is a RILEM Senior Member. He is a member of TC 152-PBM on Performance of Bituminous Materials.
0025-5432/97 RILEM

618

Lu, Isacsson

of compatible bitumens
Table 1 Binder description
and polymers may also
Binder
Bitumen SBS Content [% by mass] Penetration Softening
Viscosity
Fraass
facilitate the manufacture
Grade/
@ 25C,
Point
@ 135C
Breaking
Code (a)
D-1101
D-1184
of polymer modif ied
Source
[0.1 mm]
[C]
[mm2/s]
Point [C]
binders, which means that
A
B85
84
46.0
354
-11
homogeneous PMBs can
A
Venezuela
77
47.3
370
-11
be obtained with a short
PMB-AL3
3
64
52.1
827
-12
blending time or by using
PMB-AL6
6
49
73.5
2020
-12
a low-shear mixer [1].
PMB-AL9
9
37
84.0
4780
-12
PMB-AB6
6
50
82.3
3830
-12
However, if bitumen and
PMB-AM6
3
3
47
80.2
2360
-11
polymer are completely
compatible, one basic
B
B180
183
38.8
210
-16
B
Venezuela
165
39.5
224
-15
change in PMB properties
PMB-BL3
3
122
55.3
506
-16
may be a signif icant
PMB-BL6
6
88
77.2
1060
-17
increase in viscosity, at the
PMB-BL9
9
70
85.1
3350
-19
same time as improvePMB-BB6
6
84
82.5
2390
-18
ment in mechanical propPMB-BM6
3
3
84
81.0
1370
-18
erties (e.g. elasticity and
C
B180
180
41.0
208
-17
tensile strength) will be
C
Mexico
158
41.5
237
-16
very slight [2].
PMB-CL3
3
120
51.2
461
-18
Compatibility can be
PMB-CL6
6
88
77.2
1350
-20
defined as the state of disPMB-CL9
9
67
85.3
3450
-20
persion between two disPMB-CB6
6
89
85.4
3890
-17
similar components. In
PMB-CM6
3
3
92
82.1
2390
-18
principle, good PMB
D
B180
149
42.8
236
-16
compatibility can be
D
Saudi Arabia
130
43.0
250
-16
obtained by careful selecPMB-DL6
6
80
75.2
1220
-19
tion of its two components
PMB-DB6
6
77
84.0
4360
-19
(bitumen and polymer).
E
B180
188
44.3
172
-22
However, PMB compatiE
Russia
166
44.0
187
-22
PMB-EL6
6
70
75.2
1640
-26
bility is usually a compliPMB-EB6
6
69
81.5
3220
-25
cated phenomenon due to
the complex nature of (a) A B C D and E denote the base bitumens after being subjected to the same treatment as the polymer-bitumen
bitumens and the variably blends; L = linear, B = branched and M = mixed (linear + branched).
mutual effects of the components. In most cases,
D-1184) SBS, supplied by the Shell Chemical Company.
compatibility is influenced simultaneously by various facSBS modified bitumens were prepared using a low shear
tors such as bitumen composition [1, 3-6], polymer charmixer (RW 20 DZM-P4, Janke & Kunkel) at 180C and
acteristics [5, 7-9], polymer content [2, 5], as well as mixa speed of 125 rpm. The mixing time was two hours.
ing process [10]. Consequently, to obtain optimum
Polymer content and structure as well as binder propercompatibility, a matching of different variables is required.
ties are given in Table 1.
The primary goal of the present study is to determine
the influence of the source and grade of base bitumens,
and the characteristics and content of styrene-butadiene2.2 Methods
styrene copolymer (SBS) on the compatibility and storage stability of modified binders. Relationships between
Hot storage
compatibility, storage stability and rheological properties
An aluminium foil tube, 35 mm diameter and 190 mm
of the modified binders are also studied. In addition, a
height, was filled with about 90 g homogeneous SBS
mechanism of the phase separation of polymer modified
modified binder. After closing the tube without air
binders is briefly discussed.
enclosures, it was stored vertically at 180C for three
days. The tube with the modified binder was cooled to
ambient (room) temperature and then to about -10C,
2. MATERIALS AND METHODS
after which the foil was peeled off and the modified
binder specimen cut horizontally into three equal sec2.1 Materials
tions. The samples taken from the top and bottom of the
tube were used to evaluate the storage stability of the
The f ive different bitumens investigated were
binders by measuring their softening point and dynamic
obtained from Venezuela (Laguna), Mexico, Saudi
rheological properties.
Arabia and Russia, respectively. The polymers used were
powdered linear (Kraton D-1101) and branched (Kraton

