EUROPEAN

POLYMER
JOURNAL
PE
European Polymer Journal 41 (2005) 2831–2844
www.elsevier.com/locate/europolj

Asphalt modification with different

polyethylene-based polymers
Giovanni Polacco a,*, Stefano Berlincioni a, Dario Biondi a,
Jiri Stastna b, Ludovit Zanzotto b
a
Dipartimento di Ingegneria Chimica, Università di Pisa, Via Diotisalvi 2, 56126 Pisa, Italy
b
Department of Civil Engineering, University of Calgary, 2500 University Drive, Calgary, Canada T2N 1N4

Received 6 May 2005; received in revised form 26 May 2005; accepted 28 May 2005
Available online 22 July 2005

Abstract

Several polyethylene and polyethylene-based copolymers were used to modify a 70/100 penetration grade asphalt
from vacuum distillation. The morphological and storage stability analyses showed that, in all cases, the obtained mate-
rials were strongly biphasic and tended to separate into polymer-rich and asphalt-rich phases. However, among the
tested polymers, a linear low-density polyethylene allowed for the preparation of a mix that had strongly enhanced
mechanical properties, with respect to those of the base asphalt. Mixes with different percentages of this polymer were,
therefore, prepared and studied from a rheological point of view, both in the range of small and large deformations. The
analysis showed that, in spite of its insolubility, the polymer spread continuously through the asphalt matrix and that
the obtained properties can probably be ascribed to the formation of a very low extent of crosslinking between the poly-
mer chains.

2005 Elsevier Ltd. All rights reserved.

Keywords: Polymer modified asphalts; Polyethylene (PE); Rheology; Crosslinking

1. Introduction reduction of maintenance costs. At the same time, the

Asphalts are widely employed in several applications,
but the most important one is related to the paving
industry. In consideration of increased traffic loads
and in order to improve pavement performance, poly-
mer-modified asphalts (PMA) have been developed dur-
ing the last few decades [1]. The added polymer (usually
2–6% by weight) can strongly enhance the binder prop-
erties and permit the building of safer roads and the
*
Corresponding author. Tel.: +39 0505 11220; fax: +39 0505
11266.
E-mail address: g.polacco@ing.unipi.it (G. Polacco).
addition of a polymer causes a significant increase in
the production costs and adds operative complications
that are mostly related to the mixing and storage. With
regard to the latter, the low compatibility between as-
phalt and polymer can lead to phase separation when
the material is stored at a high temperature (160–
200 C) in the absence of stirring. In such a case, a poly-
mer-rich phase migrates to the higher part of the storage
tank, while an asphalt-rich phase segregates into the
lower part. This results in an inhomogeneous material
that is useless for paving and can cause troubles due
to the extremely high viscosity of the part with very high
polymer content.

