ISSN 1061933X, Colloid Journal, 2014, Vol. 76, No. 4, pp. 425–434. © Pleiades Publishing, Ltd., 2014.

Original Russian Text © S.O. Ilyin, M.P. Arinina, Yu.S. Mamulat, A.Ya. Malkin, V.G. Kulichikhin, 2014, published in Kolloidnyi Zhurnal, 2014, Vol. 76, No. 4, pp. 461–471.

Rheological Properties of Road Bitumens Modified with Polymer

and Solid Nanosized Additives
S. O. Ilyin, M. P. Arinina, Yu. S. Mamulat, A. Ya. Malkin, and V. G. Kulichikhin
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia
email: alex_malkin@mig.phys.msu.ru
Received December 4, 2013

Abstract—The study of the viscoelastic properties of composites based on road bitumens have shown that the
addition of polymeric modifiers (poly(bytadieneblockstyrene) or devulcanized rubber particles) substan
tially increases the storage and loss moduli and decreases the intensity of reduction in the storage modulus
with temperature by several orders of magnitude. However, at high polymer content, growth inadmissible
from the point of view of acceptable technological parameters is observed in the apparent viscosity. The intro
duction of carbon nanotubes into bitumen does not substantially affect its viscoelastic properties. Filling with
metakaolin promotes an increase in the storage modulus at elevated temperatures. It has been shown that a
direct correlation may be established between the objective characteristics of bitumenbased composites and
standard specification parameters, such as penetration depth and heat resistance.
DOI: 10.1134/S1061933X1404005X

INTRODUCTION which the influence of surfactants and dispersed fillers

Bitumens are largetonnage products that are on the structure of bitumenbased materials was inves
widely used in various building technologies all over tigated. At the same time, it was proposed to use poly
the world. In particular, they are indispensable com mer materials for modification of the properties of
ponents of asphalt coverings, which play a variegated road bitumens [8, 9]. Note that the need for quantita
role in the formation of roadbeds and are used as, e.g., tive assessment of the parameters of road bitumens
binders for multicomponent asphalts. with the use of objective characteristics of their rheo
logical properties was distinctly recognized already in
The basic technical characteristics of bitumens are early works [10–12]. The results of the first studies in
related to their rheological properties, which are nec the field of modification and assessment of the proper
essary to determine in a wide temperature range that is ties of bitumens were generalized in monograph [13].
dictated by the service conditions of these materials.
In view of the diverse climatic environments under Later, many researchers repeatedly turned to the
which bitumens are used, it is of interest to study their problem of modification of bitumens with viscoelastic
behavior in a temperature range from –40 to +60°C. polymers and dispersed fillers; works [14–18] should
A temperature range as wide as this dictates the neces be noted among the large number of communications.
sity to modify bitumens, because materials that have The contemporary theory and practice relevant to the
similar characteristics at standard temperatures (e.g., development of bitumenbased materials have been
0 and 20°C) will have greatly different properties in a comprehensively described in large monograph [19],
wider temperature range. in which numerous references devoted to this problem
In accordance with everything said above, the were also presented.
problem of modification of bitumens using different Thus, already in early researches, it was shown that
approaches, materials, and techniques is being widely the service characteristics of bitumenbased compos
discussed in the scientific and technical literature. In ites are closely related to their rheological parameters.
this connection, it should primarily be emphasized Given this, the chemical composition of bitumens, the
that any modification method is based on the consid peculiarities of their interaction with diverse additives
eration of bitumenbased composites as complex mul (polymer–bitumen and mineral component–bitumen
ticomponent disperse systems that are capable of interactions), and the relevant structuring in the bulk
structuring [1]. material are the determining factors. As to the mineral
This approach to bitumenbased technological components, the key role is played by the degree of
materials was formulated in early publications by Reh volume filling, which predetermines the possibility of
binder [2, 3] and works devoted to the study of the the formation of percolation structures, whereas, in
structure of polymer–bitumen composites [4]. This the case of polymers, the swelling of a polymer in
field of research was developed in papers [5–7], in organic components of bitumen is of importance. The

425
426 ILYIN et al.