619

Materials and Structures/Matriaux et Constructions, Vol. 30, December 1997

Thin-layer chromatography with flame ionization

detection (TLC-FID)
In TLC-FID, the sample to be analyzed is dissolved in
a solvent and spotted at one end of a chromarod (quartz
rod coated with a thin layer of sintered silica or alumina).
The rods are then developed with suitable solvents, after
which the solvents are removed by heating. The rods are
scanned at a chosen speed through a hydrogen flame, and
the separated fractions successively vaporized/pyrolyzed.
The FID signals from each fraction are amplified and
recorded as separate peaks. In this study, a commercial
equipment, Iatroscan MK-5 analyzer (Iatron Laboratories
Inc., Tokyo, Japan), was used. 2% (w/v) solutions of bitumens were prepared in dichloromethane, and 1 l sample
solution spotted on chromarods using a spotter. The separation of bitumen into four generic fractions (saturates,
aromatics, resins and asphaltenes) was performed by a
three-stage development using n-heptane, toluene and
dichloromethane/methanol (95/5 by volume), respectively.

entire surface, and the plate was then mounted in the

rheometer. After heating to the softening point of the
binder, the top plate was brought into contact with the
sample, and the sample trimmed. The final gap was
adjusted to 1 mm ( 25 mm) or 1.5 mm ( 8 mm). A
sinusoidal strain was then applied by an actuator. The
actual strain and torque were measured and input to a
computer. Various viscoelastic parameters, such as storage modulus (G), loss modulus (G), complex modulus
(G) and phase angle (), were calculated.

3. RESULTS AND DISCUSSION

3.1 Chemical characterization of bitumens
and SBS polymers

Fluorescence microscopy
Fluorescence microscopy was used to study morphology (compatibility) of polymer modified binders.
The modified binder was illuminated using a blue light
for excitation and the fluorescent yellow light re-emitted
by the swollen polymer phase observed using an optical
microscope. The instrument (Leitz, LABORLUX II)
was equipped with a Polaroid camera and a blue filter
system. The wavelength of excitation is in the range of
390 to 490 nm. Squashed slides of modified binders
were prepared using very small amounts of the heated
sample and viewed under the microscope with a magnification of 250 at room temperature.

Bitumens
The chemical composition of bitumens is extremely
complex. Various techniques such as solvent precipitation and chromatography have been developed for fractionation of bitumen. In this study, bitumens were
analysed using two chromatographic methods, TLCFID and GPC. The typical TLC-FID chromatograms of
bitumens are shown in Fig. 1. Four peaks are recognized
as saturates, aromatics, resins and asphaltenes, respectively. By area normalization, the percent generic fractions of bitumen are obtained. As can be seen in Table 2,
the five base bitumens vary in chemical composition.
There is little difference between the four generic fractions of bitumen C (Mexico B180) and D (Saudi Arabia
B180), resulting in the same value of the colloidal instability index (Ic, definition see Table 2). Bitumen A and
B show the same Ic values in spite of their differences in
generic fractions. This similarity might be attributable to
the same source for bitumen A and B. Bitumen E
(Russian) possesses the highest saturates and the lowest
aromatics, and consequently, the highest Ic value.
Examples of bitumen GPC chromatograms are also
shown in Fig. 1. The weight average (Mw) and number
average molecular (M n ) weight and polydispersity
(Mw /Mn) of the bitumens are given in Table 2. As can be
seen, there is little difference between the GPC data of
bitumens C and D. This observation correlates well with
the results obtained using TLC-FID. Compared to other
bitumens, bitumen E contains more of the larger molecular species. The fraction of molucules with Mw over
2500 g/mole is 18% by mass. This bitumen also shows
the widest molecular weight distribution (polydispersity
2.49) of the five bitumens.