0014-3057/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2005.05.034
2832 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
Unsaturated thermoplastic elastomers like styrene–
butadiene–styrene (SBS) block copolymers are probably
the most commonly used polymers. They enhance an as-
phaltÕs elastic recovery capacities and, therefore, its
resistance to permanent deformations. Even so these
polymers are not, in most cases, naturally compatible
with majority of asphalts, addition of aromatic residues,
or use of compatibilizing agents may improve their com-
patibility with asphalts significantly. SBS block copoly-
mers with higher molecular weight must often be
dispersed in asphalt using high shear mixing. However,
unsaturated elastomeric polymers are quite expensive
and subjected to degradation when exposed to atmo-
spheric agents and mechanical stress. Therefore, they
have to be added as virgin polymers and even if used
in small percentages they can double the price of the bin-
der. This is the reason why many researchers have fo-
cused on the use of cheaper materials for asphalt
modification. From this point of view, olefinic polymers
are very good candidates. They are available in large
quantities with different mechanical properties and at
low cost. Polyethylene (PE) and polypropylene (PP)
are plastomers, and they can bring a high rigidity to
the materials and significantly reduce deformations un-
der traffic load. Unfortunately, due to their non-polar
nature, PE and PP are almost completely immiscible
with asphalt, and their use is usually limited to the pro-
duction of impermeable membranes. In this case, the
polymer is added at higher quantities (6–30% by weight)
with respect to those used for paving mixes. These prod-
ucts are rapidly cooled to room temperature after the
mixing procedure, thus yielding a consistent pseudo-so-
lid material that is highly unstable from a thermody-
namic point of view, but whose phase separation does
not take place for kinetic reasons.
For paving applications, some PMAs obtained with
olefinic polymers have been prepared and characterized
[2–12], but storage stability remains an unsolved prob-
lem. A possible solution is the use of PE-based copoly-
mers, where the comonomer is a polar one, either inert
or reactive with respect to asphalt. Good examples of
the former are ethylene–vinylacetate (EVA) and ethyl-
ene–butyl acrylate (EBA) random copolymers
[2,3,8,9,13–17], while maleic anhydride (MA) and glyc-
idylmethacrylate (GMA) were added to PE for reactive
functionality. Another possibility is the use of reactive
ethylene terpolymers (RET), which are random copoly-
mers containing both reactive and non-reactive polar
groups [18–25].
However, when dealing with asphalts, due to the high
composition variability depending on their source, it is
always very difficult to generalize any conclusion or
establish a priori on the behaviour of a polymer. This
is why, in this paper, we started with a preliminary char-
acterization of different PMAs obtained by modifying
an asphalt from vacuum distillation with several PE
and PE-based polymers. Low-density polyethylene
(LDPE), linear low-density polyethylene (LLDPE),
copolymers of polyethylene with acrylic acid (PE–AA),
glycidylmethacrylate (PE–GMA) and RET copolymers
were used. Among these, one PMA showed strongly en-
hanced properties with respect to the starting base as-
phalt and, for that reason, it was deeply characterized
from a rheological point of view in order to understand
the reasons for this behaviour.
From a rheological point of view, conventional as-
phalt is a viscoelastic material having high temperature
sensitivity, which usually behaves as a low molecular
weight polymer [26]. Moreover, it is generally believed
that asphalt is also a rheologically simple material, but
this is not always true for PMAs whose properties can
be completely different from those of the base asphalt
[27,28]. Due to the high temperature sensitivity, the mas-
ter curves of the viscoelastic material functions for
PMAs have to be obtained covering a very large temper-
ature (frequency) range in which the behaviour of the
sample changes from that of a Newtonian fluid to that
of a glassy fragile solid. Most of the available studies
cover the linear viscoelastic region of small deformations
or rates of deformation [29,30]; however, it is sometimes
difficult to distinguish or to characterize different PMAs
in the linear viscoelastic region, and an extension to the
large deformations domain was performed in the present
study. Small amplitude oscillations, viscometry and step
strain experiments were used.
2. Materials and methods
One asphalt from vacuum distillation of 70/100
Pen grade, whose properties are reported in Table 1,
was modified through the addition of 6% (by weight)
of different polyethylenes that were either used as re-
ceived from commercial sources or after chemical mod-
ification through the addition of polar-reactive groups.
The typical mixing procedure is as follows: aluminium
cans of approximately 500 cc were filled with 250–
260 g of asphalt and put in a thermoelectric heater.
When the asphalt temperature reached 180 C, a high
Table 1
Base asphalt
Penetration (dmm) 69.4
Ring and Ball temperature (C) 47.3
Compositiona (%)
Saturates 10.6
Aromatics 63.3
Resins 15.2
Asphaltenes 10.9
a
Determined by Iatroscan.
 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
shear mixer was dipped into the can and set to 4000 rpm.
The polymer was added gradually (about 5 g/min) while
keeping the temperature within the range of 180 ± 1 C
during the polymer addition and the subsequent 2 h
of mixing. Finally, the obtained PMA was split in
appropriate amounts to prepare samples for character-
ization. The samples were stored in a refrigerator at

