Asphalt Modified by SBS Triblock Copolymer:

Structures and Properties

A. ADEDEJI, T. GRUNFELDER,* F. S. BATES, and C. W. MACOSKO

Department of Chemical Engineering and Materials Science

and
M. STROUP-GARDINER and D. E. NEWCOMB

Department of Civil Engineering

University of Minnesota
Minneapolis, Minnesota 55455
Microstructural transformation of a poly(styrene-b-butadiene-b-styrene),
SBS,
triblock copolymer blended with asphalt was studied as the asphalt composition
was varied from 0 wt% to 96 wt%. Transmission electron microscopy (TEM), dynamic mechanical spectrometry (DMS), and differential scanning calorimetry (DSC)
were used. The blends were made in batch mixers a t 200"C, or by solution casting
from a nonselective solvent (trichloroethane) a t -28C. Asphalt partially solubilizes
the polybutadene (PB)midblock of the SBS producing saturated PB microdomains
along with macrodomains of asphalt. When the asphalt concentration was varied
from 10 to 90 wt%, the asphalt phase separated into a variable number of large
domains, while the SBS-rich regions formed a continuous matrix. Networks of
SBS-rich regions were observed a t low magnification; these are referred to as
macro-networks. At higher magnification, networks that are stabilized by polystyrene (PS)microdomains (denoted micro-networks) are also formed. The presence of
a macro-network is also confirmed by stress relaxation tests. The macro-network
broke down into microgel-like structures when the asphalt composition exceeded
90 wt%. Examination of the interior of the SBS-rich regions showed that the shape
of the PS microdomains transformed from short cylinders to lamellae, hexagonally
perforated lamellae (HPL),back to lamellae, short cylinders, and finally to spheres.
DMS and DSC indicate a systematic increase in the PB glass transition temperature
(T,)and negligible change in the Tgof PS as the asphalt content increases. Triblock
copolymers that can form a macro-network at low concentration will be more
desirable for highway pavement modification.
INTRODUCTION

ne of the primary uses for asphalt is in road construction. A typical road pavement contains stone
aggregates surrounded by a matrix of asphalt binder
(-5 wt%). The performance of such road pavement is
controlled by the properties of the asphalt cement
since asphalt is the continuous matrix and the only
deformable component ( 1-3). At high temperatures
(40 to 65"C), asphalt exhibits a viscous, liquid-like
behavior, whereas at low-temperatures (0to -30C).
asphalt is glassy and brittle (1). Thus, pavements
made of asphalt can show distress when exposed to

* Present address: Department of Chemical Engineering, University of Karlsruhe,

Germany.

POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36,No. 12

high or low temperatures (1). At elevated temperatures

(40 to 65"C), permanent deformation (rutting) occurs
and leads to channels in the direction of travel. This is
attributed to the viscous flow of the asphalt matrix of
the road cement, which retains strain induced by the
traffic. Below a critical temperature (-10 to -3O"C),
road pavements crack a s a result of brittle failure of
the glassy asphalt matrix ( 1 ) . Hence, performance of
asphalt-based road pavements is strongly associated
with the rheology of asphalt.
Increased traffic factors such as heavier loads,
higher traffic volume, and higher tire pressure demand higher performance pavements. A high performance pavement requires asphalt cement that is less
susceptible to high temperature rutting or low temperature cracking, and has excellent bonding to stone
1707

A. Adedeji et al.

aggregates (4, 5). A common method of modifying the

rheological properties of asphalt is by blending with
polymers (4). A limited number of polymers has been
favored, including homopolymers [low density polyethylene (LDPE), high density polyethylene (HDPE),
ethylene-propylene-diene(EPDM),and atatic polypropylenes (APP)], random copolymers [styrene-butadiene random copolymers (SBR) and ethylene-vinyl
acetate copolymers (EVA)],and triblock copolymers
[styrene-butadiene-styrene(SBS), styrene-isoprenestyrene (SIS)and their hydrogenated forms]. The high
cost of these polymers compared to asphalt makes the
commercial use of modified asphalt only attractive in
road construction if the amount of polymer needed to
improve pavement performance significantly is very
small. Therefore, the major goal in asphalt modification is to find or design a polymer that improves asphalt properties to a satisfactory level at a minimum
cost.
In search of polymers that can impart optimum
improvement in rheology of asphalt at minimal loading, the miscibility of asphalt with candidate polymers
has been recognized as a critical factor. The miscibility
of asphalt has been investigated by studying structures and properties of its various blends with polymers (4, 6-9). When asphalt-miscible homopolymers
and random copolymers are used, a critical concentration at which polymers entangle is required for asphalt blends to exhibit a network behavior (10, 11).
Triblock or star copolymers (e.g. linear or radial SBS)
form a network structure with the minor component
polystyrene (PSI endblocks acting as physical
crosslinks. In asphalt blends with triblock copolymers
such as SBS that have a n asphalt-compatible polybutadiene (PB) midblock, asphalt is anticipated to
swell the midblock while maintaining the intrinsic
network of the triblock (7, 12).Such a swollen network
is illustrated in Ffg. I . However, asphalt is composed
of many components that can be broadly grouped into
two categories: polar aromatic asphaltenes and nonpolar saturated maltenes (1, 12, 13).Each component
has a different solubility parameter, and, thus, a dif-