Rheological measurements
Rheological measurements were carried out using a
rheometer (Rheometrics RDA II) with a frequency
sweep from 0.1 to 100 rad/s at 25C and temperature
sweep from -30 to 135C at 1 rad/s. Parallel plates,
diameter 8 mm and 25 mm, were used in a temperature
range of -30 to 50C and 40 to 135C, respectively. In
each test, about 0.1 g ( 8 mm) or 1 g ( 25 mm) of
binder was applied to the bottom plate, covering the

SBS polymers
SBS copolymers consist of styrene-butadiene-styrene
triblock chains and have a two-phase morphology,
showing spherical domains formed by the polystyrene
blocks (PS) within a matrix of polybutadiene (BR). The
existence of such a two-phase system can be indicated by
two distinct glass transition points (Tg), the rubbery
middle block (BR) having a Tg of -90C, and the hard
glassy domain (PS) a Tg of +100C [11]. These poly-

Gel permeation chromatography (GPC)

In GPC, molecules that differ in size are separated by
passing the sample through a stationary phase consisting
of porous cross-linked polymeric gel. The pores of the
gel exclude molecules larger than a certain critical size,
while smaller molecules can permeate the gel structure
by diffusion. The sample components are eluted in order
of decreasing size or molecular weight. The GPC systems used in this study were three ultra-styragel columns
arranged in the order of pore size (500, 103, and 104
for polymers and 100, 500 and 500 for bitumens) and
a refractive index detector (Water 410). In the analysis,
5% by mass bitumen and 0.3% by mass polymer solutions were prepared in tetrahydrofuran (THF). A broad
molecular weight polystyrene standard was used to calibrate the instrument.

620

Lu, Isacsson

Fig. 1 Thinlayer chromatography with flame

ionization detection (TLC/FID)
and gel permeation chromatography (GPC) of
base bitumen B
and E.

Table 2 Chemical characteristics of base bitumens and SBS polymers

Bitumen Code

Saturates (% by mass)
Aromatics (% by mass)
Resins (% by mass)
Asphaltenes (% by mass)
Colloidal instability index, Ic(1)

11.3
54.7
18.7
15.4
0.36

13.0
56.4
17.3
13.3
0.36

10.4
64.8
13.1
11.7
0.28

10.9
63.6
14.8
10.7
0.28

16.9
51.1
18.3
13.7
0.44

Number average, Mn
Weight average, Mw
Polydispersity (Mw /Mn)
Fraction with Mw > 2.5 x 103
(% by mass)

650
1300
2.06

600
1300
2.08

750
1400
1.84

740
1300
1.80

720
1800
2.49

13

12

12

11

18

Kraton D-1101
(Linear)

Kraton D-1184
(Branched)

istics of these two polymers are given in Table

2. As can be seen, two GPC peaks are recognized for both linear and branched SBS; each
peak has a polydispersity between 1.03 and
1.11, i.e. a narrow molecular weight distribution. Compared with the linear SBS, the
branched SBS has a higher molecular weight
and a wider polydispersity.

3.2 Compatibility of the modified

binders

Fluorescence microscopy studies

The compatibility of polymer modified
bitumens
was studied using f luorescence
Number average, Mn
Weight average, Mw
microscopy by characterizing the nature of the
Peak molecular weight
continuous phase and the fineness of the disPolydispersity (Mw /Mn)
persion of the discontinuous phase. At the
Percentage (% by mass)
studied temperature and a magnification of
Total average
250, all SBS modified binders exhibit proNumber average,Mn
180000
310000
nounced heterogeneity. A distinction can genWeight average, Mw
210000
450000
erally be made between binders whose continPolydispersity (Mw /Mn)
1.19
1.43
uous phase is a bitumen matrix with dispersed
Asphaltenes + Saturates
(1) I c =
polymer particles and binders whose continuResins + Aromatics
ous phase is a polymer matrix with dispersed
bitumen globules. Examples of photomicrostyrene domains are formed by a process of phase separagraphs showing the two types of PMB morphology are
tion arising from the incompatibility of BR and PS and
given in Fig. 2. The oil swelling SBS phase fluoresces yelgive coherent physical cross-linking points, provided the
low light (appears white) while the bitumen-rich phase
PS chains are large enough. The effectiveness of these
appears dark. Within the polymer-rich phase there are two
cross-links diminishes rapidly above the glass transition
microphases - swollen polybutadiene and essentially pure
temperature of polystyrene, i.e. 100C. On cooling, the
polystyrene domains, which act as physical crosslink sites to
polystyrene domains will reform, and the strength and
form a three dimensional network [12]. The SBS polymer
elasticity will be restored. The thermoplastic nature of
network should not be confused with the SBS continuous
SBS polymers at elevated temperatures and their ability
phase, which can be obtained at a high polymer content.
to provide a continuous network are very important
The network may exist in both the polymer-rich phase
when they are used as bitumen modifiers.
present as discrete particles (Fig. 2, PMB-BL3) and the
SBS polymers may differ in their structures, dependpolymer-rich phase as continua (Fig. 2, PMB-BL9).
ing on the copolymerization of polystyrene and polybuThe morphology (compatibility) of polymer moditadiene. In this study, one linear and one branched SBS
fied bitumens is the result of the mutual effects of polypolymer were used to modify different bitumens. The
mer and bitumen, and consequently is mainly inf lulinear and the branched SBS polymers have 31% and
enced by bitumen composition and polymer nature and
30% by mass styrene, respectively. The GPC charactercontent. As indicated in Fig. 2, at low SBS content, only
SBS polymer