20 C.
The following polymers were used: RibleneFF20
(LDPE manufactured by Polimeri Europa, MFI = 0.8,
density = 0.921 kg/m3, Tm = 110 C); RibleneFC20
(LDPE manufactured by Polimeri Europa, MFI =
0.25, density = 0.922 kg/m3, Tm = 111 C); Escor5100
(PE–AA manufactured by Exxon Mobil Chemical,
AA = 11% w, MFI = 0.8, Tm = 96 C); Lotader
AX8930 (PE–AE–GMA manufactured by Atofina,
butylacrylate = 24% w, GMA = 3% w, MFI = 4,
Tm = 70 C); LotaderAX8840 (PE–GMA manufac-
tured by Atofina, GMA = 8% w, MFI = 5, Tm =
105 C); FlexireneFF25 (LLDPE manufactured by
Polimeri Europa, MFI = 0.7, density = 0.921 kg/m3,
Tm = 125 C). Other PE–GMAs were prepared in our
laboratories by melt free radical grafting of GMA on
RibleneFF20, using a Brabender Plastograph mixer,
following a procedure described in literature [31–33].
Two polymers, with a GMA content of 0.7% and
2.16% by weight were used, in the following they are re-
ferred as PEGMA1 and PEGMA2, respectively. The
indicated melting temperatures were obtained by Dy-
namic Scanning Calorimetry (DSC) measurements, car-
ried out under nitrogen flow, with a scanning rate of
10 C/min, using a Pyris Perkin Elmer apparatus cali-
brated with indium and tin standards.
After preparation, the mixes were characterized by
the classical Ring and Ball softening point (TR&B)
(ASTM D36-76), the storage stability test (UNI EN
13399) and fluorescence microscopy (UNI prEN
13632). The stability test consists of keeping the PMA
in a test tube stored in a vertical position at 180 C for
72 ± 1 h and then taking samples from the top and bot-
tom part. The difference of TR&B between the two sam-
ples indicates how much of the polymer separates and
migrates to the upper part of the tube, due to its density
being lower than that of asphalt. For the morphological
analysis, asphalt samples were taken during the PMA
preparation directly from the mixed can, and poured
into small cylindrical moulds (1 cm diameter, 2 cm
height). In order to preserve the instantaneous morphol-
ogy, the moulds were preheated to the mixing tempera-
ture so that the asphalt was not subjected to quenching
when in contact with the metal. When filled, the moulds
were put in an oven at 180 C for 15 min, cooled to
room temperature and stored at
30 C. After extrac-
tion from the cylindrical mould, the samples were fragile
fractured and the fracture surfaces examined under a
LEICA, DM LB microscope.
2833
After a preliminary characterization, the most prom-
ising polymer was selected and used to produce PMAs
with different polymer content to be studied from a rhe-
ological point of view. In particular, three PMAs were
obtained by adding 2.0%, 4.0% and 6.0%, by weight,
of polymer. Asphalt samples were poured into rubber-
ized moulds before being used for rheological testing.
The rheometer was a Stresstech by Rheologica Instru-
ments, which operates under stress control. The test
geometry was parallel plates (diameters of 20 and
8 mm, depending on the test temperature). In dynamic
measurements, frequency sweep tests were performed
in isothermal conditions. The frequency was varied from
0.01 to 1 Hz at low temperatures and from 0.05 to 5 Hz
at mean and high temperatures. Preliminary strain
sweep tests were performed in order to be sure that all
experimental conditions remained in the linear interval.
The test temperature varied from
30 C to 110 C in
order to construct the master curves of the dynamic
material functions in a wide frequency interval by using
the time temperature superposition (TTS) principle
[34,35]. Usually, frequencies in the 10
2–102 Hz interval
are associated with the normal vehicle traffic, while high-
er and lower values are correlated to heavier and lighter
traffic, respectively [36]. Viscosity measurements were
conducted in the 30–70 C temperature range and
10
3
102 s
1 shear rate range. Step strain tests were
performed at temperatures of 10 and 35 C, with an ini-
tial step varying from 0.1% to 250%.
3. Results and discussion
A set of PMAs was prepared and characterized by
the Ring and Ball softening point, morphological analy-
sis and storage stability test. The PMAs are numbered
from M1 to M8, as reported in Table 2. The first two
polymers, used for blends M1 and M2, are low-density
polyethylenes with different molecular weights. After
mixing with the base asphalt, markedly biphasic materi-
als were obtained in both cases. As an example, Fig. 1a
shows the morphology of M1 after 30 min of high shear
mixing. It can be clearly seen that a fluorescent, poly-
mer-based phase is dispersed in a dark asphaltic phase
in the form of almost spherical particles. Both the facts
that the dispersed phase is in spherical form and that no
linkages are visible between particles indicate that the as-
phalt and polymer are strongly immiscible and very low
interfacial adhesion is present between the two phases.
This is confirmed by the Ring and Ball temperatures.
TR&B for M1 is equal to 53 C, which means an increase
with respect to the base asphalt of about 6 C, even if a