ferent degree of miscibility ( 14) with the blocks of the

SBS.
In prior studies of compatibility of triblock copolymers with asphalt via morphological and properties
changes, SBS has usually been added in small quantities (7-1 2). Occasionally, the concentration of SBS
has been increased to produce continuity inversion in
which the SBS-rich portion forms the continuous matrix (1, 12). These studies did not provide details of
swelling and of the interactions of the PB midblock
and PS endblocks with the asphalt components. In
this investigation, we chose to study the interactions
of asphalt with SBS by monitoring changes in blend
microstructures. A model blend system containing a
standard asphalt (AC-20) and a linear SBS (Kraton
D1101) was used. More importantly, we started with a
neat SBS and transformation in microstructures and
properties were studied a s the SBS was diluted with
the asphalt. The morphology and properties of these
blends were studied using transmission electron microscopy (TEM), differential scanning calorimetry
(DSC),and dynamic mechanical spectroscopy (DMS).
Possible physical or chemical changes that occurred
during sample preparation were cross-checked using
size exclusion chromatography (SEC) and thermogravimetric analysis (TGA).

EXPERIMENTAL
Materials
The asphalt used in this study is a standard asphalt
named AAF-1 (grade AC-20. crude W TX Sour), provided by the SHRP Materials Reference Library. The
AAF-1 contains 14.1% asphaltene (n-heptane soluble)
or 3.1 % asphaltene (iso-octane soluble), 38.3%polar
aromatics, 37.7% napthene aromatics, and 9.6%saturates. The styrene-butadiene-styrenetriblock copolymer (SBS)is a commercial product of Shell Chemical
Co. (Kraton D1101). supplied in the form of porous
pellets. It is reported to contain 28.8 wt% PS. Size
exclusion chromatography (SEC) indicates that the
Kraton is a mixture of triblock and (-20%) diblock
copolymers. The triblock component has a weight avof 180,000 g/mol based
erage molecular weight (Mw)
on PS calibration: thus, each endblock has Mw of
about 27,000 g/mol. In general, SEC will overestimate
the true Mw by a s much as 100% since, in a good
solvent, the size of a PB chain will be much larger than
a PS chain of equal Mw.The asphalt and the SBS were
used without further purification.

Sample Preparation

Fig. 1. Schematic illustration of a network in asphalt/SBS

blend showing the PS endblocks forming spherical miceUes
and the polybutadiene midblock (connectors of the spheres)
being swollen by asphalt oligomer.
1708

Samples were prepared either by solution casting or

melt blending. Solution Casting: Stock solutions of
asphalt and SBS in trichloroethane (5g/ 100 mL)were
each prepared and blended in varying proportions to
produce 40 mL sample solutions. The solvent was
slowly removed at room temperature (-28"C), under a
fume hood, over the course of two weeks until no
further change in mass of the blend.
POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36, No. 12

Asphalt Modifiid by SBS Triblock Copolymer

Melt Blending: Melt-mixed samples were prepared

in a batch mixer (Haake-Buchler HBI System 90, a
torque rheometer with rollerblades) for SBS concentrations above 10%using a rotor speed of 100 rpm,
corresponding to a maximum shear rate of 130 s-'.
This mixer will, henceforth, be referred to as the
Haake mixer. The mixer was purged before loading
with industrial grade nitrogen gas in order to reduce
degradation and crosslinking, and blending was done
under a nitrogen blanket. Because of the large difference in the viscosity of SBS and of asphalt, 20 g of SBS
was premixed at 200C for about 4 min, followed by
stepwise addition (2 to 3 g) of asphalt at 1 min increments until the desired composition was attained. A
total of 50 g was always used, which means the mixer
chamber is -75% filled. For high concentrations of
asphalt, the blending procedure had to be modified
because of the limited volume of the mixer: instead of
starting with pure SBS we started with a pre-blended
asphalt/SBS mixture (containing 40 wt% SBS) followed by the stepwise addition of neat asphalt. Total
blending times ranged from 16 min for the blend containing 10 wt% asphalt to 145 min for 94 wt% asphalt.
At low concentrations of SBS we also utilized a
pitched-blade propeller mixer (Silverson, model L4R).
In the Silverson mixer, the asphalt was first heated to
200C and the SBS was added all at once while stirring the asphalt. Samples were removed from the
batch mixers and compression molded into rheology
test specimens.
DMS
Dynamic mechanical tests for glass transition temperature determinations were done in a shear mode
using a Rheometrics RMS-800 Mechanical Spectrometer with 10 mm diameter parallel plates. Temperature scans were conducted at a heating rate of 2 to
3"C/min with a fured measurement frequency of 10
rad/s; the material was kept under a nitrogen atmosphere. Stress relaxation tests of low SBS concentration blends (520%)were performed with a Rheometrics RSA I1 Solids Analyzer by applying 0.3% strain at
room temperature (-28C) and then monitoring the
force vs. time. Disks of 15 mm diameter and thicknesses ranging from 3 to 5 mm were used.
DSC
Five to 10 mg samples were cut from the compression molded specimens. These were loaded in sealed
aluminum pans and tested in a differential scanning
calorimeter (Perkin-Elmer DSC 7) with liquid nitrogen
coolant. Calibration was done with high-purity standards of indium (meltingpoint 156.6"C)and cyclohexane (crystal transition -87.06"C). The scans were performed at a heating rate of 40"C/min from -170 to
either 150 or 200C, and data were collected during
the second scans.
Microscopy
Ultra-thin films (about 70 nm thick) were obtained
by ultra cryomicrotomy using a Reichert Ultracut miPnl VMER