Peak 1
221000
241000
198000
1.09
81.3

Peak 2
99600
102000
101000
1.03
18.7

Peak 1
480000
531000
522000
1.11
78.6

Peak 2
142000
146000
142000
1.03
21.4

621

Materials and Structures/Matriaux et Constructions, Vol. 30, December 1997

Fig. 2 Fluorescence photomicrographs of PMB-BL3

and PMB-BL9.

PMB-BL3

PMB-BL9

partial swelling of the dispersed polymer particles occurs,

with no interaction among them; by increasing SBS
content, a continuous polymer-rich phase may be
obtained. The minimum percentage of SBS polymer to
ensure the formation of continuous polymer phase
depends to a great extent on the base bitumens. It was
observed that the continuous SBS phase was more difficult to form in B85 bitumen than in B180 bitumens.
The effect of bitumen source on the dispersion of
SBS polymer in the modified binders was studied. It was
observed that the SBS modified bitumen B displays a
higher distribution in large polymer particles than the
modified bitumens C and D. Unlike these three SBS
modified binders, the modified binder containing bitumen E shows SBS aggregates, which seem to be isolated
by the components of the bitumen. These observations
can be related to the chemical compositions of the bitumens (Table 2). The bitumens with higher aromatic and
lower asphaltene contents (C and D) result in better
compatibility for the modified binders. In contrast, bitumen E shows the lowest aromatic and highest asphaltene
contents, and consequently the poorest compatibility.
Evidently, to produce a polymer modified binder with
good compatibility, the content of aromatics of the base
bitumen should be sufficiently high for the polymer to
compete with asphaltenes. Therefore, it is reasonable to
expect that the compatibility of SBS modified binders
may be improved by the addition of aromatic oil or deasphaltenation of bitumens. However, an excessive content of aromatics or an insuf f icient content of
asphaltenes in base bitumens may lead to modif ied

binders with a single phase showing no signif icant

improvement in mechanical properties.
The morphology of SBS modified binders is also
inf luenced by the characteristics of SBS polymers.
Compared to modified binders containing linear SBS,
modified binders with branched SBS show larger polymer domains, suggesting a lower degree of compatibility.
This is probably caused both by a difference in polymer
structure and molecular weight. GPC analyses have
shown that the average molecular weight of the
branched SBS is about twice that of the linear SBS
(Table 2). An increased difference in molecular weight
of the components may lead to lower compatibility of
the system. Moreover, the branched structure of SBS,
for a given molecular weight, could result in a relatively
stronger interaction between polymer molecules, which
is unfavourable when blending the polymer with other
substances homogeneously.
Compatibility and viscoelastic properties
The viscoelastic properties of a polymer modified
binder are influenced by the morphology of the system.
SBS modified binders with a continuous polymer-rich
phase can behave like a crosslinked rubber and display rubber-like elasticity, while modified binders with discrete
small polymer particles in principle behave like unmodified bitumens. This difference is illustrated in Fig. 3 (a). As
can be seen, for PMB-BL9 which displays a continuous
SBS polymer-rich phase in its photomicrograph (Fig. 2),
there is a plateau region in the plot of storage modulus versus temperature. The plateau region corresponds to a phase

Fig. 3
Storage modulus and phase
angle versus
temperature
at 1 rad/s for
bitumen B,
PMB-BL3,
BL9, DL6
and EL6,
respectively.