quite significant amount of polymer has been added (a
similar increase in TR&B is generally obtained with very
small polymer percentages). This indicates that the poly-
meric phase behaves as a rigid dispersed phase. Of
2834 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
Table 2
PMAs content and softening point
Mix Polymer (6% by weight) Temperature (C)
M1 RibleneFF20 180
M2 RibleneFC20 180
M3 Escor5100 180
M4 LotaderAX8930 (10%) 180
RibleneFC20 (90%)
M5 LotaderAX8840 (7%) 180
RibleneFC20 (93%)
M6 PEGMA1 180
M7 PEGMA2 190
M8 FlexireneFF25 190
course, after storage at a high temperature, the poly-
meric phase completely separated and the obtained
micrographs (not reported) of the top and bottom part
of the tube test appear completely white and black,
respectively. Very similar results were obtained for M2
(Fig. 1b).
Comparing the morphologies of Fig. 1a and b, it can
be seen that the latter shows a larger diameter of the
spheres as could be expected since the molecular weight
of RibleneFC20 (used in M2) is higher than that of
RibleneFF20 (used in M1). A lower solubility is intrin-
sically related to a higher molecular weight. However, in
this case the solubility between the two phases is almost
zero and the final dimension of the droplets is, therefore,
predominantly determined by physical factors, e.g. den-
sity and viscosity, rather than chemical factors. In fact, a
high shear mixing needs a similar viscosity of the two
components to be efficient, and this is the main problem
in all PMAs production where the asphalt has a very low
viscosity in comparison to the one of the polymer. When
polymer and asphalt are highly incompatible, the result
is a liquid–liquid dispersion where the dimension of the
droplets is determined purely by hydrodynamic
conditions.
The third modifier (M3) is a copolymer polyethyl-
ene–acrylic acid (PE–AA), which was supposed to be
more compatible due to both the presence of the carbox-
ylic functionalities, which enhance the polarity of the
polymer with respect to PE, and the lower molecular
weight. Nevertheless, the results were almost identical
to the previous ones: a polymer-rich phase dispersed in
the asphaltic one in the form of droplets, a very low in-
crease in TR&B and a complete instability to high tem-
perature storage were observed. For this reason, a new
attempt (M4) followed, now using as the modifier a
mix of a low-density PE and a reactive polymer that is
a random terpolymer of ethylene, butylacrylate and
glycidylmethacrylate. The latter is often used as a com-
patibilizer due to its epoxy ring, which can react with
several functional groups. As an example, the three-term
Mixing time (min) TR&B (C)
After mix After cure
30 53.0 –
30 53.7 –
30 49.4 –
30 52.6 66.0
30 53.8 58.1
30 59.2 73.6
120 52.3 68.9
120 120.5 –
ring can react with end groups of polyesters or polyam-
ines; and therefore, the polymer can be useful in blends
like polyethylene and polyamide-6 [37], or polyolefins
and polyesters [38–40]. For the same reason, RET poly-
mers of this kind have been proposed for asphalt modi-
fication considering that carboxylic groups are present
in asphaltenic molecules, and they can react with the
oxiranic ring. The reaction creates a chemical link be-
tween polymer and asphalt micelles that prevents, or
at least strongly limits, phase separation and can im-
prove storage stability. Moreover, the high polarity of
the polymer enhances its solubility with asphalt. On
the other hand, the high number of functional groups
present in a single RET macromolecule increases the risk
of gel formation. For this reason, when an asphalt is
modified with RET, the polymer amount has to be cho-
sen very carefully, because an excessive quantity can
cause the formation of an insoluble, infusible asphalt
gel. This is why RET polymers can be added only in very
small quantities, which limit their efficacy as modifiers;
and today, their use is mainly limited to a small number
of cases or to the role of compatibilizer between an as-
phalt and another polymer.
RibleneFC20 and LotaderAX8930 were added in
a weight ratio equal to 90/10, in such a quantity that
the total amount of polymer was equal to 6% in the final
PMA. In this case, a period of curing at a high temper-
ature is required in order to let the epoxy ring react;
therefore, the sample was analyzed both at the end of
mixing and after 24 h of storage in an oven at 180 C.
It can be seen that after the high shear mixing
(Fig. 1c), the dimensions of the particles are smaller than
those reported in Fig. 1b (obtained with the same Rib-
lene). This is an indication that some enhancement in
compatibility was probably obtained, even if without
significant effect on TR&B. After the cure, TR&B was sig-
nificantly higher, showing that some interaction between
polymer and asphalt was finally obtained. However, the
cure was done in the absence of stirring and the chemical
reaction proceeded in parallel with phase separation.
 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844 2835