specificity of the intercomponent interaction affects used in combination with the secondary rubber of
both the viscoplastic properties of a composite mate wornout tires [28]. However, in this case, the matter
rial and its relaxation characteristics. concerned the search for the methods of the recycling
Moreover, the intercomponent interaction in a waste polyethylene materials rather than targeted
bitumenbased composite predetermines the stability modification of bitumen composites.
of the material, which is of special importance for Thus, elastomers and thermoplastics have become
longterm service. Many polymer additives are incom rather traditional modifiers for bitumen. In relation
patible or only kinetically compatible with bitumen with this, we should mention attempts to use poly(eth
liquid components, thereby leading to phase separa ylenecovinyl acetate) in combination with clay
tion after a long exposure to temperatures of material nanoparticles for asphalt modification [29, 30].
service [20]. The separation of components into The application of thermosetting materials is a new
microphases may take place at both elevated tempera method for bitumen modification. In this case, oligo
tures, at which the viscosity of a binder substantially meric precursors of polyurethanes occupy the main
decreases, thereby accelerating the phase separation, place [31–35]. In addition, the use of an isocyanate
and at low temperatures, at which intercomponent terminated polymer has been described [36]. The vis
compatibility may be deteriorated in a material, pro coelastic properties of resulting composites were stud
vided that the system is characterized by an upper crit ied in detail under laboratory conditions [37], and the
ical solution temperature. use of inert and reactive polymers was comparatively
It may be stated that the longterm studies of bitu analyzed [38]. The advantages and drawbacks of dif
menbased composites resulted in two most widely ferent methods of modification were considered from
used methods for bitumen modification, i.e., with the the point of view of variations in the properties of final
use of polymer additives and/or solid micro or nano products used for both roadbuilding and other tech
sized fillers. nical applications [38].
In addition to urethaneforming oligomers, fur
fural resins [39] and polyphosphoric acid [40] have
Polymeric Modifiers been proposed for modifying road bitumens, because
Early attempts to use polymeric modifiers for the latter can chemically interact with bitumen com
improving road bitumens, which are being continued ponents.
at present, include diverse variants of using wornout Parallel investigations of the viscoelastic character
tires. This is due to not only the necessity of improving istics and morphology of polymer–bitumen compos
the elasticity of bitumenbased composites, but also ites are of greatest interest [41]. However, this problem
attempts to solve the important ecological and eco remains to be studied.
nomical problem of utilizing exhausted tires. The
influence of the products of secondary recycling of
wornout tires on the properties of bitumens is being Modification with Solid Particles
continuously investigated. The results of structural The introduction of solid structureforming parti
studies of such composites include data on the distri cles into a liquid is a traditional technological tech
bution of rubber particles in a bitumen matrix, this dis nique for material modification and creation of visco
tribution affecting the performance characteristics of plastic media. This in full measure concerns hydrocar
roadway coverings, have been reported in [21]. Rubber bon media, industrial rubber composites modified
of wornout tires has been shown to decelerate asphalt with technical carbon being a classical example. Actu
aging, provided that the rubber crumb is ground to the ally, nanosized structureforming particles interacting
nanosized level [22]. with the matrix had been used long before the burst of
In a number of works (see, e.g., [23, 24]), it has the interest in nanocomposites and nanotechnologies.
been proposed to use butadiene–styrene–butadiene An analogous approach has been developed for
triblock copolymer (SBS) as a modifier. The efficiency bitumenbased composites. In this field, sand particles
of this material was assumed to be associated with the have been used as a traditional filler for many years.
fact that one of the copolymer components (polybuta The interest in this filler has by no means disappeared,
diene) must be compatible with the hydrocarbon com especially, because sand always remains to be a com
ponents of bitumen, thereby affecting the spatial ponent of road asphalt. However, a new step in this
structuring of the material. As was mentioned above, field is the modification of bitumen with silica nano
this traditional approach to bitumen modification is particles rather than natural sand [42]. Analogously,
still being developed and supported by detailed studies studies in the field of bitumen modification with
[25]. Moreover, attempts have been made to use SBS quartz microparticles are being continued [43, 44]. At
as a modifier for bitumen in more complex compos present, the use of various micro and nanosized par
ites, in which clay nanoparticles were used as a third ticles has become a basic method for modifying road
reinforcing component [26, 27]. bitumens [45]. In addition to traditional and widely
Polyethylene is one of the polymeric modifiers that used solid nanoparticles produced from technical car
have been proposed for use most seldom; it has been bon and bentonite [46], the attention of researchers is,