622

Lu, Isacsson

angle minimum, as discussed in [13]. On the other hand,

the modified binder (PMB-BL3) with discrete small polymer particles (Fig. 2) does not display the plateau region, as
is the case for the unmodified bitumen (B).
At the same polymer content, modified binders differing in morphology may display different viscoelastic
properties. As has been discussed above using f luorescence micrographs, the modified bitumen E shows the
poorest compatibility among the five bitumens studied.
Consequently, the rubber-like elasticity of this modified
binder is much weaker than that of other modif ied
binders, as indicated in Fig. 3 (b). However, such a comparison cannot be made among the modified binders
containing an identical bitumen but different types of
polymer. For example, despite the fact that branched
SBS shows coarser polymer dispersion than linear SBS,
the former is still more effective in binder elasticity
improvement [13]. Furthermore, no relationships
between compatibility as characterized by fluorescence
microscopy and low temperature properties (e.g. complex modulus at low temperatures and Fraass breaking
point) and between compatibility and temperature susceptibility were established in this study.
Despite the qualitative evidence that the degree of
compatibility inf luences the rheological properties of
polymer modified binders, it is not clear what degree of
compatibility will provide modified binders with optimum properties, especially when modif ied binders
showing the same type of continuous or dispersed phase
are compared. Probably, it is very difficult to establish a
Table 4 Rheological properties of the binders before
and after storage at 180C for three days
G* (Pa) at 25C, 10 rad/s
Binder

Original
sample

After storage
Top
Bottom
section
section

(Deg) at 25C, 10 rad/s

Original
sample

After storage
Top Bottom
section section

Table 3 Softening point (ASTM D 36) of modified

binders before and after storage at 180C for three days
Binder

Original
sample
[C]

After storage [C]

TR&B (1)

Top
section

Bottom
section

[C]

PMB-AL3
PMB-AL6
PMB-AL9
PMB-AB6
PMB-AM6

52.1
73.5
84.0
82.3
80.2

55.5
92.5
101.0
110.0
108.0

54.5
60.0
65.0
57.5
57.0

1.0
32.5
36.0
52.5
51.0

PMB-BL3
PMB-BL6
PMB-BL9
PMB-BB6
PMB-BM6

55.3
77.2
85.1
82.5
81.0

55.0
89.5
98.0
104.5
92.5

50.0
52.0
58.5
50.5
51.5

5.0
37.5
39.5
54.0
41.0

PMB-CL3
PMB-CL6
PMB-CL9
PMB-CB6
PMB-CM6

51.2
77.2
85.3
85.4
82.1

51.5
89.0
108.5
112.0
103.0

52.0
56.0
58.5
52.5
52.5

0.5
33.0
50.0
59.5
50.5

PMB-DL6
PMB-DB6

75.2
84.0

95.0
115.0

66.0
51.5

29.0
63.5

PMB-EL6
PMB-EB6

75.2
81.5

89.5
104.0

68.0
63.5

21.5
40.5

(1) TR&B = Softening point of top section sample - Softening point of bottom
section sample.

quantitative relationship between PMB compatibility,

defined by microstructure, and rheological properties.
The reason is that the assessment of compatibility by
microscopy is only qualitative, and the great variety of microstructures does not permit a clear
classification of the modified binders with regard
to compatibility.
Is

