Construction and Building Materials 16 (2002) 473–487

Rheological evaluation of ethylene vinyl acetate polymer modified

bitumens
Gordon D. Airey*
Nottingham Centre for Pavement Engineering, School of Civil Engineering, University of Nottingham, University Park, Nottingham NG7 2RD,
UK

Received 15 February 2002; received in revised form 10 July 2002; accepted 28 August 2002

Abstract

The morphological, thermal and fundamental rheological characteristics of ethylene vinyl acetate (EVA) copolymer modified
bitumens are studied in this paper. Nine plastomeric EVA polymer modified bitumens (PMBs) have been produced by laboratory
mixing bitumen from three sources with an EVA copolymer at three polymer contents. The morphology, thermal properties and
rheological characteristics of the EVA PMBs have been analysed using fluorescent microscopy, differential scanning calorometry
and dynamic mechanical analysis using a dynamic shear rheometer, respectively. The results of the investigation indicate that
EVA polymer modification increases binder stiffness and elasticity at high service temperatures and low loading frequencies with
the degree of modification being a function of bitumen source, bitumen–polymer compatibility and polymer concentration. Filler
type modification is evident at low temperatures, temperatures above the melting temperature of the semi-crystalline EVA
copolymer and for those modified binders that do not exhibit a dominant polymer network.
䊚 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Polymer modified bitumens; EVA; Dynamic mechanical analysis; DSR

1. Introduction generally possess improved resistance to permanent

Conventional bituminous materials have tended to
perform satisfactorily in most highway pavement and
airfield runway applications. However, in recent years,
increased traffic levels, larger and heavier trucks, new
axle designs and increased tyre pressures, have added to
the already severe demands of load and environment on
the highway system. This has resulted in the need to
enhance the properties of existing asphalt material.
Bitumen modification offers one solution to overcome
the deficiencies of bitumen and thereby improve the
performance of asphalt mixtures w1–3x. The best known
form of modification is by means of polymer modifi-
cation, traditionally used to improve the temperature
susceptibility of bitumen by increasing binder stiffness
at high service temperatures and reducing stiffness at
low service temperatures w1,4–6x. In addition, PMBs
*Tel.: q44-115-9513913; fax: q44-115-9513909.
E-mail address: gordon.airey@nottingham.ac.uk (G.D. Airey).
deformation, thermal and fatigue cracking.
The polymers that are used for bitumen modification
can be divided into two broad categories, namely plas-
tomers and elastomers. Plastomers modify bitumen by
forming a tough, rigid, three-dimensional network to
resist deformation, while elastomers have a characteris-
tically high elastic response and, therefore, resist per-
manent deformation by stretching and recovering their
initial shape. One of the principal plastomers used in
pavement applications is the semi-crystalline copolymer,
ethylene vinyl acetate (EVA). EVA polymers have been
used in road construction for more than 20 years in
order to improve both the workability of the asphalt
during construction and its deformation resistance in
service w7–9x.
However, despite considerable research in this area,
plastomeric PMBs have still not been comprehensively
characterised, due to the complex nature and interaction
of the bitumen and polymer system w1,10x. This paper
presents a laboratory evaluation of the morphology,
thermal analysis and fundamental rheological character-

0950-0618/02/$ - see front matter 䊚 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 0 - 0 6 1 8 Ž 0 2 . 0 0 1 0 3 - 4
474 G.D. Airey / Construction and Building Materials 16 (2002) 473–487

Table 1
Conventional physical properties of the base bitumens

Binder Penetration Softening Penetration Viscosity Viscosity

@ 25 8C point (8C)b index (PI)c @ 60 8C @ 135 8C
(dmm)a (Pa.s)d (Pa.s)d
Bitumen A 60 48.8 y1.08 262 0.510
Bitumen B 73 47.0 y1.08 165 0.370
Bitumen C 81 46.8 y0.86 213 0.380
a
BS 2000, part 49.
b
BS 2000, part 58.
c
PIs(1952y500 log Pen25 8C y20 SP)y(50 log Pen25 8C ySPy120).
d
ASTM D4402.

istics of a number of base bitumens and EVA PMBs.
The EVA PMBs have been produced by means of
laboratory mixing using three different base bitumens
and three polymer contents. The effects of bitumen
sourceygrade, polymer content and bitumen–polymer
compatibility on the morphology and thermal properties
of the PMBs have been evaluated by means of fluores-
cent microscopy and differential scanning calorimetry,
respectively. The fundamental rheological (viscoelastic)
properties of the PMBs have been determined using
dynamic (oscillatory) mechanical analysis and presented
in the form of temperature and frequency-dependent
rheological parameters.
bitumens at three polymer contents by mass. The poly-
mer contents ranged from low polymer modification at
3% to higher degrees of modification at 5% and 7%.
All the PMBs were prepared with a Silverson high shear
laboratory mill at temperatures between 170 8C and 185
8C, depending on the viscosity of the PMB, until steady
state conditions were achieved.
The different EVA PMBs were coded as PMB- ‘base
bitumen’, ‘polymer type’, ‘polymer content’ such as
PMB-AE5 for the EVA PMB produced with Bitumen
A, EVA copolymer and 5% polymer content.
2.2. Fluorescent microscopy

2. Experimental programme Fluorescent microscopy was used to study the mor-

2.1. Materials
Three base bitumens (A, B and C) from different
crude sources (Middle East, Venezuela and Russia) were
used to produce a number of laboratory blended, semi-
crystalline EVA PMBs. All three base bitumens have
similar consistencies (penetrations between 60 and 81
dmm and softening points between 46.8 and 48.8 8C)
and differ only slightly in their chemical composition
wsaturates, aromatics, resins and asphaltenes (SARA)
fractionsx. The physical and chemical properties of the
base bitumens are given in Tables 1 and 2, respectively.
Nine EVA PMBs were produced by mixing an EVA
20y20 semi-crystalline copolymer, containing 20% vinyl
acetate with a melt index of 20, with each of the base
phology of the EVA PMBs by determining the quality
and nature of the dispersion of the polymer within the
modified binder. Fluorescent microscopy is based on the
principle that polymers swell due to absorption of some
of the constituents of the base bitumen (primarily some
of the light oil fractions found in the maltenes) and,
subsequently, fluoresce in ultraviolet light. The bitumen-
rich phase appears dark or black while the polymer-rich
phase appears light or yellow–green. This fluorescence
from the polymer-rich phase is due to the fluorescence
of the aromatic oils that have been absorbed by the
polymer during the swelling process.
Samples of each PMB where prepared using a stan-
dard sample preparation method incorporating a re-
heating and homogenising procedure, a sample cooling
regime, a surface preparation procedure and recom-
mended magnifications w11x. All the samples were