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 RHEOLOGICAL PROPERTIES OF ROAD BITUMENS MODIFIED WITH POLYMER 427

at present, focused on two types of materials that have opment of elastic turbulence. This method promotes
recently become widely known. These are montmoril disaggregation and dispersion of filler nanoparticles
lonitetype layered silicas [47–52] and carbon nano [58]. The mixing duration was 15 min, and the CNT
tubes [53–57]. Since the use of carbon nanotubes is a content in the MPB superconcentrate was 1.4 wt %.
novel field of research, it may be believed that only Bitumen was mixed with polymer additives and fill
preliminary results have been obtained in it. ers using a blade stirrer operating at a rotor speed of
Bitumen modification still encounters the question 500 rpm. After stirring for 3 h at 160°C, the tempera
of the correspondence between laboratory data, in ture was elevated to 175°C and the mixture was stirred
particular, the results of measuring the rheological for 40 min more.
properties of these materials with the help of precision The following mixed composites were prepared
experimental equipment, and the technical character and investigated:
istics of these materials determined by the available (a) 60/90 bitumen filled with APDDR (15, 20, or
technological procedures. 25 wt %);
Thus, analysis of the state of the art in the field of (b) polymercontaining Bituway 60P bitumen
the production of bitumenbased composites leads us modified with the CNT/MPB mixture (1.25 wt %)
to conclude that, despite the long history of the inves and MK (1.6, 3.2, or 10 wt %); and
tigation of these materials, the development of new (c) bitumen of the 90/130 brand modified with the
composites and the study of their properties remain CNT/MPB mixture (1.25%), SBS (3.5%), and kaolin
urgent problems in which new questions arise and new (10%); SBS (3.5%) and APDDR (10%); and
solutions are proposed periodically. SBS (7.5%) and APDDR (10%).
This work was devoted to studying the properties of The rheological properties were studied with a
road bitumens using promising composites resulting Physica MCR 301 rotational viscometer (Anton Paar)
from the combination of polymeric and solid nano equipped with a plane–plane measuring unit (diame
sized modifiers. Moreover, it is of importance that, ter, d = 25 mm; interplanar gap, h = 1 mm).
when examining bitumenbased composites, their
objective characteristics, namely, the parameters of
viscoelastic properties of these materials measured in a RESULTS AND DISCUSSION
wide temperature–frequency range, were applied. PolymerModified Bitumens
Let us consider the rheological properties of com
EXPERIMENTAL mercial composites produced by the modification of
bitumen matrices with polymers. Figure 1 shows the
Unmodified commercial bitumens of the penetra frequency dependences of the components of
tion grade 50/70, 60/90, and 90/130 brands; elas dynamic moduli of corresponding samples tested at
tomermodified bitumens of the 22/5555 A, Bituway two temperatures. These composites have higher stor
40R, and Bituway 60P brands; and multicomponent age and loss moduli than do initial bitumens under
bitumenbased blends containing mixtures of poly both ordinary and elevated temperatures. This must
meric modifiers with nano and/or microsized addi increase the stability of bituminous concretes based on
tives were studied. the composites with respect to rutting upon repeated
Branched styrene–butadiene block copolymer deformations. Moreover, at room temperature, the
(SBS Sibur DST30R01; intrinsic viscosity, modified bitumens are characterized by smaller
[η]toluene = 1.2 dL/g; 27% styrene content) and mechanical loss tangents; i.e., these bitumens must
maleinized polybutadiene (MPB) (Tekhprogress1; retain their properties better under lowfrequency
Mw = 3500, Mw/Mn = 3.4), which enhances the adhe effects (lowspeed traffic).
sion of bitumen composites to stones, were used as The advantage of polymermodified bitumens
polymeric additives. (high viscoelasticity characteristics) remains preserved
Activated powder of discretely devulcanized rubber up to the elevated temperatures (Fig. 2).
(APDDR; diameter 5−20 μm); metakaolin (MK), The flow curves of the examined systems are pre
which represents dehydroxylated kaolin; and sented in Fig. 3. Polymermodified bitumens are dis
Taunit M multiwalled carbon nanotubes (CNTs; tinguished by a higher viscosity and a slightly pro
diameter 30−80 nm) were used as nano and micro nounced nonNewtonian behavior. Note that, accord
sized fillers. ing to the criteria of Superpave (United States) that are
CNTs were introduced at 120°C via the prelimi imposed on binders, in order to ensure proper wetting
nary preparation of a superconcentrate using MPB as and mixing with a stone material, the viscosity of a
a matrix. The components were mixed with the help of binder at 135°C must be no higher than 3 Pa s [59].
an IKA UltraTurrax T18 disperser operating at a rotor This requirement is not met in the case of Bituway 40R.
speed of 24 × 103 rpm. According to the used proce Thus, the incorporation of a polymer into bitumen
dure, the components were mixed at a high shear rate increases its stiffness and, hence, the stability of bitu
on the order of 8 × 103 s–1, which gave rise to the devel minous concretes to rutting; however, the polymer