Fig. 1. (a) M1 30 min, (b) M2 30 min, (c) M4 30 min, (d) M4 24 h, (e) M7 30 min mix, (f) M7 24 h curing, (g) M7 48 h curing, and
(h) M8 2 h mix.

This resulted in a morphology that, in some part of the
analyzed surface, showed big spots of polymer-rich
phase (Fig. 1d). The morphology of the polymer ‘‘is-
lands’’ was very different from the previous ones and
indicates that a significant improvement of interfacial
adhesion was obtained but, at the same time, the dimen-
sions of the dispersion indicates that the reaction was
not fast enough with respect to migration and aggrega-
tion of the dispersed droplets and, therefore, not able
to prevent phase separation. In this case, a three-day
storage test was not necessary because the morphology
cannot return to a better dispersion. A possible solution
would be continuous stirring during the cure, but this is
not convenient in industrial applications where storage
is always performed in tanks, without or with very slow
mixing.
A further attempt (M5) was made by using Lot-
aderAX8840, which has a higher percentage of GMA
groups, but without obtaining significant differences
with respect to M4. Continuing with the same idea of
the reactive polymer, another two PMAs were prepared
using two polyethylenes modified with the addition of
GMA functional groups, which were grafted directly
on RibleneFF20. The two polymers, referred to as
2836 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
PEGMA1 and PEGMA2, were used in runs M6 and
M7, respectively. The advantage with respect to M4
and M5 should be that, in this case, all the polymer mac-
romolecules were functionalized. After mixing, the
PMAs were cured for 24 h at 180 C. Fig. 1e–g shows
the morphology of M7 after mixing and after curing.
It can be noted that, at the end of the mixing, the dis-
persed phase is composed of particles still well separated
but with a quite irregular shape, indicating a better
mixing and possibly an enhanced compatibility of the
asphaltic and polymeric phases. After curing, coales-
cence is visible, but in a less dramatic extent than that
observed for M4 and M5. TR&B in M6 after curing
reached 73.6 C, which was the highest TR&B yet. Again,
a complete separation was observed when the high tem-
perature storage was prolonged for three days.
In mix M8, the modifier was linear low-density
polyethylene. In this case, a completely different mor-
phology was obtained (Fig. 1h). As can be seen, large
irregularly shaped islands of polymer-rich phase were
dispersed in the asphalt-rich phase. Of course, this
morphology was destined to separation at high temper-
atures and, therefore, to storage instability, but there is
an indication of intimate mixing witnessed by the pres-
ence of small, irregular, dark regions inside the fluores-
cent one, which allows the polymer to really ‘‘modify’’
the asphalt properties. In fact, a very interesting Ring
and Ball temperature of 120.5 C was measured for this
mix.
At the end of this preliminary section, we can say that
no storage stability was achieved for all the PE-based
polymers, even for bituminous systems with added com-
patibilizing groups. This confirms the well-known prob-
lem of compatibility between asphalt and olefinic
polymers. Considering the poor results found with
LDPE modified with polar or reactive groups and the
high cost of this kind of polymer, we choose to study
the rheological properties of PMAs prepared with
Fig. 2. Storage compliance for BA, PMA2, PMA4, and PMA6.
LLDPE. The base asphalt and PMAs with 2%, 4%
and 6% LLDPE were prepared and characterized rheo-
logically. In what follows, these materials will be re-
ferred as BA (base asphalt) and PMA2, PMA4 and
PMA6, respectively.
At first, from the dynamic data taken in isothermal
frequency sweep tests, master curves were obtained;
and, it was found that the time–temperature superposi-
tion principle held for all the tested materials. In Figs.
2 and 3, the master curves (reference temperature equal
to 0 C) of storage (J 0 ) and loss (J00 ) compliance for the
base asphalt and PMA2, PMA4 and PMA6 are re-
ported. At high frequencies, which correspond to low
temperatures, the three PMAs showed a similar behav-
iour, with jJ*j in the 1 · 10
8–1 · 10
9 Pa
1 range. The
storage compliance of BA was in the same range of val-
ues but was lower than the three PMAs. The fact that
the different content of polymer was not strongly repre-
sented in the dynamic functions at this high frequency
domain is not surprising. It is well known that various
systems have almost universal behaviour when the glass
transition domain is approached [41,42].
More striking is the curve of BA which, starting at
higher values, crossed the other curves and tended to
the lower values of the storage compliance. This is prob-
ably due to the fact that the polymer, which has a very
low glass transition temperature, gives an ‘‘elastic’’ con-
tribution to the PMAs when the asphalt alone is under
its glass transition and is, therefore, stiffer. In fact, this
could be interpreted as confirmation that the polymer
forms a continuum inside the PMA and does not behave
as a completely separate filler. Approaching the lower
frequencies, the storage compliance of the PMAs be-
came lower than that of BA, and this difference rapidly
became of an order of magnitude.
Unmodified and modified asphalts also differed from
a qualitative point of view. J 0 of BA and PMA2
increased following a power law dependence. This
 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844 2837

Fig. 3. Loss compliance for BA, PMA2, PMA4, and PMA6.