ENGINEERING AND SCIENCE, JUNE 1-

VOl. 36,NO. 12

crotome (equipped with a Reichert FCS cryo-chamber)

and operated at -110C. The films were stained in
osmium tetroxide, OsO,, vapor by suspending them
over a 4% aqueous solution of OsO, in a n enclosed
glass chamber for 35 to 40 min. OsO, preferentially
stains the PB midblock of SBS. Bright field images
were obtained by mass-thickness contrast on a JEOL
JEM- 1210 transmission electron microscope, at a n
accelerating voltage of 120 kV. Thus, the PB-rich regions appear darkest in the electron microphotographs, and the fine and the coarse bright domains
are the PS and the asphalt-rich regions, respectively.

SEC
Size exclusion chromatography (Waters, 150-C
ALC/GPC) was used to determine molecular weights
of the material, and to evaluate melt processed products for any degradation incurred during processing.
Columns of pore sizes of 500, 1000, and 10,000 A
(Polymer Laboratories) were used, and calibrated with
standard polystyrene homopolymers. The solvent medium was tetrahydrofuran, and sample solution was
injected at a flowrate of 1 mL/min. A refractive index
detector was used.
TGA

Thermogravimetric analysis (Perkin-Elmer TGA 7,

1020 series) was used to estimate the possible mass
loss that could be caused by melt blending at 200C.
The samples were held at 200C for 90 min, and mass
was monitored.

RESULTS
Electron micrographs of the "as-supplied'' SBS material annealed at 180C for 96 h, of the SBS melt
processed at 200C for 10 min, and of the solutioncast SBS are shown in Figs. 2a, b, and c, respectively.
The PS (lighter portion) forms disordered short cylinders and spheres dispersed in a PB matrix (15, 16).
End-on views of the cylinders appear a s spherical domains. The morphology of the melt processed asphalt/SBS blends are displayed in Fig. 3 as the asphalt content is increased from 0% (Fig. 3a) to 92%
(Fig.31). When the asphalt content is between 10 and
90%. the SBS-rich portion forms the continuous matrix. At 92% (Rg.3). 94% (Fig. 7),and 96% (Fig. not
shown), the SBS-rich portions become discontinuous
microgel regions. Morphologies of the solution cast
blends are shown in Fig. 4. These morphology are not
very different from those of the melt processed blends.
SBS-rich regions form the continuous matrix and only
microgels are formed in the blends containing 80 and
90% asphalt (Figs.4i and 4j).Note that Figs. 2b and 2c
are high magnification versions of Figs. 3a and 4a,
respectively.
An example of a large field view of macrophase separated asphalt is shown in Fig. 5 for a blend containing 60% asphalt in which the SBS-rich portion constitutes the continuous matrix. A large field view of the
melt-processed asphalt /SBS blend containing 90%
1709

A. Adedeji et al.

Fig. 2 . Morphology of (a)an as-supplied SBS annealed f o r 96 h at 180C; (b)a melt-processed SBS; and (c)a solutioncast SBS.

1710

POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 3s, No. 12

Asphalt Modifiid by SBS Triblock Copolymer

(b) 10 %

(a) 0 %

(d) 30 %

(c)20 %

Fig. 3. Microstructures of meltprocessed asphalt/SBS blends containing asphalt concentrationof (a)0%,(b)lo%,(c)20%, (d)30%. (el
40%, If) 50%, (9)60%. [hJ70%,(i) 80%.Li, 88%,(k)90%,and (Z) 92%.

POLYMER ENGINEERINGAND SCIENCE, JUNE 1-

Vol. 3s, No. 12

1711

A. Adedeji et al.

(e)40 %

(f) 50 %

(h) 70%
Fig. 3e-h.-Continued.

asphalt is shown in Fig. 6. Even at this relatively high

asphalt loading the SBS-rich region remains as the
continuous matrix. When the concentration of asphalt
1712

is 94% (mixed in the Silverson mixer), the SBS-rich

portion starts to lose its continuity a s displayed in

Fig. 7.
POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 3f5,No. 12

Asphalt Modfled b y SBS Triblock Copolymer

(i) 80 %

(i) 88 %

(k) 90 %

(1) 92 %
Fig. 3i-1.-Continued

POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36 No. 12

1713

A. Adedeji et al.

(a) 0 %

(b) 10%

(c) 20 %

(d) 30 %

Fig. 4 . Microstructures of solutwncast asphaltlSBS blends containing asphalt concentration of (a)0%,(b)10%.(c) 20%. (d)30%, (e)
40%, If) 50%, (g) 60%,(h) 70%, (i) 80%.and 0) 90%.