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428 ILYIN et al.

G', G'', Pa (a) η, Pa s (a)

1
106 2
20 3

105
G' G''
1 1' 10
104 2 2'
3 3'

103 0
0.1 1 10 100 0.1 1 10 100 1000
10 4 (b) 6 (b)

102 4
3
G' G''
1 1' 2
100 2 2'
3 3' 2
1
0.1 1 10 100
ω, s–1 1 10 100 1000
σ, Pa
Fig. 1. Frequency dependences of the (1–3) storage and
(1'–3') loss moduli for bitumen of different brands. Fig. 3. Flow curves for bitumen of different brands.
Panel (a): (1, 1') 90/130, (2, 2') Bituway 60P, and (3, 3') Panel (a): (1) 60/90, (2) 50/70, and (3) 22/5555A at
Bituway 40R at 25°C and panel (b): (1, 1') 50/70, (2, 2') 100°C and panel (b): (1) 90/130, (2) Bituway 60P, and
60/90, and (3, 3') 22/5555A at 100°C. (3) Bituway 40R at 135°C.

content is limited by a superlimiting increase in the

viscosity, which degrades the technological properties
of a material at the stage of its preparation.

G', G'', Pa Bitumens Filled with Rubber Crumb

G' G''
1 1' The addition of rubber crumb to a binder is an
105
2 2' alternative method for increasing binder stiffness. In
3 3' this work, APDDR powder was used as this filler.
103 Figure 4 presents the frequency dependences of the
components of the dynamic modulus of the compos
ites at 0°C. Commercial bitumens, including those
101 containing polymers, are actually indistinguishable at
this temperature, while the addition of APDDR to
unmodified bitumen increases both components of
10–1 the dynamic modulus by more than a decimal order of
30 60 90 120 magnitude. At the same time, for unfilled systems, the
T, °C components of the modulus are frequencyindepen
dent, thereby indicating that the bitumen is in the rub
berlike state (at the rubberlike elasticity plateau). The
incorporation of stiff APDDR particles into the sys
Fig. 2. Temperature dependences of the (1–3) storage and
(1'–3') loss moduli for bitumen of brands (1, 1') 90/130, tem causes the transition from the rubberlike state to
(2, 2') Bituway 60P, and (3, 3') Bituway 40R at a heating an intermediate state that is sometimes called as a
rate of 5 K/min. “leatherlike” one.