Table 2
SARA analysis of the three base bitumens

Binder Saturates Aromatics Resins Asphaltenes Colloidal

(%)a (%)a (%)a (%)a indexb
Bitumen A 5 69 15 11 0.190
Bitumen B 4 68 19 9 0.149
Bitumen C 11 58 17 14 0.333
a
Iatroscan thin film chromatography SARA analysis.
b
Colloidal index (Ic)s(asphaltenesqsaturates)y(resinsqaromatics).
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 475

examined under a Leitz Medilux microscope with inci-

dent UV-light (wavelength between 420 and 490 nm)
generated from a high-pressure 75 W Xenon lamp.
Images were typically examined at 25–400= magnifi-
cation depending on the polymer structure w12x.

2.3. Differential scanning calorimetry

Differential scanning calorimetry (DSC) was used to

characterise the thermal behaviour of the EVA PMBs.
DSC can be used to characterise the thermal behaviour
of pure bitumen w13x as well as the thermal behaviour
of semi-crystalline, ethylene copolymer modified bitu-
mens by indicating the presence of specific crystalline Fig. 1. Dynamic shear rheometer testing configuration using a Bohlin-
components in the PMBs w14x. The technique provides controlled stress rheometer.
the values of temperature (8C) and enthalpy (Jyg)
corresponding to the following transitions: where g0speak strain; s0speak stress, Pa; vsangular
frequency, radys; tstime, seconds; and dsphase angle,
● glass transition (2nd order transition);
degrees.
● melting (fusion) (1st order transition); and
The loading frequency, v, also known as the angular
● crystallisation (1st order transition).
frequency or rotational frequency is defined as:
DSC can be performed in either a heating mode, to
vs2pf (3)
obtain melting peaks associated with endothermic reac-
tions, or in a cooling mode, to obtain crystallisation where f sfrequency, Hz.
peaks associated with exothermic reactions. Using the The sinusoidally varying strain and stress can also be
heating mode of testing, the first-order transition, asso- represented by the following complex notation as:
ciated with the melting of the crystalline fractions of
g*sg0eivt (4)
the copolymer, are accompanied by endothermic signals
which are easily characterised by DSC analysis. The and
parameters recorded from these tests are the enthalpy
s*ss0ei(vtqd) (5)
associated with the endothermic reaction and the peak
temperature at which these crystalline EVA components The complex shear modulus (G*) is then defined as:
melt. All the EVA PMB samples were subjected to DSC
s* s0 id
testing using a Mettler DSC 30 analyser performed in G*s s e (6)
its heating mode using a heating rate of 5 8C per minute g* g0
from 0 to 120 8C. The above equation for the complex modulus can
also be written as:
2.4. Dynamic mechanical analysis
Bs E Bs E
G*sC FcosdqiC FsindsG9qiG0
0 0
(7)
At present the most commonly used method of fun- D g0 G D g0 G
damental rheological testing of bitumen is by means of
dynamic mechanical methods using oscillatory-type test- where G*scomplex shear modulus, Pa; G9sstorage
ing, generally conducted within the region of linear modulus, Pa; and G0sloss modulus, Pa.
viscoelastic (LVE) response. These oscillatory tests are The in-phase component of G*, or the real part of
undertaken using dynamic shear rheometers (DSRs), the complex shear modulus, is defined as:
which apply oscillating shear stresses and strains to G9sG*cosd (8)
samples of bitumen sandwiched between parallel plates
at different loading frequencies and temperatures as and the out-of-phase component, or the imaginary part
depicted in Fig. 1 w15–17x. of the complex shear modulus, as:
The sinusoidally varying shear strain can be expressed G0sG*sind (9)
as:
The principal viscoelastic parameters that are obtained
gŽt.sg0sinvt (1) from the DSR are, therefore, the magnitude of the
and the resulting stress as: complex shear modulus (±G*±) and the phase angle (d).
±G*± is defined as the ratio of maximum (shear) stress
sŽt.ss0 sinŽvtqd. (2) to maximum strain and provides a measure of the total
476 G.D. Airey / Construction and Building Materials 16 (2002) 473–487
resistance to deformation when the bitumen is subjected
to shear loading. It contains elastic and viscous compo-
nents which are designated as the (shear) storage mod-
ulus (G9) and (shear) loss modulus (G0), respectively.
These two components are related to the complex
(shear) modulus and to each other through the phase
(or loss) angle (d) which is the phase, or time, lag
between the applied shear stress and shear strain
responses during a test. Where G* or the term ‘complex
modulus’ are used in this paper, it is understood that
they refer to the magnitude of the complex shear
modulus (±G*±).
The phase angle, defined above as the phase differ-
ence between stress and strain in an oscillatory test, is
a measure of the viscoelastic balance of the material
behaviour. If d equals 908 then the bituminous material
can be considered to be purely viscous in nature,
whereas a d of 08 corresponds to purely elastic behav-
iour. Between these two extremes the material behaviour
can be considered to be viscoelastic in nature with a
combination of viscous and elastic responses.
Various geometries, such as cone and plate, parallel
plates, and cup and plate, can be used in dynamic
mechanical testing. For many materials cone and plate
geometry is preferred as shear stress and shear rate are
constant over the entire area of the plate, thereby
simplifying calculations and giving accurate fundamen-
tal rheological properties. However, for bitumen testing
parallel plate geometry is almost invariably used to
avoid the very small gap present at the centre of the
cone and plate geometry.
In general two testing (plate) geometries are com-
monly used with the DSR, namely an 8-mm diameter
spindle with a 2-mm testing gap and a 25-mm diameter
spindle with 1-mm testing gap. The selection of the
testing geometry is based on the operational conditions
with the 8-mm plate geometry generally being used at
low temperatures (y5 8C to 20 8C) and the 25-mm
geometry at intermediate to high temperatures (20 8C to
80 8C). However, it is possible to use the same testing
geometry over a wide temperature range, although the
precision of the results may be limited as a result of
compliance errors and the reduction in precision with
which the torque can be measured at low stress levels.
The DSR tests reported in this paper were performed
under the following test conditions:
● Mode of loading: Controlled-strain.
● Temperatures: 10, 15, 25, 35, 45, 55, 65 and 75 8C.
● Frequencies: 0.01, 0.015, 0.02, 0.05, 0.1, 0.15, 0.2, 0.5,
1, 1.5, 2, 5, 10 and 15 Hz.
● Spindle geometries: 8 mm f and 2 mm gap (10–35 8C), 25 mm
f and 1 mm gap (25–75 8C).
● Strain amplitude: Within LVE response (0.5–10%)
dependent on G*.
For each test, samples were prepared by means of a
hot pour method, based on Method A of the IP Standard
w18x, Methods 1 and 3 of the SHRP DSR Protocol w16x
and Alternative 1 of the AASHTO Standard w19x. The
gap between the upper and lower spindles of the DSR
was set to a height of 50 mm plus the required testing
gap at the mid-point of the testing temperature range.
Once the gap had been set, a sufficient quantity of hot
bitumen (typically at 100–150 8C) was poured onto the
bottom (lower) plate of the DSR to ensure a slight
excess of material appropriate to the chosen testing
geometry. The upper plate of the DSR was then gradu-
ally lowered to the required nominal testing gap plus 50
mm. The bitumen that was squeezed out between the
plates was then trimmed flush to the edge of the plates
using a hot spatula or blade. Finally, the gap was closed
by a further 50 mm to achieve the required testing gap
as well as a slight bulge around the circumference of
the testing geometry (periphery of the test specimen).
The rheological properties of the binders were meas-
ured in terms of their complex (shear) modulus (stiff-
ness and overall resistance to deformation), G*; storage
modulus (binder elasticity), G9; and phase angle (vis-
coelastic balance of rheological behaviour), d.
3. Results and discussion
3.1. Morphology
Fluorescent microscopy images of the EVA PMBs
were obtained at 100= magnification. The fluorescent
images of PMB-CE3, PMB-CE5 and PMB-CE7 are
shown in Fig. 2. The fluorescent images show a change
in the morphology of the PMBs as the polymer content
increases. The image for PMB-CE3 shows a continuous
bitumen-rich phase with a dispersed polymer-rich phase,
while the image for PMB-CE7 shows the opposite with
a continuous polymer phase with a dispersed bitumen
phase. The image for PMB-CE5 displays a relatively
unstable, intertwined phase structure with neither phase
dominating the overall system. The relative proportion
of bitumen to polymer phase has been determined by
means of image analysis and shows an increase in the
polymer phase from 29% for PMB-CE3 to 42% and,
finally, to 59% for PMB-CE7. Similar results were seen
for the other EVA PMBs.
The different morphologies seen in Fig. 2 are a
function of the swelling potential of the polymer (nature
of the polymer), the nature of the base bitumen (com-
position of the maltenes fraction), the polymer content
of the PMB and the bitumen–polymer compatibility.
The different morphological nature of the PMBs will
inevitably affect the rheological characteristics of these
modified binders. EVA PMBs that have a continuous
polymer-rich phase (i.e. PMB-CE7) generally produce
polymeric type modification rather than filler type (stiff-
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 477