A
PMB-AL3
PMB-AL6
PMB-AL9
PMB-AB6
PMB-AM6

5.65E+5
6.56E+5
9.07E+5
1.10E+6
8.60E+5
9.14E+5

5.67E+5
1.16E+5
5.47E+4
6.91E+4
6.54E+4

5.78E+5
1.81E+6
3.80E+6
1.70E+6
1.67E+6

72
67
60
53
59
60

68
55
41
44
48

68
60
53
61
61

0.01
1.19
1.84
1.39
1.41

B
PMB-BL3
PMB-BL6
PMB-BL9
PMB-BB6
PMB-BM6

1.29E+5
1.56E+5
2.28E+5
3.81E+5
2.26E+5
2.20E+5

1.78E+5
3.80E+4
3.30E+4
3.00E+4
2.72E+4

1.75E+5
5.64E+5
1.32E+6
5.78E+5
5.65E+5

77
71
62
53
60
61

71
50
42
46
48

71
65
58
66
65

0.00
1.17
1.62
1.28
1.32

C
PMB-CL3
PMB-CL6
PMB-CL9
PMB-CB6
PMB-CM6

1.62E+5
2.11E+5
2.73E+5
4.21E+5
3.32E+5
2.83E+5

1.66E+5
7.98E+4
4.17E+4
6.18E+4
5.95E+4

1.78E+5
3.29E+5
8.05E+5
4.23E+5
4.18E+5

76
70
62
53
61
61

71
60
43
51
54

70
67
62
68
67

0.03
0.62
1.29
0.84
0.85

D
PMB-DL6
PMB-DB6

2.22E+5
4.21E+5
3.91E+5

1.25E+5
7.01E+4

3.35E+5
6.10E+5

75
60
62

62
51

66
67

0.43
0.94

E
PMB-EL6
PMB-EB6

1.66E+5
3.28E+5
3.60E+5

3.31E+4
2.52E+4

1.22E+6
9.95E+5

61
43
43

40
36

43
45

1.57
1.60

623

3.3 Storage stability of the modified

binders
Phase separation
The phase separation of polymer modified bitumens was determined by hot tube storage test. After
storing the tube at 180C for three days, tests of
softening point and rheological measurements with
a frequency sweep from 0.1 to 100 rad/s at 25C
were carried out on the samples taken from the top
and the bottom of the tube. The corresponding
measurements were also run on original modified
and unmodified bitumens. Results of softening
point test and dynamic mechanical measurement at
a frequency of 10 rad/s are given in Tables 3 and 4,
respectively.
A comparison between stored and original
binders indicates that samples from the bottom
section become harder and from the top section
softer and more elastic (lower phase angle). These
changes indicate separation of the SBS rich phase
and asphaltene rich phase of the modified binders.
The polymer swollen by the light fractions of the
bitumen rises to the top of the tube, while the

Materials and Structures/Matriaux et Constructions, Vol. 30, December 1997

heavy fractions (mainly asphaltenes) concentrate at the

bottom of the tube. The amount of light fractions of the
bitumen absorbed by the polymer may increase with
polymer content. A marked change was observed as SBS
content exceeds three per cent. The phase separation was
also confirmed by the fluorescence micrographs taken at
room temperature and a magnification of 250 before and
after hot storage.
To evaluate the storage stability of the modified
binders, a separation index, Is, defined as:
Is = log

G Bottom phase
G Top phase

is used. Modified bitumens without phase separation

during hot storage show Is values close to zero. Since G
is temperature and frequency dependent, the values of Is
are influenced by test conditions. Is values given in Table
4 were obtained at 25C and 10 rad/s. As can be seen in
Table 4, the degree of phase separation is dependent on
polymer content and bitumen source/grade. Among the
modified binders tested, those with bitumen C and bitumen D are the most stable and modified binders with
bitumen E the most unstable. These findings can be
explained by the chemical compositions of the base bitumens. The storage stability of modified binders increases
with aromatics content of base bitumens, while an
increase in asphaltenes content adversely affects the storage stability, as indicated in Fig. 4. Moreover, no relationship between storage stability of modified binders
and GPC parameters (e.g. average molecular weight) of
the base bitumens was established. However, to draw a
definite conclusion in this respect, further types of base
bitumens need to be investigated.
The storage stability of modified binders is also influenced by the characteristics of SBS polymers. As indicated in Table 4, the modified binders with linear SBS
display higher storage stability than the modified binders
with branched SBS. This difference is attributable to the
state of SBS dispersion in the modified binders. As
shown by f luorescence microscopy, the dispersion of
linear SBS is much finer than that of branched SBS,
which also indicates that linear SBS are easier to incorporate in bitumen than branched SBS [14].
Since the storage stability of polymer modif ied
binders is traditionally evaluated by testing softening

point (R&B temperature) of the top and bottom sections

after hot storage [15], comparison has been made
between the difference in R&B temperature (TR&B)
and separation index (IS). No significant relationship was
established between these two parameters. In some cases
(e.g. the modified binders with bitumen E), a high phase
separation, as measured by dynamic mechanical analysis,
is contrarily reflected by a small difference in softening
point. Obviously, different conclusions could be drawn
on the storage stability of modified binders if the results
obtained using these two methods are evaluated separately. It should be noted that testing of softening point
is generally accepted for unmodified bitumens but can
give non-relevant results when testing highly elastic
modified binders. Consequently, softening point may be
related to different properties when applied to unmodified and SBS modified bitumens. Since the hot storage
process increases the elasticity of top samples and the
hardness of bottom samples, and such changes will be
confounded in R&B temperatures, the softening point
test is probably not adequate for evaluation of storage
stability of polymer modified binders.
Mechanism of phase separation
Bitumen is traditionally regarded as a colloidal system
consisting of a suspension of high molecular weight
asphaltene micelles dispersed in a lower molecular
weight oily medium (maltenes) [16-18]. The micelles are
considered to be asphaltenes together with an absorbed
covering sheath of high molecular weight aromatic resins
as a stabilizing solvating layer. Further away from the
centre of the micelle there is a gradual transition to the
less aromatic resins and such layers extend outwards into
the less aromatic oily dispersion medium [19]. The colloidal model describes bitumen as a multi-phase system.
In the presence of sufficient quantities of resins and aromatics of adequate solvating power, the asphaltenes are
fully peptized and the resulting micelles have good
mobility within bitumen. These bitumens are known as
solution or sol type bitumens [20]. On the other
hand, insufficient quantities (insufficiently solvating
power) of resins and aromatics may lead to association of
several micelles. These bitumens are known as gelatinous or gel type bitumens [20]. To characterize the
stability of the colloidal system, a colloidal instability

Fig. 4
Relationship
between separation index
and bitumen
composition.