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 RHEOLOGICAL PROPERTIES OF ROAD BITUMENS MODIFIED WITH POLYMER 429

G', G'', Pa G',G'', MPa

with APDDR 30
G'
107 G''
1 1'
20
2 2'
3 3'
105 without APDDR
4 4'
5 5' 10
6 6'
103 0
0.1 1 10 100 1000 0 15 20 25
ω, s–1 w, %
Fig. 4. Frequency dependences of (1–6) storage and (1'–
6') loss moduli for bitumen of different brands: (1,1')
60/90, (2, 2') 50/70, (3, 3') 22/5555A and mixed compos Fig. 5. Histogram illustrating the dependence of the stor
ites containing (4, 4') 15, (5, 5') 20, and (6, 6') 25% age and loss moduli on APDDR content for bitumen of the
APDDR at 0°C. 60/90 brand at 0°C.

G', G'', Pa G', G'', Pa

103 105

101 G' G'' G' G''

1 1' 102 1 1'
2 2'
10–1 2 2'
3 3' 3 3'
4 4' 4 4'
10–3 10–1
0.1 1 10 100 0 50 100 150
ω, s–1 T, °C

Fig. 6. Frequency dependences of (1–4) storage and (1'– Fig. 7. Temperature dependences of (1–4) storage and
4') loss moduli for (1'–1') bitumen of the 60/90 brand con (1'–4') loss moduli for (1, 1') bitumen of the 60/90 brand
taining (2, 2') 15, (3, 3') 20, and (4, 4') 25% APDDR at containing (2, 2') 15, (3, 3') 20, and (4, 4') 25% APDDR at
100°C. a cooling rate of 5 K/min.

In general, the addition of relatively small amounts The consideration of the temperature dependences
of APDDR to composites seems to be sufficient to of the components of the dynamic modulus shows that
improve their viscoelastic properties. This may be the difference between initial bitumen and the
explained by a high coefficient of rubber swelling in a APDDRcontaining composite remains preserved
bitumen matrix. No positive effect is observed upon a (Fig. 7). The difference of the filled composites from
further increase in the content of rubber (Fig. 5). the initial bitumen is that the former are characterized
by a monotonic reduction in the viscoelastic proper
At 100°C, the difference between the samples is ties with increasing temperature, while pure bitumen
more pronounced (Fig. 6). The storage modulus of exhibits an inflection point at a temperature of about
pure bitumen is low, which indicates the transition to a 30°C.
flowing state. At the same time, for bitumens contain It should be emphasized that the temperature
ing stiff filler (20 and 25%), the moduli begin to weakly dependence of the storage modulus is smoothed when
depend on the frequency and are characterized by high bitumen is filled with APDDR. For example, whereas,
eigenvalues; hence, the transition from a leatherlike within the considered temperature range, the storage
(at high frequencies) to a rubberlike (at low frequen modulus of pure bitumen decreases by eight decimal
cies) state takes place. orders of magnitude, the filling shortens the range of

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430 ILYIN et al.

η, Pa s G', G'', Pa (a)

6
10

104
4 105

3 G' G''
102 10 4 1 1'
2
2 2'

1
103
100 1 10 100 1000
0.1 10 1000
ω, s–1
σ, Pa η, kPa s (b)
Fig. 8. Flow curves for (1) bitumen of the 60/90 brand con 24
taining (2) 15, (3) 20, and (4) 25% APDDR at 100°C.