Fig. 4. tan d for BA, PMA2, PMA4, and PMA6.

behaviour resembled an amorphous polymer of low
molecular weight where no equilibrium or steady state
compliance is visible. On the other hand, J 0 of PMAs
with higher polymer content showed a marked plateau,
corresponding to a quite low compliance modulus,
which extended until the end of the investigated fre-
quency region. The shape of J 0 in PMA4 and PMA6
was one usually observed in very lightly crosslinked
polymers [35] where, in some cases, both a shear compli-
ance associated with entanglement network (JN) and an
equilibrium compliance (Je) can be observed. In fact, the
curve of J 0 for the higher polymer content PMA showed
a barely visible inflection point that could strengthen
this hypothesis (Fig. 2). The shape of J 0 was also similar
to one of an amorphous polymer of high molecular
weight; however in that case, the loss compliance curve
would be expected to increase while approaching lower
frequencies. The loss compliance J 0 Õ of PMA4 and
PMA6 had a plateau (Fig. 4) and probably decreased
slightly instead of marked increasing, as would occur
in the absence of crosslinking. Moreover, the loss tan-
gent curves (Fig. 4), which clearly showed a maximum
in all the PMAs, are further indication of the presence
of some degree of crosslinking. A possible explanation
is that the thermal treatment causes the formation of
free radicals, which induces a small degree of polymer
degradation. Of course, PE is expected to be stable at
our operating conditions. However, it cannot be ex-
cluded that the combined action of temperature and
shear stress could induce the formation of free radicals,
which may interact prevalently with tertiary carbon
atoms on the chain and induce a polymer degradation.
Once a macromolecule contains a free radical, it can
either be subjected to chain scission or react with an-
other chain forming a bridge and giving rise to crosslink-
ing. In any case the crosslinking, if present, must be to a
very small extent as it was not revealed with the solubil-
ity test.
2838 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
A final consideration is that, from the presented mas-
ter curves of PMA2, it seems that the tan d curves were
more sensitive to the polymer content than the compli-
ance curves. In fact, the compliance of PMA2 was more
similar qualitatively to the base asphalt than to the other
PMAs, while it was the contrary for the loss tangent.
However, in this case an even more highlighted differen-
tiation of the rheological curves can be seen using vari-
ous modifications of the Cole–Cole plot [43], see Fig. 5.
Whatever the real internal structure of the high poly-
mer content PMAs, their rheological behaviour supports
the hypothesis that the LLDPE used has a significant
interaction with the asphalt matrix. A continuum ‘‘ma-
trix’’ of the polymer chains has to be present in order
to yield the curves like the ones presented in Figs. 2–5.
The peculiar characteristic of the presented master
curves can be ascribed to an equilibrium between incom-
patibility and miscibility of the two components. The
incompatibility is high so that the morphological analy-
sis easily reveals distinct polymer zones where the poly-
mer preserves its structure and, therefore, its mechanical
properties. At the same time, there is enough miscibility
to have a polymer network that involves the whole mate-
rial and is responsible for the strong effect on mechanical
properties, if compared to those of the base asphalt. This
was not the case for the other tested polymers. The poly-
mer continuum ‘‘matrix’’ allowed the material to show a
markedly ‘‘polymer-like’’ behaviour even if the polymer
content was not particularly high.
Viscosity function at different temperatures was mea-
sured for all the materials. For the base asphalt, all the
curves (not reported for the sake of brevity) were similar
from a qualitative point of view. Starting at low shear
rates, there is a Newtonian plateau up until a limit shear
rate, where shear thinning behaviour started. The higher
the test temperature, the later the shear thinning ap-
Fig. 5. Modified Cole–Cole plot for BA, PMA2, PMA4, and PMA6.
peared. For the lowest temperature, the beginning of
the shear thinning could not be observed because, at
high shear rates, measurements are affected by macro-
scopic instability of the material. It is not completely
clear how to interpret these curves. However, the sim-
plest explanation is that the imposed shear stress reaches
a critical value where asphaltenic micelles or micelles
aggregates are broken, together with the colloidal struc-
ture of the material, and an analogue of gel–sol transi-
tion occurs.
The behaviour gradually changed when BA was
modified with an increasing amount of polymer. At
low temperatures, PMA2 showed viscosity curves quite
similar to those of BA; however, for the highest temper-
ature, there was a gradual shear thinning with a very
small first derivative, which extended to the whole range