624

Lu, Isacsson

3.4 Comparison of compatibility and storage

stability

Fig. 5 Separation index of modified binders as a function of colloidal index of base bitumens.

index or Gaestel index (Ic) has been proposed, which is

def ined as the ratio of the sum of the amounts of
asphaltenes and saturates to the sum of the amounts of
resins and aromatics.
The introduction of any polymer with high molecular weight will disturb the dynamic equilibrium and
reduce the homogeneity of the bitumen system. When
SBS polymer is added to hot bitumen under agitation, it
absorbs maltenes from the bitumen and can swell by up
to nine times its initial volume [21]. The polymer competition for the light fractions of the bitumen will result
in the association of asphaltene micelles or increase the
degree of the association depending on the nature of
original bitumen. Moreover, at high temperatures, a relatively low viscosity of the melted micro-heterogeneous
polymer modified bitumens allows the substances with
similar structure and polarity to form their domains - the
swollen polymers and the asphaltenes. In view of thermodynamics, this kind of system is unstable and a phase
separation or sedimentation may occur under the influence of gravitational fields. This means the associated
asphaltenes may settle to the bottom of the modified
binders during static hot storage.
According to this mechanism, the degree of the
phase separation of polymer modified binders may be
inf luenced by storage conditions such as temperature
and time. However, the phase separation will mainly be
governed by the nature of the base bitumen and the
characteristics and content of the polymer. The base
bitumens with low value of colloidal instability index
should improve PMB storage stability. This effect is
illustrated in Fig. 5. It can also be seen that, at a given
value of colloidal instability index, the modified binders
with branched SBS generally show higher phase separation than the modified binders with linear SBS.
Since many polymer modified bitumens display a
tendency in phase separation, some agitation is recommended during the storage of hot blends. However, such
a measure should not be taken without limit and at the
expense of the oxidative degradation of polymers.

A qualitative comparison made between separation

index and fluorescence photomicrograph indicates that,
at a given SBS content, the modified binders showing a
f iner polymer-dispersion in micrographs generally
exhibit less phase separation during static hot storage. In
this case, the separation index (storage stability) can be
regarded as a measurement of the compatibility of polymer modified binders. However, a high phase separation
was observed in modified binders with high SBS content showing a continuous polymer phase in their
microstructures; the modified binders with such desirable microstructures cannot be judged as incompatible
systems. Moreover, when the phase separation is characterized by softening point, no relationship between storage stability and micrograph of SBS modified binders
was observed. Obviously, the compatibility of polymer
modified binders defined in different ways or evaluated
by different methods is not necessarily consistent. This
also indicates that using only one method for determination of the degree of compatibility of polymer modified
binders may be misleading.

4. CONCLUSIONS
Compatibility is a critical property of SBS polymer
modif ied bitumens. It may be characterized by the
nature of the continuous phase and the fineness of the
dispersed phase. At the microscopic level, all SBS modified binders exhibit a pronounced heterogeneity, and a
general distinction can be made between binders with a
continuous bitumen phase in which the polymer particles are dispersed and the binders with a polymeric continuous phase in which bitumen globules are dispersed.
The introduction of SBS polymer disturbs the
dynamic equilibrium and reduces the homogeneity of
the bitumen system. Under the inf luence of gravitational fields, a phase separation can occur in which the
associated asphaltenes settle to the bottom, while the
swollen SBS polymers move to the top of modified
binders. The phase separation may be determined by
storage test. To characterize the phase separation, softening point is often used. However, the use of this parameter in the case of modified binders may be inadequate.
Instead, a separation index based on dynamic mechanical
analysis is used in this study.
It has been shown that the compatibility and storage
stability of SBS modified binders are influenced by the
nature of the base bitumen and the characteristics and
content of the polymer. At a given SBS content, the
modified binders produced from the bitumens with a
higher content of aromatics exhibit better compatibility
and higher storage stability. An increase in asphaltenes
may adversely affect the storage stability. By mixing a
small amount (3% by mass in this case) of SBS with
bitumens, modified binders reveal the dispersed polymer
particles. At an increased SBS content, a continuous