the modulus fall to four orders of magnitude. Thus, at 21

elevated temperatures, filled composites retain the
stiffness caused by the modification much better. 2
18
The consideration of the flow curves of the com
posites (Fig. 8) shows that APDDRfilled systems 1
have a structure formed by filler particles in the bulk 15
material, which is evident from the existence of the 10 100 1000 10000
yield stress. At 15% filling, the structure is rather weak, σ, Pa
and the yield stress is equal to nearly 1 Pa, and, at Fig. 10. (a) Frequency dependences of (1–2) storage and
higher stresses, the mixture flows exhibiting almost (1'–2') loss moduli and (b) flow curves for (1) pure MPB
Newtonian behavior (although the viscosity of the and (2) sample containing 1.4% CNTs at 20°C.
composition is noticeably higher than that of pure
bitumen). However, already at 25% filling, the viscos
ity dramatically increases and the apparent viscosity increase in bitumen viscosity, which limits the possible
becomes markedly dependent on the shear stress, content of the crumb in bitumen due to technological
which indicates the breakage of the structural network reasons.
of filler particles upon deformation.
The concentration dependence of the viscosity at Bitumens Modified with Polymer and Filler
the selected constant shear stress (100 Pa) is linearized
in semilogarithmic coordinates (Fig. 9). Thus, the Filling of bitumens with nano and/or microsized
addition of rubber crumb causes an exponential particles is a promising method for bitumen modifica
tion. It may be assumed that, owing to the highly
developed surface of such particles, very small addi
tives thereof are necessary for substantial improvement
η, Pa s of the physicochemical properties of a binder.
104 It is reasonable to incorporate nanoparticles (in our
case, carbon nanotubes) into a polymer matrix that
has a moderate viscosity but rather pronounced elastic
properties, which make it possible to disperse the filler
in the regime of elastic turbulence [58].
102
MPB, which was used in this work as an adhesive
additive, meets this requirement and can be used as a
matrix for the preparation of a concentrate of nano
100
tubes. The rheological properties of this concentrate
0 10 20 30 are compared with unfilled MPB in Fig. 10.
w, % These data lead us to conclude that the incorpora
Fig. 9. Viscosity of bitumen of the 60/90 brand as a func tion of a rather large amount of nanotubes (1.4%) only
tion of APDDR content at 100°C and a shear stress of slightly increases the polymer viscoelasticity and does
100 Pa. not lead to the formation of a network of filler particles

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 RHEOLOGICAL PROPERTIES OF ROAD BITUMENS MODIFIED WITH POLYMER 431

G', G'', Pa (a) G', G'', Pa G' G''

1 1'
105
6
2 2'
10 3 3'
4 4'
G' G'' 103 5 5'
1 1'
105
2 2'
3 3' 101
4 4'
104 5 5'
0.1 1 10 100 30 60 90 120
ω, s–1 T, °C
G', G'', МPa (b)
G'
Fig. 12. Temperature dependences of (1–5) storage and
G'' (1'–5') loss moduli for (1, 1') bitumen Bituway 60P (2, 2')
0.4 modified with 1.25% CNT/MPB mixture and containing
(3, 3') 1.6, (4, 4') 3.2, and (5, 5') 10% MK at an angular fre
quency of 10 s–1 and a heating rate of 5 K/min.

0.2 The analysis of the temperature dependence of the

viscoelastic properties of the MKfilled composites
showed their somewhat higher stiffness at elevated
temperatures (Fig. 12).
0 The flow curves of MKcontaining binders show
0 1.6 3.2 10 their slightly pronounced nonNewtonian behavior,
w, %
which, nevertheless, becomes stronger with an
increase in the filler content (Fig. 13). It should be
Fig. 11. Panel (a): frequency dependences of (1–5) storage emphasized that the performed studies have shown the
and (1'–5') loss moduli for (1, 1') bitumen Bituway 60P (2,
2') modified with 1.25% CNT/MPB mixture and contain absence of a yield stress for these composites. Together
ing (3, 3') 1.6, (4, 4') 3.2, and (5, 5') 10% MK and with the results of dynamic tests, this finding shows the
panel (b): histograms of storage and loss moduli for bitu absence of a structural network. At the same time, the
men Bituway 60P with different kaolin contents at a fre
quency of 10 s–1 and 25°C. nonNewtonian character of the flow may indicate the
aggregation of organophobic particles in the bitumen
matrix.
(Fig. 10a). At the same time, the viscosity of the com
posite increases by nearly 30% and the nonNewto
nian behavior (Fig. 10b) manifests itself at lower η, Pa s
stresses and becomes more pronounced, which may
attest to partial adsorption of macromolecules on par
5
ticle surface. 4
Nevertheless, the formation of a network from filler
nanoparticles seems to be reasonable for increasing 4
the viscoelastic properties of a binder at elevated tem
peratures and the impact characteristics at decreased 2 3 2
ones.
1
Clay, which consists of nano and microstructural
elements, was proposed to be used as another alterna
tive filler. For example, MK is such a filler. However, 0
the incorporation of MK into the composite in 0.1 1 10 100 1000
amounts below 10 wt % appeared not to cause the for σ, Pa
mation of a network from filler particles (Fig. 11a) and Fig. 13. Flow curves for (1) bitumen composite Bituway
only slightly to increase the viscoelastic characteristics 60P (2) modified with 1.25% CNT/MPB mixture and
of the mixed composite (Fig. 11b). containing (3) 1.6, (4) 3.2, and (5) 10% MK at 135°C.