of the shear rates used. The phenomenon was more pro-
nounced in PMA4 and extremely evident for PMA6
(Fig. 6). In the latter case, the Newtonian behaviour
could be observed only at 30 C and, for the very left
part of the curve, at 40 C. The other curves showed a
continuous decrease in viscosity and, in particular at
70 C, a slope reduction appears for a shear rate around
10
1 s
1.
The viscosity curves of PMAs with different polymers
(styrene–butadiene–styrene block copolymers SBS, eth-
ylene–vinylacetate random copolymers and RET) used
as modifiers were extensively studied in a previous work
[44]. In all cases, when the polymer was able to form a
network structure, a shear thinning behaviour was
found, which started at shear rates lower than those ob-
served for the base asphalt and with a quite complex
shape to the curves. For certain materials and tempera-
tures (e.g. 4% SBS modified asphalts, 110 C), a double
step shear thinning like the one first described by Onogi
and Asada [45] was observed. Otherwise, curves similar
 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
Fig. 6. Viscosity curves for PMA6.
to those reported in Fig. 6 were found. Considering the
nature of the materials and comparing similar behaviour
observed in other systems [46–50], the polymer-related
shear thinning was interpreted as a consequence of the
temporary nature of the physically crosslinked structure
of the polymer in PMA. A well-defined, double step
shear thinning means that, at first, the induced shear rate
destroys this network thus reducing the viscosity of the
system; and then, after an intermediate Newtonian pla-
teau, the second shear thinning is related to the colloidal
structure of the asphaltic matrix.
In the case of the LLDPE we used, as is shown in
Fig. 6, the shear thinning was more or less homoge-
neously distributed along the shear rate axis and, in this
respect, the only anomaly is the slope change observed
at 70 C. To interpret the curves, the internal structure
of the PMAs has to be considered. The materials are
markedly biphasic, as clearly evidenced by the morpho-
logical analysis. However, at the same time the mechan-
ical properties demonstrated that the polymer islands
were not simply dispersed in the asphaltic phase. If this
was the case, no significant improvement in TR&B and
modification in the rheological properties would be
observed. Therefore, the PE macromolecules form a
continuum, which bridges between two or more poly-
mer-rich zones. Thus, a physical network where ‘‘rigid’’
PE domains are interconnected through polymer chains
is formed. Considering its high heterogeneity, the system
is composed of domains with a large distribution of
dimensions and, at the same time, probably connected
with bridges of different length and strength. As a conse-
quence, there are domains with very different ‘‘mobil-
ity’’, determined by both their dimension and the
number and strength of bridges that bond them to other
domains. In shearing, a progressive disruption of the
network structure occurs, starting from the most weakly
2839
bonded domains and gradually proceeding to those that
are ‘‘stronger’’. This explains the observed curves, where
the above-mentioned slope changes were just a hint of
what could be a plateau modulus in a more homoge-
neous system. With regard to the viscosity measure-
ments, it must be underlined that BA satisfied the
Cox–Merz rule, while none of the PMAs did (curves
are not reported). In fact, this was expected and is fur-
ther confirmation of the complexity and heterogeneity
of the produced materials.
The last part of the rheological characterization is re-
lated to step strain experiments. The stress relaxation
modulus G is defined as the stress/strain (s/c) ratio at
constant deformation. For small shear strains, the func-
tion G is independent of the magnitude of shear strains
and G is a function of time only. For large strains, the
relaxation modulus is a function of two variables,
G = G(t, c). This function is experimentally accessible
in the step strain experiment [35].
The step strain experiments were performed at tem-
peratures T = 10 C for BA, 30 C for PMA2, and
35 C for PMA4 and PMA6, for a set of strains that
would be considered small in most of the dynamic tests
for bituminous materials. Interestingly enough, even at
such small strains all the tested materials showed a clear
dependence of the relaxation modulus on the strain;
however, no master curves were obtainable by vertical
shifting. Figs. 7–10 show 3D representation of G(t, c)
for several strains. The observation, made from the dy-
namic master curves, is confirmed by plotting the 3D
graphs of G(t, c). In the ‘‘glassy’’ domain (t < 1 s), the
base asphalt reached a plateau that seems to be higher
than the values of G(t, c) measured for the tested PMAs.
One has to be cautious in stating this observation, since
only in the base asphalt is there an indication of such a
plateau, and it was quite difficult to recognize the
2840 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844