Fig. 2. Fluorescent images of EVA modified Bitumen B.

ening) modification generally seen for continuous bitu- consistent within each EVA polymer modified bitumen
men phase PMBs (i.e. PMB-CE3). The nature of the group and there being an increase in enthalpy with
polymer–bitumen phase matrix for the nine EVA PMBs increasing polymer content. Based on the peak DSC
is listed in Table 3. Based on the morphology of the fusion temperature, the upper extend of polymeric type
PMBs, Bitumen B should demonstrate the highest degree modification for the EVA PMBs should be approximate-
of polymer modification while Bitumen A should be ly between 60 and 70 8C. On average the Bitumen B
limited to filler type modification. EVA PMBs tend to have the highest value of enthalpy
with the Bitumen A PMBs having the lowest. If it is
3.2. Differential scanning calorimetry accepted that there is a relationship between enthalpy
and degree of modification, the results suggest that the
The DSC parameters of enthalpy associated with the Bitumen B EVA PMBs will show the highest degree of
fusion of the EVA crystalline fractions and the peak modification, followed by Bitumen C and then Bitumen
temperature at which this occurs for the EVA PMBs are A.
presented in Table 4. The peak temperature at which the
first-order transition occurs depends on the type of 3.3. Conventional physical properties
ethylene copolymer and base bitumen but is generally
considered to be insensitive to polymer content w13,20x. The effect of polymer modification for the different
However, the copolymer content does have an effect on PMB groups can be seen in Table 5 as a decrease in
the enthalpy associated with the endothermic reaction, penetration and an increase in softening point with
there being an increase in enthalpy with increasing increasing modification. The magnitude and extent of
polymer content w20x. these changes do, however, vary as a function of the
The results in Table 4 tend to confirm these previous base bitumen–polymer combination. The decrease in
findings with the peak temperature being relatively
Table 4
Table 3 Variations in DSC parameters due to EVA modification
Polymer–bitumen phase morphology of EVA modified bitumens
Binder Enthalpy Temperature fusion range
Binder Bitumen Intermediate Polymer
phase phase (Jyg) Peak temp Low temp High temp
dominant dominant (8C) (8C) (8C)
PMB-AE3 ⻬ PMB-AE3 2.4 69.7 41 81
PMB-AE5 ⻬ PMB-AE5 3.0 69.9 46 82
PMB-AE7 ⻬ PMB-AE7 3.2 69.9 47 86
PMB-BE3 ⻬ PMB-BE3 2.7 66.7 44 80
PMB-BE5 ⻬ PMB-BE5 3.4 69.6 44 83
PMB-BE7 ⻬ PMB-BE7 4.3 69.9 43 85
PMB-CE3 ⻬ PMB-CE3 2.5 61.9 43 77
PMB-CE5 ⻬ PMB-CE5 3.1 61.5 42 81
PMB-CE7 ⻬ PMB-CE7 4.4 65.4 42 82
478 G.D. Airey / Construction and Building Materials 16 (2002) 473–487