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POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36, No. 12

Asphalt Modifiid b y SBS Triblock Copolymer

( f ) 50 %

(e) 40 %

(h) 70 %
Fig. 4e-i. -Continued.

SEC chromatographs of the as-supplied SBS and

melt processed blends are shown in FYg. 8. As-supplied SBS is shown to contain -20% poly(styrene-bPOLYMER ENGINEERING AND SCIENCE, JUNE

Vol. 36,No. 12

butadiene) (SB)diblock copolymer. Melt blending generates -20% large molecular weight molecules
(predominantly twice the molecular weight of the pri1715

A. Adedeji e t al.

(i) 80 %

(i)90 %
Fig. 4i-J. -Continued.

mary triblock ones). The fraction of the higher molecular weight species are similar for different blend compositions that were processed at different processing
times. This coupling reaction probably occurs during
the 4 min of h g h stress shearing of the neat SBS prior to
1716

blending. Size exclusion chromatographs of the asphalt

components show no evidence of new higher or lower
molecular weight species incurred by asphalt during the
high-shear-high-temperature melt-blending (@re not
shown). One might expect a signlflcant mass loss of the
POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36,No. 12

Asphalt ModiJed b y SBS Triblock Copolymer

Fig. 5. A largefwld view of morphology of the melt processed

asphalt/SBS blend containing 60%asphalt.

Fg. 7. Morphology of the melt-processed asphaltlSBS blend

containing 94% asphalt.

DSC thermographs of the melt processed blends are

shown in Fig. 9. The glass transition temperature (T,)
of the PB midblock increases as the asphalt content is
increased. Figure 10 also indicates a systematic increase in Tg of PB as the asphalt content increases.
The transition peak in the dynamic loss modulus also
broadens with the increase in asphalt content presumably because the transition peaks of the asphaltand PB-rich portions overlap. The changes in Tg of
asphalt-rich and PB-rich regions that are estimated in
the DSC and DMS measurements are summarized in
Table 1 and plotted in Fig. 11. The shift in T, is much
less than would be anticipated by the Fox equation.
DMS also indicates that the T, of the PS endblocks
show no significant changes a s illustrated in Fig. 12.
Stress relaxation plots in the form of compressive
moduli E(t)vs. time ( t ) ,after applying 0.3% strain to
melt-processed blends containing 0, 6, 8, 10 and 20%
SBS, are displayed in Fig. 14. Addition of SBS apparently lowers the stress relaxation rate, and infinite
relaxation times (stress plateaus) when 3-D macronetworks are produced in the blends (i.e. blends containing 10 and 20% SBS).
DISCUSSION
Q. 6. A largefleld view of morphology of the melt processed

asphalt/SBS blend containing 90% asphalt. The SBS-rich

phase surprisinglyforms the continuous matrix.

asphalt by processing at 200C via evaporation of the

low molecular welght components. However, TGA shows
negligible mass loss (<0.05%).
POLYMER ENGINEERING AND SCIENCE, JUNE 19S6, Vol. 3s, No. 12

Size exclusion chromatographs of the as-supplied

SBS (Fig.8)revealed -20% diblock copolymer in the
neat material. McKay et al. (8)demonstrated that the
presence of a diblock (5to 50%)in a triblock of similar
chemistries and compositions lowers the plateau storage modulus and raises the loss tangent as the
diblock chains dilute the bridging blocks of the
1717

A. Adedeji et al.

10%

SBS

-100

AAF-1 as supplied

-50

50

100

Temperature ['C]
15 16 1 7 18 19 2 0 21 22 23

FYg. 9. DSC themographs of neat asphalt, neat SBS, and melt

processed asphalt / SBS blends.

Elution Volume [ml, min]

Fg. 8. Size exclusion chromatographs of SBS components of
melt processed asphaltlSBS blends, as-supplied SBS. and
asphalt.

triblock. We conjecture that the stability of the networks in these blends are promoted by the bridging
process of the triblock. The stability of these networks
may thus be lowered by the presence of the diblock
copolymer chains in the triblock copolymer.
TEM micrographs of annealed as-supplied, meltblended, and solution-cast SBS show almost identical
structures, as shown in Fig. 2. This implies that the
reported microstructures are not significantly
changed by the blending procedures that are used in
this study. However, SEC chromatograph of 100%
SBS in Fig. 8 reveals that high molecular weight products are generated during processing a s indicated by a
pronounced shoulder at about 410,000 g/mol, elution
volume = 17.3 mL (twice the primary molecular
weight of the triblock) in the melt-processed blends.
This high molecular weight SEC peak is also observed
in all the melt-processed blends that were processed
in the Haake mixer. However, blends prepared by solution-casting or melt-blending in the Silverson mixer
(results not shown) show no evidence of such high
molecular weight species. The high molecular weight
species are thus attributed to coupling of the PB mid1718