625

Materials and Structures/Matriaux et Constructions, Vol. 30, December 1997

SBS-rich phase may be observed. The minimum percentage of the polymer to ensure the formation of its
continuous phase depends on the base bitumen. On the
other hand, the storage stability of the modified binders
may decrease with increasing SBS content. Compared
with modified binders containing branched SBS, linear
SBS modified binders display finer polymer dispersion
in morphology and lower phase separation during hot
storage.
A qualitative comparison between separation index
and f luorescence micrograph indicates that, at a given
SBS content, the modified binders showing finer polymer dispersion in micrographs generally exhibit less
phase separation during hot storage. However, such a
comparison cannot be made among modified binders
with different polymer contents. This means that the
compatibility defined by different methods is not necessarily consistent, and a compatible or an incompatible
polymer modified bitumen cannot be determined using
only one method.
Compatibility and storage stability may influence the
rheological properties of modified binders; unfortunately, no definite relationships between these parameters were established in this study. The complexity in
such relationships increases when modified binders with
different kinds of polymer are compared.

Arodromes, Dossier, Bitumes modifis 711 (1) (October 1993) 18-22.

[3] Madella, A., Le Bourlot, F. and Brl, B., Selection of asphalt
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International Symposium on Chemistry of Bitumen, Vol. II,
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[4] Mancini, G., del Manso, F. and Bocchi, L., Correlations between
the chemical type of bitumen fractions and their interactions
with SBS copolymers, Ibid, 952-967.
[5] Collins, J. H., Bouldin, M. G., Gelles, R. and Berker, A.,
Improved performance of paving asphalts by polymer modification, Proc. Assoc. of Asphalt Paving Technologists 60 (1991) 43-79.
[6] Piazza, S., Arcozzi, A. and Verga, C., Modified bitumens containing thermoplastic polymers, Rubber Chemistry and Technology
53 (1980) 994-1005.
[7] Bredael, P., Andriolo, P. and Killens, E., A structural study of the
hot storage stability of SBS-modified bitumens, Proceedings of
the International Symposium on Chemistry of Bitumen, Vol. II,
Rome, June 1991, 932-951.
[8] Choyce, P. and Woolley, K., EVA modified binders, Highways
(January 1988) 18-21, 34.
[9] Woolley, K.G., Polymer modified bitumen for extra value asphalt,
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[10] Brl, B., Brion, Y. and Tanguy, A., Paving asphalt polymer
blends: relationships between composition, structure and properties, Proc. Assoc. of Asphalt Paving Technologists 57 (1988) 41-64.
[11] Bull, A. L. and Vonk, W. C., Cariflex thermoplastic rubber:
The living polymer, Shell Bitumen Review 66, May 1992, 1-3.
[12] Kraus, G., Modification of asphalt by block polymers of butadiene and styrene, Rubber Chemistry and Technology 55 (1982)
1389-1402.
[13] Lu, X. and Isacsson, U., Rheological characterization of
styrene-butadiene-styrene block copolymer modified bitumens,
Construction and Building Materials 11 (1997) 23-32.
[14] Cariflex TR in bitumens for road construction and maintenance, Thermoplastic Rubbers Technical Manual TR 6.6, Shell
Elastomers, 1987.
[15] Isacsson, U. and Lu, X., Testing and appraisal of polymer modified road bitumens - state of the art, Mater. Struct. 28 (1995)
139-159.
[16] Pfeiffer, J. Ph. and Saal, R. N. J., Asphaltic bitumen as colloid
system, J. Phys. Chem. 44 (1940) 139-149.
[17] Traxler, R. N. and Coombs, C. E., The colloidal nature of
asphalt as shown by its flow properties, J. Phys. Chem. 40 (1936)
113-1147.
[18] Mack, C. J., Colloid chemistry of asphalts, J. Phys. Chem. 36
(1932) 2901-2914.
[19] Girdler, R. B., Constitution of asphaltenes and related studies,
Proc. Assoc. of Asphalt Paving Technologists 34 (1965) 45-79.
[20] Whiteoak, D., The Shell Bitumen Handbook, Shell Bitumen
U. K., 1991, Chapter 6.
[21] Valkering, C. P., Vonk, W. C. and Whiteoak, C. D., Improved
asphalt properties using SBS modified bitumens, Shell Bitumen
Review 66, May 1992, 9-11.

ACKNOWLEDGEMENTS
The authors gratefully acknowledge the Swedish
Transport and Communications Research Board (KFB)
for financial support of this work. The authors are also
indebted to Mr. J. Ekblad for skillful technical assistance
in the laboratory.

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626