Table 5 of the base bitumen, the chemical composition of the

Changes in conventional binder properties following EVA polymer, and base bitumen–polymer compatibility.
modification
Rotational viscosities for Bitumen A (60–160 8C)
Binder Penetration Softening Penetration Fraass Ductility and its three EVA PMBs (100–200 8C) are shown in
@ 25 8C point index (8C)a @ 10 8C Fig. 3. The results show a consistent increase in viscosity
(dmm) (8C) (PI) (cm)b with polymer modification. Similar plots were also seen
Bitumen A 60 48.8 y1.08 y18 21 for Bitumens B and C and their EVA PMBs. Rotational
PMB-AE3 53 54.8 0.08 – 13 viscosities (h) at 100 8C and 160 8C for all the binders
PMB-AE5 43 61.0 0.86 y12 8 are presented in Table 6 together with modification
PMB-AE7 37 69.4 1.99 y11 5 indices (h for PMB divided by h for the base bitumen)
Bitumen B 73 47.0 y1.08 y12 63 at these two temperatures. As with the penetration and
PMB-BE3 61 59.5 1.45 – 16 softening point tests the viscosities give a clear indica-
PMB-BE5 51 66.6 2.31 y13 20
PMB-BE7 47 69.2 2.54 y13 19
tion of the stiffening effect of EVA modification. In
addition, the modification indices at 100 8C and 160 8C
Bitumen C 81 46.8 y0.86 y28 130 are almost identical within each bitumen group and
PMB-CE3 65 53.7 0.35 – 22
PMB-CE5 58 63.8 2.15 y14 10 relatively similar between the different groups. The
PMB-CE7 53 69.2 2.86 y10 12 effect of modification on high temperature viscosity is,
a
therefore, more indicative of a filler type modification
IP80.
b
ASTM D113. than a polymeric type modification. This is because the
EVA copolymer melts at a temperature between 65 and
80 8C and is, therefore, already in its melted state at
penetration and increase in softening point indicate an temperatures of 100 8C and higher. Therefore, high
increased hardness or stiffness of the modified binders. temperature viscosity, as with penetration, only indicates
In addition to this increase in hardness, the penetration the effect of EVA polymer modification as a simple
indices (PIs) w21x indicate an improvement in tempera- filler-like modification or hardening (stiffening) of the
ture susceptibility with polymer modification. bitumen.
The Fraass breaking point results show a reduction in
low temperature flexibility with increasing modification, 3.4. Dynamic viscoelastic properties
although the results for the PMB-BE PMBs show
consistent Fraass results before and after modification. Isochronal plots of complex modulus (G*) vs. tem-
The ductility results show a decrease in ductility with perature, at 0.02 Hz and 1 Hz, for Bitumens A and B
modification. The Fraass and ductility results show the are shown in Figs. 4 and 5. The isochronal plots in Fig.
high degree of dependence of intermediate and low 4 show a considerable difference in the degree of
temperature physical properties of PMBs on the nature modification between Bitumen A and B. The nature of

Fig. 3. Rotational viscosities of base and EVA modified Bitumen A.

 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 479

Table 6
Rotational viscosities following EVA modification

Binder Rotational Rotational hPMByhBitumen hPMByhBitumen

viscosity @ viscosity @ @ 100 8C @ 160 8C
100 8C (mPa.s) 160 8C (mPa.s)
Bitumen A 4530 170 1.00 1.00
PMB-AE3 7830 290 1.73 1.71
PMB-AE5 12 900 440 2.85 2.59
PMB-AE7 18 100 650 4.00 3.82
Bitumen B 3060 130 1.00 1.00
PMB-BE3 4490 210 1.47 1.62
PMB-BE5 6790 310 2.22 2.38
PMB-BE7 11 400 480 3.73 3.69
Bitumen C 3400 130 1.00 1.00
PMB-CE3 6460 240 1.90 1.85
PMB-CE5 10 100 370 2.97 2.85
PMB-CE7 15 900 620 4.68 4.77

Fig. 4. Isochronal plots of complex modulus at 0.02 Hz for base and EVA modified Bitumens A and B.

Fig. 5. Isochronal plots of complex modulus at 1 Hz for base and EVA modified Bitumens A and B.

the increase in G* for Bitumen A is similar to that seen
for the high temperature viscosity results in Fig. 3 (filler
type modification). However, the Bitumen B EVA PMBs
show a more pronounced increase in G* and improved
temperature susceptibility (decrease in the slope of the
complex modulus isochrones) with increasing polymer
content up to a temperature of 55 8C. In addition, PMB-
BE5 and PMB-BE7 exhibit a plateau region indicative
of a dominant polymer network within the modified
binder. At approximately 55 8C, the crystalline melting
of the EVA polymers (as identified by DSC analysis)
results in a sharp increase in the slope of the PMB-BE
complex modulus isochrones and, therefore, a lower
increase in G* and an increase in temperature suscepti-
bility. This transitional temperature of approximately 55
8C is slightly lower than the temperature range estab-
lished by means of DSC analysis (60–70 8C). The
isochronal plots at 1 Hz for the two bitumen groups in
480 G.D. Airey / Construction and Building Materials 16 (2002) 473–487

Fig. 6. Modification indices at 0.02, 0.1, 1 and 10 Hz for PMB-BE7.

Fig. 5 tend to be more comparable. Both bitumen groups
show a relatively consistent increase in G* with modi-
fication although the increases are limited at low tem-
peratures. The polymeric type modification for Bitumen
B compared to the filler type modification of Bitumen
A is more noticeable at the lower frequency of 0.02 Hz
(Fig. 4) than at the higher frequency of 1 Hz (Fig. 5).
This is due to the lower stiffness of the base bitumen at
0.02 Hz allowing the polymer (elastic) network to
influence the rheological characteristics of the polymer-
bitumen blend. The significance of loading frequency
on the effect of polymer modification can also be seen
in Fig. 6 where modification indices of PMB-BE7 have
been plotted as a function of temperature at four fre-
quencies. The results show the considerable increase in
modification at low frequencies and the dominant mod-
ification peak at 55 8C.
The observations in Figs. 4 and 5 agree with those of
Lenoble et al. w22x, that at low temperatures (-10 8C)
the complex modulus for a pure bitumen and various
PMBs (EVA, EMA and SBS copolymers) are very
similar and that most binders tend towards the same
complex modulus at these low temperatures irrespective
of the polymer and the bitumen grade. At temperatures
above 10 8C, the influence of the polymer begins to
appear and PMBs tend to show superior thermal suscep-
tibility compared to pure bitumen. These findings are,
however, dependent on the rheological characteristics of
the polymer and the compatibility of the PMB system.
In general a binder should have high values of G*
and G9 at high temperatures for deformation resistance.
The isochronal plots of G* (Figs. 4 and 5) and the
modification indices plots (Fig. 6) have indicated that
the degree of EVA modification is most significant