-a

lo8

b
1o7

106
-100

-80

-60

-40

-20

20

Temperature ['C]

Fig. 10. Changes in the Tgof the PB midblock of the SBS as

observed by changes in the loss modulus. G", us. temperature
at strain = 1 %,frequency = 10 rad/s.

block of SBS, which is caused by high-temperaturehigh-shear processing in the Haake mixer. After fitting
the observed SEC distribution of molecular sizes to
the sum of two Gaussian curves, the area ratio of both
peaks is used to estimate the amount of coupled SBS,
which is approximately 20% of the loaded SBS. Also,
POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36,No. 12

Asphalt Modijied by SBS Triblock Copolymer

Table 1. Summary of the Observations in the Melt Processed AsphalffSBS Blends.
Separated asphalt
Tgm ("C)

Tg,asphalt

% asphalt

DSC

DMS

0
10
20
30
40
50

-91
-87
-88
-82
-78
-74
-70
-68
-62

-95

60
70
80
88
90
92
94

("C)

DSC

-76
-65
-60
-50
-50

96
100

(Yo)

Microstructure of
PS

Macro-network ?

DMS

TEM low mag.

TEM high mag.

TEM, RSA

1
2
4
5
8
30
31
48
34
69

cylinder
lamellar
HPL
lamellar
cylinder
cylinder
sphere
sphere
sphere
sphere
sphere
sphere

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
no
no

95
95
95

-89
-83

To,, ("C)

-42
-35
-3 1
-2 7
-2 7
-20
-1 7
-22

95

-29
-29
-32
-29

0.5

-20
ca
*

co
*

-80

20

40

60

80

100

Asphalt [wt %]

Fig. 1 1 . Changes in T,'s of the asphalt and of the PB midblock

of the SBS compared to the anticipated change based on the
Fox equation.

Fq. 12. Loss tangent us. temperature for the PS segment of

the melt-processed neat SBS triblock copolymer and of the
SBS in asphalt/SBS blends at strain = 1%, frequency = 10
rad/s.

on the low molecular weight side (Fig.8).a broadening

of the peak is observed that is presumed to indicate
scission of a relatively small percentage of the SBS
triblock copolymer into S B diblock copolymer chains.
TEM micrographs of the melt-processed blend containing 10% asphalt shows a few macrodomains of
-100 nm diameter (the lighter elongated structure in
Flg. 3b). This is surprising since the asphalt concentration is small. However, this observation has also
been made in blends of homopolymer with triblock
copolymers ( 17, 18). Formation of homopolymer macrodomains at low concentrations in a homopolymer /
triblock copolymer blend is apparently a characteristic of triblock copolymer. In addition, the observed
macrodomains of asphalt may be regions rich in polar
aromatic asphaltene since they are immiscible (by virtue of different solubility parameters) with either segment of SBS (14).At higher concentrations of asphalt,
discrete macrodomains of asphalt with diameter of 1
pm are formed in continuous matrices of SBS-rich

regions. A typical large-field view of the morphology of

melt-blends containing asphalt concentration ranging
from 20 to 80%is displayed in Fig. 5 (for60%asphalt).
Surprisingly, the SBS-rich portion forms the continuous matrix even when the SBS content is just 10%.as
illustrated in Fig. 6. The asphalt macrodomain size
remains at about 1 pm, but the number density increases as the asphalt concentration increases. On
reducing the SBS concentration to 6%(blended in the
Silverson mixer), the SBS-rich continuity breakdown
occurs in many locations, and apparently there is a
continuity inversion in which asphalt becomes the
continuous matrix with discrete but stretched multiarmed regions of SBS-rich portions (Fig. 7). When the
SBS concentration is further lowered to 4% (morphology not shown), the SBS-rich regions forms discrete,
nearly spherical macrodomains of -200 nm diameter,
in a continuous matrix of asphalt. Continuity inversion in asphalt/SBS blend is a result of a stepwise
breakdown of SBS-rich region as the SBS concentra-

POLYMER ENGINEERING AND SCIENCE, JUNE 19Qf3, Vol. 36,No. 12

1719

A. Adedeji et al.

20

40

60

80

100

Concentration of asphalt in blend [%]

FUJ. 13. Plot of area fractions of asphalt macrodomains estimatedfrom electron micrographs us. massfractions of asphalt
in the blendformulations. Broken line is the expected result i
j
asphalt were totally immiscible in the SBS.
108

10'

106

105

lo4

lo3
10.'

loo

10'

lo2

to3

lo4

Time (s)
Fig. 14. Stress relaxation responses of neat asphalt and asphalt/SBS blends containing 6, 8, 10.or 20% SBS after application of 0.3%strain at 28C.

tion is systematically lowered. This represents a n important result of this study.