Fig. 7. Damping and fit of BA.

Fig. 8. Damping and fit of PMA2.

approach to the ‘‘glassy’’ plateau in the tested PMAs. (function of strain only). The linear viscoelastic part is
What is clear, from these plots, is that G(t, c) is decreas- usually approximated by the superposition of Maxwell
ing much faster in the direction of increasing c in all modes [35],
tested PMAs. X
N
In studying the relaxation after large strains, it is fre- GðtÞ ¼ gi exp½
ðt=ki Þ
quently assumed [51] that the relaxation modulus G(t, c) i¼1
can be represented by the factorized function and several (simple) monotonically decreasing functions
Gðt; cÞ ¼ GðtÞ  hðcÞ of h(c) as used in the literature [52–54], mostly in studies
of polymeric systems. We have found that a better
where, G(t) is the linear viscoelastic relaxation modulus description of G(t, c) in bituminous systems can be
(function of time only), and h is the damping function achieved if one assumes that
 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844 2841

Fig. 9. Damping and fit of PMA4.

Fig. 10. Damping and fit of PMA6.

X
N drastically reduced. Hence, for the description of G(t, c)
Gðt; cÞ ¼ Gi ðtÞ  hi ðcÞ (given by the data of the step strain experiment), we
i¼1
have assumed the following form:
"

d i #!
i.e. each linear viscoelastic relaxation mode has its own X N
t i
b
c
damping function. Gðt; cÞ ¼ gi exp
þ
i¼1
ai c i
In shearing, the magnitude of the shear strain is just
the time scaled by the applied shear rate, thus we assume Note that with bi = di = 1, the Maxwell type of modes
that h(c) has the same functional form as G(t). Gener- damping is obtained.
ally, when Maxwell modes are considered, one needs The fit of the step strain data, for all the discussed
many modes to describe the linear viscoelastic relaxation materials, is given by the surface represented in Figs.
modulus G(t). With the stretch exponential type of relax- 7–10, with N = 2. It is seen from these figures that when
ation modes [55] (exp(
(t/a)b)), the number of modes is the measured G(t, c) increased quickly (for higher c and
2842 G. Polacco et al. / European Polymer Journal 41 (2005) 2831–2844
shorter t), the model has problems with capturing the
data. For PMA2 and PMA4, one will need additional
data at higher strains to avoid the large gradients of
the fit surface in the strain direction. On the other hand,
the base asphalt and PMA6 seem to be reasonably well
fitted by the form of G(t, c). With the three Maxwell type
modes (accompanied by the appropriate damping), the
large gradients in the c direction can be avoided; how-
ever, the residual between the fit surface and data are
larger than for the case of the stretch exponential relax-
ation modes with a similar damping. In a crude approxi-
mation, one can assume that two or three main
relaxation mechanisms are necessary for the basic
description of nonlinear mechanical response in bitumi-
nous systems.
4. Conclusions
Several polyethylenes and polyethylene-based poly-
mers were used to modify an asphalt from vacuum dis-
tillation. As expected, in all cases the obtained
polymer-modified asphalt had a heterogeneous structure
and was subjected to storage instability. The modifica-
tion of the olefinic chain with the addition of functional
groups allowed for an improvement of the miscibility be-
tween polymer and asphalt but, in no case, was the
enhancement sufficient to obtain a homogeneous and
stable mix. Among the tested polymers, a linear low-
density polyethylene showed a greater compatibility
with the asphalt and, quite surprisingly, led to the prep-
aration of an asphalt binder with strongly enhanced
mechanical properties when compared with other
blends. The rheological properties of the base asphalt
and of polymer-modified asphalts containing different
percentages of this modifier were studied in the ranges
of small and large deformations. The obtained results
suggest two main pictures. Different from the other
polymers used, the LLDPE was not confined in droplets
separated from each other and dispersed in the asphaltic
matrix, but probably was somehow spread continuously
through the domain in space. The rheological analysis
suggested a possible formation, to a small extent, of
crosslinking, which may form due to thermomechanical
stress during mixing. The presence of such crosslinking
has to be confirmed with other experimental evidence;
however it is consistent and could explain the observed
macroscopic behaviour and mechanical properties.
Step strain experiments were performed at mid-range
temperatures where the tested materials could be classi-
fied as soft solids (liquid-like character is more pro-
nounced at temperatures higher than 30 C), and the
wall slip may have played a role in some experiments.
Moreover, the step strain experiment performed in a
stress-controlled rheometer might suffer from the effect
of imperfect strain history [56]. Thus, the domains of
very high gradients may not properly reflect the material
behaviour, and the proposed simulation of G(t, c) fails in
such domains. On the other hand, the possibility of hav-
ing at least a rough description of relaxation in asphalt
(conventional and also PMA) with only three damped
relaxation modes is ‘‘attractive’’. Further experiments
need to be performed in order to improve the storage
stability of these blends and to understand why different
polyethylenes showed such marked dissimilarities in
their interactions with asphalt.
Acknowledgements
The authors express their gratitude to the Natural
Sciences and Engineering Research Council of Canada
and to Husky Energy Inc. for their financial support
of this work, and to Dr. Mariano Pracella and Dr. Do-
natella Chionna for kindly providing polymers PEG-
MA1 and PEGMA2.
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