Table 7
Changes in rheological parameters following EVA modification at 45 8C and two different frequencies

Binder G* @ 45 8C (Pa) G*PMByG*Bitumen G9PMB yG9Bitumen d @ 45 8C (degrees)

0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz
Bitumen A 4.47Eq2 1.85Eq4 1.0 1.0 1.0 1.0 88 81
PMB-AE3 1.09Eq3 3.34Eq4 2.4 1.8 6.5 3.6 84 73
PMB-AE5 1.97Eq3 4.45Eq4 4.4 2.4 22.9 6.7 78 66
PMB-AE7 3.70Eq3 6.88Eq4 8.3 3.7 63.4 12.2 73 61
Bitumen B 2.78Eq2 1.24Eq4 1.0 1.0 1.0 1.0 88 85
PMB-BE3 7.96Eq2 1.92Eq4 2.9 1.6 34.2 4.4 65 75
PMB-BE5 2.57Eq3 2.86Eq4 9.2 2.3 221.8 10.9 33 65
PMB-BE7 5.64Eq3 4.41Eq4 20.3 3.6 484.7 22.5 33 55
Bitumen C 2.86Eq2 1.19Eq4 1.0 1.0 1.0 1.0 88 81
PMB-CE3 7.97E2 2.09Eq4 2.8 1.8 15.1 3.7 81 72
PMB-CE5 2.24Eq3 3.64Eq4 7.8 3.1 97.1 9.8 69 62
PMB-CE7 5.93Eq3 5.50Eq4 20.8 4.6 451.2 19.3 51 52
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 481

Table 8
Changes in rheological parameters following EVA modification at 55 8C and two different frequencies

Binder G* @ 55 8C (Pa) G*PMByG*Bitumen G9PMB yG9Bitumen d @ 55 8C (degrees)

0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz
Bitumen A 8.15Eq1 3.78Eq3 1.0 1.0 1.0 1.0 89 85
PMB-AE3 1.84Eq2 7.18Eq3 2.3 1.9 8.7 4.7 86 78
PMB-AE5 3.30Eq2 1.04Eq4 4.0 2.8 34.2 9.8 82 73
PMB-AE7 6.35Eq2 1.60Eq4 7.8 4.2 123.1 18.2 75 69
Bitumen B 5.00Eq1 2.40Eq3 1.0 1.0 1.0 1.0 89 87
PMB-BE3 1.81Eq2 4.05Eq3 3.6 1.7 93.3 7.9 55 76
PMB-BE5 9.48Eq2 6.85Eq3 19.0 2.9 805.4 24.9 19 64
PMB-BE7 1.76Eq3 1.09Eq4 35.2 4.5 1475.3 48.7 21 57
Bitumen C 5.80Eq1 2.81Eq3 1.0 1.0 1.0 1.0 89 85
PMB-CE3 1.55Eq2 5.27Eq3 2.7 1.9 21.5 5.6 85 76
PMB-CE5 4.59Eq2 1.02Eq4 7.9 3.6 188.0 16.9 74 67
PMB-CE7 1.06Eq3 1.31Eq4 18.2 4.6 894.3 30.2 55 58

within the temperature range of 45–65 8C. The improve-
ment in terms of deformation resistance (G*PMB y
G*Bitumen) and elasticity (G9PMB yG9Bitumen ) as well as the
values of G* and d at 45, 55 and 65 8C are given in
Tables 7–9. The results indicate that there are significant
differences in the modification indices of G* and G9
amongst the different bitumen groups. The differences
are more pronounced at higher polymer contents, lower
frequencies (0.02 Hz compared to 1 Hz), temperatures
of 55 8C and 65 8C, and for the binder elasticity
measurements (G9PMB yG9Bitumen ). The polymeric phase
dominant PMBs (PMB-BE5, PMB-BE7 and PMB-
CE7), as identified by fluorescent micrsoscopy analysis,
showed the largest increases in binder stiffness (G*),
binder elasticity (G9) and elastic behaviour (d).
3.5. Phase angles
Phase angle isochrones at 0.02 Hz and 1 Hz for the
EVA PMBs are presented in Figs. 7 and 8. The phase
angle (d) is generally considered to be more sensitive
to the chemical structure and, therefore, the modification
of bitumen than complex modulus. The figures clearly
illustrate the temperature dependence of the modified
binders and the effectiveness of the EVA polymer. As
temperature increases, the phase angles for the base
bitumens at both 0.02 Hz and 1 Hz approach 908 and,
therefore, predominantly viscous behaviour, while the
polymer begins to significantly improve the elasticity of
the modified binders. This increase in elasticity at high
temperatures can be attributed to the viscosity of the
base bitumens being low enough to allow the elastic
network of the polymer to influence the mechanical
properties of the modified binders w5x. The presence of
this polymer network can be identified as a plateau
region situated between the points where the phase angle
passes through a maximum and then a minimum with
increasing temperature. This plateau is synonymies with
the plateau region defined for polymers and demon-
strates the ability of the polymer to form a continuous
elastic network when dissolvedydispersed in the bitumen
w23x. The presence and nature of the plateau and the
polymer network is a function of the chemical and

Table 9
Changes in rheological parameters following EVA modification at 65 8C and two different frequencies

Binder G* @ 65 8C (Pa) G*PMByG*Bitumen G9PMB yG9Bitumen d @ 65 8C (degrees)