If all the added asphalt is macro-phase separated in
the blends, we should observe area fractions in the
TEM images that are comparable to the mass fraction
of asphalt in the blend formulations since the macrodomains are much larger than the microtomed film
thickness (70 nm). However, if a portion of the asphalt
is solubilized in the PB region, the estimated area
fraction should be less than the mass fraction of the
asphalt in the blend formulations. We estimated the
area fractions of asphalt that is phase separated as
macrodomains (coarse bright regions in the micrographs) in these blends using the area coverage ratio
of the asphalt to that of the SBS-rich regions from low
1720

magnification micrographs (such as Figs. 5, 6, and 7).

The results are presented in Fig. 13 as a plot of area
fractions against mass fractions of asphalt in the formulations. When the mass fraction of asphalt in the
blend formulations varies from 10 to 50 wt%, the estimated area fractions of the phase separated asphalt
are much less than the asphalt mass fractions in the
blend formulations. This result is consistent with the
notion that the PB-miscible portion of the asphalt is
solubilized in the PB microdomains while the PB-immiscible asphaltene fraction is phase separated a s
macrodomains (12). When the mass fraction of asphalt in the blend formulation is raised to 60%, there
is a sudden rise in the area fraction that increases
further a s the mass fraction of asphalt in the blends is
further increased. We interprete this sudden rise in
area coverage as a n indication of saturation of the PB
midblock with PB-miscible saturated maltene. The
area increases a s some saturated maltene is also
phase separated along with PB-immiscible asphaltene. The macrodomains will then be mixtures of asphaltene and maltene.
Examination of the interior of the SBS-rich regions
in the melt-processed blends at a higher magnification
(40,OOOX) reveals that different microstructures are
present at different concentrations of asphalt a s indicated by the varying shape of the PS microdomains in
the PB-rich matrix. The microstructures of the SBSrich regions at different concentrations of asphalt
(ranging from 0 to 92%)are each displayed in Q. 3 .
The microstructure of the neat SBS is characterized a s
disordered short cylinders of PS in a continuous matrix of PB (Fig.3a) (15, 16). Addition of 10% asphalt
(Fig. 3b) does not seem to significantly alter the microstructure of the SBS-rich regions. At 20% asphalt, a
short-range layered (lamellar) structure is observed
(Fig. 3c). The blend containing 30% asphalt is strikingly different, with a hexagonally perforated lamellae
morphology (HPL)(19).HPL contains hexagonally perforated layers of the minor component (PS-rich portion) and layers of the major component (PB-rich portion) that are connected through the perforations in
the layers of the minor component. This description
can be seen in Fig. 3d as the upper portion of the
image shows dark PB-rich and bright PS-rich layers,
and the lower left hand corner shows that the PB-rich
dark layers are connected. This result is surprising
since the HPL phase has only been observed in tailored neat diblock copolymers and homopolymer/
diblock copolymer blends, in which the minor component constitutes a volume fraction of 0.37 to 0.4 (19).
Note that the initial PS composition is 0.29 to 0.30 in
the neat SBS, and the observation of the HPL phase
implies that the PS segment has been swollen by some
component(s) of the asphalt. The observed transformation of discrete short cylinders of PS to lamellae
and to HPL thus suggests to us that some asphalt
component(s1must be miscible with PS, leading to PS
microdomains that are more swollen than the PB domains. In this way, the microstructural changes proPOLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36, No. 12

Asphalt Modifiwd by SBS Triblock Copolymer

vide a delicate indicator of partitioning of asphalt components between the block domains.
At 40% asphalt, a lamellar structure is again observed, which we interpret a s a n indication of increased swelling of the PB that balances that of the PS
domains (20-23). Disordered short cylinders returned
at 50 and 60% asphalt. When the asphalt content is
70, 80, 88,90, 92, and 94%. Figs. 3 h through 1 and
Fig. 7, respectively, show that the PS-segment of the
SBS forms spherical domains in the continuous matrix of PB-rich phase. The transformation of the PS
domain shape from lamellae (at 40% asphalt) to
spherical particles (at 80%asphalt) is interpreted as
evidence for swelling of the PB midblock chains, and
to a lesser extent the PS, by the asphalt. But the
overall trend of the change in microstructure with
increasing asphalt content suggests that the PS segment is more swollen than the PB segment when the
asphalt content is less than 30%,and the PB is more
swollen when the asphalt concentration is between 40
and 94%.This unusual trend might be attributed to a)
fractionation of the components of the asphalt into the
PS and PB microdomains, b) the complexity of the
thermodynamic relationships between the asphalt
components and the SBS segments, and c) the possible looping and bridging conformations of SBS
triblock copolymer chains (24-26). which might restrict equilibrium structure formation. Bridging is a
case where two ends of a triblock are located in two
different domains; looping is when two ends of the
triblock are located in the same domain. We note that
when the asphalt content is 94% (Fig.7).the interior of
the microgel-like SBS-rich regions show spherical
particles of PS in continuous matrix of PB that is
swollen by asphalt. At 96% asphalt (imagenot shown),
the microstructure of the interior of the SBS-rich macrodomains becomes more difficult to resolve microscopically. The SBS-rich macro domains are seen as
discrete dark regions.
We point out that the morphology of the blend containing 90% asphalt that is shown in Fig. 6, at a low
magnification (5000X). is also displayed in Fig. 3k but
at a much higher magnification (40,OOOX).In the low
magnification image (Fig. 3)a network is formed by the
SBS-rich portion, while in the high magnification image, a network of PB-rich region that is stabilized by
the PS spherical particles is observed at a molecular
level. The network observed at the low magnification
matches the description of a network in asphalt/SBS
mixture proposed by Kraus ( 12). and the network observed at the high magnification coincides with the
anticipated morphology that is schematically illustrated in Fig. I . Thus, we described the low magnification network of the type that is shown in Q. 6 as
macro-network because it is discernible at low magnification, and the type that is shown in Q. 3k is
hence described a s micro-network a s it can only be
seen at high resolution.
In addition to the melt-blends discussed above, the
blends were each solution-cast. Large field view of
morphology of these blends are similar to those of the
POLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36, No. 12