0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz 0.02 Hz 1 Hz
Bitumen A 2.01Eq1 9.82Eq2 1.0 1.0 1.0 1.0 89 88
PMB-AE3 4.49Eq1 1.92Eq3 2.2 2.0 11.8 7.6 87 81
PMB-AE5 8.09Eq1 2.80Eq3 4.0 2.9 53.0 17.2 83 77
PMB-AE7 1.53Eq2 4.47Eq3 7.6 4.6 159.1 35.2 79 73
Bitumen B 1.24Eq1 6.01Eq2 1.0 1.0 1.0 1.0 89 88
PMB-BE3 2.42Eq1 9.05Eq2 2.0 1.5 24.6 6.1 83 83
PMB-BE5 7.75Eq1 1.46Eq3 6.2 2.4 385.1 23.1 51 73
PMB-BE7 1.87Eq2 2.48Eq3 15.1 4.1 1119.7 55.8 41 65
Bitumen C 1.43Eq1 7.20Eq2 1.0 1.0 1.0 1.0 90 88
PMB-CE3 3.46Eq1 1.34Eq3 2.4 1.9 47.9 7.1 83 82
PMB-CE5 1.06Eq2 2.57Eq3 7.4 3.6 338.5 29.3 75 72
PMB-CE7 2.23Eq2 3.38Eq3 15.6 4.7 1292.4 54.3 61 64
482 G.D. Airey / Construction and Building Materials 16 (2002) 473–487
Fig. 7. Isochronal plots of phase angle at 0.02 Hz for base and EVA modified bitumens.
physical properties of the polymer and bitumen and the
compatibility of these two components w4x.
The isochronal plots for the Bitumen B modified
binders in Fig. 7 show a reduction in d with increasing
polymer content with the phase angle reaching a mini-
mum value at 55 8C, after which there is a sharp
increase towards a more viscous behaviour as the poly-
mer melts. There is a similar decrease in d towards a
more elastic behaviour for the Bitumen A and C modi-
fied binders, although to a lesser degree, particularly for
the Bitumen A group. The effect of increasing the
loading frequency in Fig. 8 is to reduce the extent of
the decrease in phase angle with modification while at
the same time decreasing d for the unmodified bitumen.
This apparent reduction in modification is a result of
the viscosity of the base bitumens being high enough to
partially mask the influence of the polymer network on
the mechanical properties of the modified binders. The
isochronal plots in Figs. 7 and 8 are similar to those
seen by other researchers w22x, who found that at low
temperatures (-10 8C) there is no significant difference
in the phase angles of pure bitumen and PMBs (EVA,
EMA and SBS copolymers), and, therefore, proposed
that the rheological properties of PMBs are dominated
by the bitumen and not the polymer at low temperatures
and high loading frequencies. Above 10 8C, the prop-
erties of PMBs tend to be more influenced by the
polymer w5x.
Fig. 8. Isochronal plots of phase angle at 1 Hz for base and EVA modified bitumens.
In addition to the isochronal plots, a number of
parameters can be defined in order to quantify the effect
of EVA modification. The point at which the binders
become predominantly viscous in nature can be arbitrary
defined as the temperature at which the phase angle
becomes greater than 758 w24x. This upper temperature
limit of elasticity has been determined for the binders
included in this study at two frequencies and presented
in Table 10. The values of the maximum and minimum
phase angles, corresponding to the polymer network
plateau regions, and their associated temperatures at
0.02 Hz have also been listed in Table 10. The data in
Table 10 and Figs. 7 and 8 clearly illustrate distinctions
between the different base bitumen modified binder
groups. Although all the EVA PMBs show an increase
in T75 8C compared to the base bitumens, the nature of
the increase is different at 0.02 Hz compared to that at
1 Hz. Whereas the increase in T75 8C at 1 Hz is similar
amongst the three binder groups, the increase in the
upper limit of elasticity at 0.02 Hz is greater for the
polymeric phase dominant PMBs (Bitumens B and C).
For Bitumen B the phase angle minimum and maximum
deepen (decrease in phase angle) with increasing poly-
mer content. For Bitumens A and C, particularly at low
polymer contents, the phase angle is a smoothly increas-
ing function of temperature with both the maximum and
minimum phase angle parameters being indistinguisha-
ble. Differences in the plots of phase angle vs. temper-
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 483

Table 10
Phase angle data for EVA PMBs

Binder T75 8C @ 0.02 T75 8C @ 1 dmax @ Tdmax @ 0.02 dmin @ 0.02 Tdmin @ 0.02
Hz (8C) Hz (8C) 0.02 Hz (8) Hz (8C) Hz (8) Hz (8C)
Bitumen A 20 35 – – – –
PMB-AE3 32 49 – – – –
PMB-AE5 41 61 – – – –
PMB-AE7 54 67 – – – –
Bitumen B 14 28 – – – –
PMB-BE3 62 46 72 35 55 55
PMB-BE5 72 66 60 15 19 55
PMB-BE7 72 70 52 10 21 55
Bitumen C 17 32 – – – –
PMB-CE3 37 53 – – – –
PMB-CE5 65 68 – – – –
PMB-CE7 70 71 47 15 46 25

ature and the parameters in Table 10 can be related to
the differences in the molecular interaction (i.e. disper-
sion, swelling and compatibility) between the base
bitumens and the EVA polymer.
The mechanism of polymer modification can be
explained by plotting complex modulus and phase angle
vs. temperature for the pure EVA polymer and bitumen
B in Fig. 9. The isochronal plot, at a frequency of 0.1
Hz, shows the difference in temperature susceptibility
between the EVA polymer and Bitumen B. A blend
consisting of the base bitumen and the polymer, where
the compatibility of the system allows the mechanical
properties of the polymer to be evident, should have
improved temperature susceptibility and increased G* at
high temperatures. In terms of the phase angle, the
figure shows that the phase angle for the pure polymer
remains relatively constant at approximately 58, while
the phase angle of the bitumen increases from approxi-
mately 508 to 908. A blend of the polymer and bitumen
should, therefore, result in a reduction of the phase
angle as seen in Figs. 7 and 8. The decrease in phase
angle and the increased elastic behaviour of the modified
binder will be more evident when the viscosity of the
base bitumen is low enough at high temperatures and
low loading frequencies to allow the polymer network
to dominate.
3.6. Rheological master curves
The frequency dependence of complex modulus and
phase angle for the EVA PMBs has been assessed by
means of rheological master curves. As an example,
Fig. 10 shows the rheological data obtained for PMB-
BE7 in the form of G* isotherms which have been
shifted to produce a master curve at a reference temper-
ature of 25 8C using the time–temperature superposition
principle (TTSP) w23x. In addition to the G* master
curve, a phase angle master curve has been produced
by shifting the d isotherms using the shift factors
determined for the G* master curve. The resulting master
curves differ from those usually produced for penetration
grade bitumens in that there is evidence of a breakdown
of time-temperature equivalence, particularly at inter-
mediate and low frequencies. The breakdown of the
smoothness of a master curve can be attributed to a
number of factors. These include loss of LVE response
due to DSR testing at strain levels outside the linear
region, compliance errors associated with the testing
apparatus and testing configuration, and the presence of
structural changes with temperature within the bitumen
as found for waxy bitumens, highly structured ‘GEL’
type bitumens and some PMBs.
As the DSR tests were conducted in such a manner
to ensure LVE response and appreciating that time–
temperature equivalence does not hold across a phase
transition such as crystallisation or glass transition w25x,
the ‘branching’ and discontinuous ‘waves’ in the master
curves can be attributed to the presence of the semi-
crystalline EVA copolymer. The ‘branches’ in the com-
plex modulus master curve are due to the occurrence of
different EVA crystalline structures in the PMB at
different temperatures, ranging from 35 to 65 8C. Once
the semi-crystalline EVA copolymer has melted at
approximately 75 8C, a temperature slightly higher than
the DSC peak temperature associated with this first-
order transition, the isotherm and low frequency portion
of the master curve reverts back to a unit slope associ-
ated with the viscous asymptote found for unmodified
bitumens. The discontinuous ‘waves’ of the phase angle
master curve clearly demonstrates the breakdown of the
time-temperature equivalence for highly modified, semi-
crystalline PMBs.
484 G.D. Airey / Construction and Building Materials 16 (2002) 473–487