melt-blends that are represented in Fig. 5. The morphology of the solution-cast blends also shows macrodomains of asphalt-rich regions that supports the
notion that the observed asphalt macrodomains in the
melt-blends are not a result of inefficient mixing. However, there are differences in the microstructures of
the SBS-rich region. The microstructure of neat SBS
solution-cast from trichloroethane is shown inFig. 4a.
At 10% asphalt content short-ranged lamellar morphology is observed. More interestingly, no macrodomains are observed at this concentration unlike in the
melt-processed counterpart. However, this is not very
surprising since a good solvent enhances solubilization of homopolymers or oligomers in block copolymers (27). At 20% asphalt content, macrodomains of
asphalt are observed (Fig. 4c1. We did not study systematic addition of asphalt to SBS in order to determine the concentration at which macro-separation of
the asphalt is initiated. The occurrence of asphalt
macrodomains persists a s asphalt content increases.
The occurrence of asphalt-rich macrodomains in the
solution cast blends thus confirms that the existence
of macrodomains in the melt processed blends is not a
reflection of inefficient mechanical mixing. They result
because of the thermodynamic interactions between
the components of asphalt and of the SBS segments,
coupled with limited swelling of the PB midblock produced by bridging of its chains. Examination of the
interior of the SBS-rich regions at a high magnification (40,OOOX) shows that the microstructure of the
blend of 20% asphalt contains lamellae and cylinders
of PS block segments in PB-rich matrix. When the
asphalt content is increased to 30, 40, or 50%. the
interior of the SBS-rich phase shows predominantly
cylinders of PS. We observed no HPL phase in these
solution blends. Disordered short cylinders of PS are
observed at 60% as we observed in the melt-processed
blend. Again, at 70% asphalt (Fig. 4h),cylinders of the
PS block segment are produced. At 80%asphalt, the
SBS-rich region apparently still forms the continuous
matrix (Fig. 4h) but the thickness of the SBS-rich
region is not a s uniform a s was found in the meltprocessed blends. In addition, the interior of the SBS
shows spherical particles of PS in continuous matrix
of PB. Furthermore, at 90% asphalt, the asphalt is
found to constitute the continuous matrix, and the
SBS-rich region forms microgel-like structures. The
interior of the SBS-rich region also shows spherical
particles of PS. The microgel-like structures at 90%
asphalt are different from what is produced in the melt
blends in which the SBS-rich phase forms the continuous matrix. This is probably because of the fact that
the solution blends started with dissolved individual
chains while the melt blends started from ordered SBS
chains (processing temperature is lower than the order-disorder temperature of the SBS).
DSC and DMS were used to determine how T,
changes in the asphalt-rich, PS-rich and PB-rich regions of the blends. Neat asphalt exhibits a relatively
broad Tg.In the blends, only the transitions of the
asphalt-rich and of the PB-rich regions are discernible
1721

A. Adedeji et al.

(Fig.9).Tgof the PS-rich region is best detected with

DMS (Fig. 12),and no significant shift is observed.
Hence, there are three co-existing compositionally different regions in the blends. In neat SBS, Tg of the PB
midblock is found to be -95C. The transition peak of
the PB-rich region becomes broader (Fig. 10) a s the
asphalt content increases. This suggests that the asphalt components swelling the PS block do not affect
its Tg significantly. Below 50% SBS, Tg of PS is not
detectable because of its low concentration in the
blend.
Tgof the PB-rich and of the asphalt-rich regions are
each plotted vs. composition in Fig. 1 1 . The Tgof the
PB-rich region determined by DSC or DMS shows systematic increase a s the asphalt content increases.
This suggests that some component(s)of asphalt that
have Tg(s)
higher than pure PB has mixed with the PB
midblock resulting in a higher T,. When compared to
the prediction of the Fox equation (based on pure
asphalt Tg= -30C and PB Tg= -95C) the experimental Tgsare lower, suggesting incomplete mixing of the
asphalt with the PB midblock of the SBS triblock copolymer. This is in agreement with the morphological
observations.
The Tgof the asphalt-rich portions rises from 20 to
80% asphalt, then decreases from 80 to 90%, and
remains approximately constant from 90 to 100%asphalt. This trend is in agreement with the notion that
the asphalt fractionates into low TgPB-miscible, and
high TgPS-miscible components. At 20% asphalt, the
higher Tg.PS-miscible components of the asphalt are
solubilized in the PS end-blocks, and the low Tgcomponents in the PB midblock to generate the lamellar
microstructure (Fig.3c).The PB midblock is, however,
not saturated. Solubilization of the high Tg components of the asphalt in the PS end-block produces
asphalt-rich macrodomains with low concentration of
the high Tgcomponents of the asphalt. This explains
the observed low Tgof the asphalt-rich portion. When
the asphalt concentration increases, the concentration of the PB-miscible components of the asphalt also
increases, which subsequently increases the extent of
swelling of the PB chains. Swelling of the PB chains
produces a positive curvature towards the PB (20-23).
This process induces reduction in the PS domain size
(23),and rejection of the high Tgasphalt components
into the asphalt-rich regions a s the asphalt concentration increases. Hence, the curvature of the PS domain increases to finally produce spherical microdomains, and the Tg of the asphalt-rich portion
increases, as the asphalt concentration increases.
We have utilized the stress relaxation technique to
evaluate the elastic nature of the neat and blended
materials containing 6, 8, 10, or 20% SBS (mixed in
the Haake mixer) (28, 29). The changes in stress are
monitored in form of compressive modulus E ( t ) for
different compositions of asphalt /SBS blends and are
shown in Fig. 14. The neat asphalt shows the fastest
stress relaxation. When the SBS contents are 6 and
8%,stress is continuously dissipated and the modulus fails to reach a plateau at the longest experimental
1722

times. However, when the SBS content is 1 0 or 20%.

the long time stress levels reach a plateau, which is an
indication of the presence of global network behavior.
These observations are in agreement with the morphological results discussed earlier where a macronetwork is seen when the SBS content is larger than
10%. while only microgels are formed when SBS content is less than 10%.In addition, within experimental
accuracy, the initial stress level decreases with SBS
content, which can be attributed to the low Tg (PB)
component. We also exploited this stress relaxation
test to establish that the solution-cast blends containing 10 or 20% SBS do not form macro-networks as
constant stress plateaus were not achieved (stress
relaxation plots not shown). This test provides a quick
method for testing whether an elastic macro-network,
or microgel, is formed in a modified asphalt, rather
than the laborious TEM technique.
SUMMARY

The miscibility of asphalt components with segments of a SBS triblock copolymer has been investigated using a model asphalt (AAF- l ) / S B S blend system. Melt processing in batch mixers and solutioncasting techniques are used to make different
compositions of asphalt/SBS blends. Starting with
neat SBS, changes in morphology were studied as a
function of asphalt. Asphalt composition was varied
from 0 to 96%, and the microstructures of the blends
are characterized using SEC, DSC, DMS, TGA, and
TEM techniques.
Two types of network classified as macro- and micro-network were formed. Macro-network was formed
by phase separation of asphalt as macrodomains of
- 1 pm diameter in a continuous matrix of the SBSrich portion. The SBS-rich regions formed a continuous matrix when the SBS concentration was varied
from 90 to 10%. Continuity inversion occurred by
stepwise breakdown of the SBS-rich continuous matrix a s the SBS concentration was reduced below 10%.
The presence of the macro-network was also been
confirmed by a constant stress plateau using stress
relaxation tests.
High magnification examination of the interior of
the SBS-rich portions revealed the micro-network of
asphalt-swollen PB midblock with swollen PS microdomains as physical crosslinks. When the asphalt
concentration was varied from 10 to 30%.the shape of
the PS microdomain transformed from short cylinders
to lamellae and hexagonally perforated lamellae indicating that the PS segment was swollen by some PScompatible component(s) of the asphalt. As the asphalt concentration was increased from 40 to 94%.
the shape of the PS microdomain changed from lamellae to short cylinders and finally to spheres, which
indicated stronger swelling of the PB segment by the
PB-compatible component(s) of asphalt than the
swelling of the PS segment by the PS-compatible component(s) at low SBS concentrations. Mixing of component(s) of asphalt with PB segment was confirmed
by a systematic increase in PB Tg.as the asphalt conPOLYMER ENGINEERING AND SCIENCE, JUNE 1996, Vol. 36, No. 12

Asphalt Modijkd b y SBS Triblock Copolymer

centration was increased; the Tg of the PS remained
approximately constant. A summary of these observations is presented in Table 1 . The formation of the
macro-network is desirable, and a SBS (e.g. higher
molecular weight) that can produce such macro-network at a low concentration (- <5%) will be of a
practical interest.

ACKNOWLEDGMENTS
This research project was supported by the Minnesota Department of Transportation and the Federal
Highway Administration. T. G. also acknowledges a
scholarship from the Ernest-Solvay-Stiftung (Germany). We are grateful to Dr. David Giles for helping
with rheology tests.

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