Fig. 9. Isochronal plots of complex modulus and phase angle at 0.1 Hz for EVA copolymer and Bitumen B.

The master curves of complex modulus and phase
angle for the three EVA polymer modified bitumen
groups are shown in Fig. 11. All three bitumen groups
show a similar increase in complex modulus with
increasing polymer content, particularly at low frequen-
cies. This can be attributed to the stiffening effect of
the EVA copolymer and the improved temperature sus-
ceptibility of the PMBs. The main difference between
the complex modulus master curves is the occurrence
of ‘branching’ at low frequencies for the PMB-BE
modified binders, PMB-CE5 and PMB-CE7. These
‘branches’ indicate the occurrence of polymeric type
modification of the EVA PMBs rather than filler type
modification seen for the Bitumen A PMBs and PMB-
CE3. The phase angle master curves differ considerably
in appearance for the three groups. This is not surprising
as, firstly, the phase angle is more sensitive to the
modification of the different PMBs than G* and, sec-
ondly, the data presented in this chapter has indicated
that the EVA PMBs differ considerably with regard to
their rheological characteristics as a function of the
compatibility of the different bitumen-polymer blends
The phase angle master curves for the Bitumen A
PMBs show a reduction in phase angle and the presence
of a slight phase angle plateau with increasing modifi-
cation, but still have a relatively smooth curve. The
only variation from the smooth curve occurs at the low
frequency end, where there is a shifting and discontinuity
of the curve, due to the completed melting of the semi-
crystalline EVA polymer at a temperature of 75 8C. The
phase angle master curves for the Bitumen B PMBs
show a considerable alteration to the smooth shape of
the unmodified bitumen. The master curve consists of
discontinuous ‘waves’ indicating the presence of differ-
ent crystalline structures at different temperatures within
the EVA PMBs. The only similarities between Bitumens

Fig. 10. Master curves of complex modulus and phase angle at 25 8C for PMB-BE7.
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487 485

Fig. 11. Master curves of complex modulus and phase angle at 25 8C for polymer-modified bitumens.

A and B is at the high frequency end, where the bitumen-
rich phase of the PMB is dominant, and at the low
frequency end, which is equivalent to high temperatures,
where the semi-crystalline polymer has melted. The
extent of the discontinuity and severity of the ‘waves’
increases with increasing polymer content. The master
curves for the Bitumen C PMBs are similar to those
seen for Bitumen A. However, the master curve for
PMB-CE7 shows considerable discontinuity and the
presence of ‘waves’ as seen for Bitumen B. The shape
of the ‘waves’ differ between Bitumens B and C and
can be considered to be indicative of the different
modified chemical structures of the EVA PMBs.
4. Conclusions
The rheological properties of bitumens are improved
by means of EVA polymer modification. The semi-
crystalline EVA copolymer provides the modification of
bitumen through the crystallisation of rigid three-dimen-
sional networks within the bitumen. Different crystalline
structures are formed at different temperatures, as shown
486 G.D. Airey / Construction and Building Materials 16 (2002) 473–487
by the occurrence of ‘branching’ in the complex mod-
ulus master curves and ‘waves’ in the phase angle
master curves. The polymeric modification is confined
to an upper temperature limit of approximately 55 8C,
related to the melting temperature of the semi-crystalline
EVA copolymer, where after the process is limited to a
filler type modification. Filler type modification is also
evident at low temperatures (-10 8C) and for those
modified binders that do not have a dominant polymeric
phase or network. Evidence of the melting of the EVA
copolymer can be seen in the viscosity, complex mod-
ulus and phase angle vs. temperature plots, frequency-
dependent master curves and quantified by means of
differential scanning calorimetry (DSC).
Conventional penetration, softening point, Fraass,
ductility and high temperature viscosity tests have dem-
onstrated the increased stiffness (hardness) and
improved temperature susceptibility of the EVA PMBs.
Fluorescent imaging, DSC analysis and fundamental
rheological testing have shown the considerable changes
that can occur in the physical, chemical, morphological
and rheological properties of different EVA PMBs as a
function of polymer type, base bitumen type, polymer-
bitumen compatibility and polymer content. Fluorescent
microscopy has been used to group the EVA PMBs into
two groups either displaying a continuous polymer-rich
(dominant) phase with a dispersed bitumen-rich phase
(Bitumen B and high polymer content Bitumen C) or a
continuous bitumen-rich (dominant) phase with a dis-
persed polymer-rich phase (Bitumen A and low polymer
content Bitumen C).
EVA polymer modification increases the temperature
and frequency-dependent binder stiffness (complex
modulus), binder elasticity (storage modulus) and elastic
behaviour (phase angle) with larger increases being
experienced by the polymeric dominant PMBs (Bitu-
mens B and C). All the EVA PMBs showed a reduction
in phase angle and an increase in the upper limit of
elasticity with polymer modification, although the nature
of the modification is influenced by the base bitumen–
polymer compatibility and the degree of modification.
The PMBs produced with Russian base bitumen (Bitu-
men B) showed the greatest degree of modification
evident as ‘branching’ and ‘waves’ in the complex
modulus and phase angle master curves and the presence
of a plateau region in the phase angle and G* isochronal
plots. The modified binders containing Middle East base
bitumen showed the lowest degree of modification. In
addition the degree of modification was more evident at
high temperatures and low frequencies where the vis-
cosity (stiffness) of the base bitumen was low enough
to allow the polymer network to dominant the mechan-
ical properties of the modified binder.
Acknowledgments
Some of the research reported in this paper formed
part of a Brite Euram research project entitled: ‘Quality
Analysis of Polymer Modified Bitumen Products by
Microscopic Image Analysis with Fluorescent Light’.
The Author acknowledges the work of the Danish Road
Institute, Dansk Vejteknologi Ramboll, Jean Lefebvre
and Ooms Avenhorn Holdings, partners in this project,
in producing the chemical and conventional binder test
data presented in this paper.
References
w1x Brule B, Brion Y, Tanguy A. Paving asphalt polymer blends:
relationship between composition, structure and properties.
Proc AAPT 1988;57:41 –64.
w2x Brown SF, Rowlett RD, Boucher JL. Asphalt modification.
Proceedings of the Conference on US SHRP Highway Research
Program: Sharing the Benefits, ICE, 1990. pp. 181–203.
w3x Isacsson U, Lu X. Testing and appraisal of polymer modified
road bitumens – state of the art. Mater Struct 1995;28:139 –
59.
w4x Collins JH, Bouldin MG, Gelles R, Berker A. Improved
performance of paving asphalts by polymer modification.
AAPT 1991;60:43 –79.
w5x Goodrich JL. Asphaltic binder rheology, asphalt concrete rhe-
ology and asphalt concrete mix properties. AAPT 1991;60:80 –
120.
w6x King GN, King HW, Chaverot P, Planche JP, Harders O. Using
European wheel-tracking and restrained tensile tests to validate
SHRP performance-graded binder specifications for polymer
modified asphalts. Proceedings of the 5th Eurobitume Con-
gress, Stockholm, Volume 1A, 1.06, 1993. pp. 51–5.
w7x Cavaliere MG, Diani E, Vitalini Sacconi L. Polymer modified
bitumens for improved road application. Proceedings of the
5th Eurobitume Congress, Stockholm 1993;1A(1.23):138 –42.
w8x Goos D, Carre D. Rheological modelling of bituminous binders
a global approach to road technologies. Proceedings of the
Eurasphalt & Eurobitume Congress, Session 5: Binders-Func-
tional Properties and Performance Testing, E&E.5.111, Stras-
bourg, 1996.
w9x Loeber L, Durand A, Muller G, Morel J, Sutton O, Bargiacchi
M. New investigations on the mechanism of polymer-bitumen
interaction and their practical application for binder formula-
tion. Proceedings of the Eurasphalt & Eurobitume Congress,
Session 5: Binders-Functional Properties and Performance
Testing, E&E.5.115, Strasbourg, 1996.
w10x Isacsson U, Lu X. Laboratory investigation of polymer modi-
fied bitumens. AAPT 1999;68:35 –63.
w11x Wegan V. Sampling for microscopy—test procedure. Danish
Road Institute, 1996.
w12x Wegan V, Brule B. The structure of polymer modified binders
and corresponding asphalt mixtures. AAPT 1999;68:64 –88.
w13x Shutt R, Turmel C, Touzard B. Differential scanning calorim-
etry analysis and rheological properties of bitumens modified
by semi-crystalline polymers. Proceedings of the 5th Eurobi-
tume Congress, Stockholm 1993;1A(1.11):76 –80.
w14x Brule B, Gazeau S. Characterisation of rheological and thermal
behaviour of asphalt cements modified by ethylene copolymers.
Proceedings of the ACS Symposium on Modified Asphalts,
Orlando, Florida, 1996.
 G.D. Airey / Construction and Building Materials 16 (2002) 473–487
w15x Goodrich JL. Asphalt and polymer modified asphalt properties
related to the performance of asphaltic concrete mixes. Proc
AAPT 1988;57:116 –75.
w16x Petersen et al. Binder characterisation and evaluation, volume
4: test methods. SHRP-A-370, Strategic Highways Research
Program, National Research Council, Washington, D.C., 1994.
w17x Airey GD, Brown SF. Rheological performance of aged poly-
mer modified bitumens. AAPT 1998;67:66 –100.
w18x Institute of Petroleum. Determination of the complex shear
modulus and phase angle of bituminous binders – dynamic
shear rheometer (DSR), Method, IP PM CMy99, 1999.
w19x AASHTO Designation: TP5, Standard method of test for
determining the rheological properties of asphalt binder using
a dynamic shear rheometer (DSR), 1994.
w20x Gazeau S, Maze M, Brule B, Perret P. Application of differ-
ential scanning calorimetry (DSC) to the characterisation of
ethylene copolymers modified bitumen. Proceedings of the
Eurasphalt & Eurobitume Congress, Session 5: Binders –
487
Functional Properties and Performance Testing, E&E.5.109,
Strasbourg, 1996.
w21x Pfeiffer JPh, Van Doormal PM. The rheological properties of
asphaltic bitumens. J Instit Petroleum, 1936.
w22x Lenoble C, Vercoe T, Soto T. Rheology as a performance
indicator for modified bitumen. Proceedings of the 5th Eurob-
itume Congress, Stockholm, Volume 1A, 1.10, 1993, pp. 71–
5.
w23x Ferry JD. Viscoelastic properties of polymers. New York: John
Wiley and Sons, 1980.
w24x Lu X, Isacsson U. Rheological characterization of styrene-
butadiene-styrene copolymer modified bitumens. Construct
Build Mater 1997;11:23 –32.
w25x Phillips MC. Developments in specifications for bitumens and
polymer modified binders, mainly from a rheological point of
view. In: Cabrera JG, editor. Proceedings of the 2nd European
Symposium on the Performance and Durability of Bituminous
Materials, Leeds, 1997. pp. 3–18.