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432 ILYIN et al.

η, Pa s Similarly to the rubber filler, the concentration

5 dependence of the viscosity, as determined in the lim
iting case of the zero shear rate, is linearized in the
4 semilogarithmic coordinates (Fig. 14), with, however,
a much smaller slope.
3

CONCLUSIONS
2
It is reasonable, within the framework of the goals
of this work, to compare the aboveconsidered quanti
tative characteristics of the rheological properties of
the bitumenbased composites with the standard
1 parameters of their properties. For this purpose both
0 3 6 9 commercial and modified binders were tested (three
w, % samples of each).
Fig. 14. Dependence of viscosity on MK content at zero The results of the standard tests (Table 1) lead us to
shear and 135°C for bitumen composite Bituway 60P. conclude that the sample of the composite containing
the rubber filler ranks above the claymodified sample
in all of the parameters and both modified composites
h, mm 10–1 exhibit much better properties than the matrix bitu
90/130 men sample does.
120
Penetration is one of the basic standard parameters
of bitumen properties. It is obvious that the depth of
90 Bituway 60P the needle penetration into a binder sample in the
90/130 course of the measurements must be related to the vis
+3.5% SBS coelastic characteristics of the sample. As an example,
+10% APDDR Fig. 15 shows the superposition of the complex
60 dynamic moduli of the samples, which were measured
90/130 Bituway 40R at a fixed angular frequency of the action on the sam
+3.5% SBS ples of 10 s–1 and 25°C, with depths h of needle pene
+10% MK tration into the materials. It appeared that, being pre
sented in the semilogarithmic coordinates, this depen
0.3 0.6 0.9 dence is almost linear (Fig. 15):
G *, MPa
h = 6.9 × 10 5(G *) − 0.7.
Fig. 15. Correlation between the depth of needle penetra
tion and complex modulus at an angular frequency of Heat resistance may be estimated from the temper
10 s ⎯1 and 25°C. ature dependence of the dynamic modulus using the
technique proposed in the Superpave standard
(United States). According to this standard, the max
TGOST, °С imum service temperature of a freshly prepared binder
100 is determined as a temperature at which the G*/sinδ
100/130
value of a material at an angular deformation fre
+3.5% SBS quency of 10 s–1 is no lower than 1 kPa [59]. The data
80 +10% MK obtained with the application of this approach to all
Bituway 40R samples studied in this work are listed in Table 2.
Bituway 60P
60 The following conclusions may be drawn from the
100/130 data presented in Table 2: the addition of CNTs, MPB,
+3.5% SBS or MK has no effect on the heat resistance, while the
40 90/130 +10% APDDR incorporation of SBS or APDDR noticeably increases
this parameter. Moreover, the heat resistance of
APDDR and SBScontaining composites obtained
20 in the work is much higher than that of commercial
80 100 120 brands of bitumen, with the highest effect being
TSuperpave, °С observed in the presence of both components in a
composite. Therefore, we may speak of the synergistic
effect in the enhancement of the heat resistance upon
Fig. 16. Correlation between the GOST softening temper simultaneous addition of the filler particles and the
ature and the Superpave maximum pavement temperature. polymer.

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 RHEOLOGICAL PROPERTIES OF ROAD BITUMENS MODIFIED WITH POLYMER 433

Table 1. Results of standard tests of bitumen samples

Sample

Parameter Modified
Unmodified
3.5% SBS and 10% APDDR 3.5% SBS and 10% MK

Softening temperature, °C 44 77 58
Fraas brittle temperature, °C –25 –37 –22
Penetration at 25/0°C, 0.1 mm 118/31 58/43 55/30
Ductility at 25°C, cm 98 88 87
Change in thinfilm softening temperature af 5 4 7
ter heating, °C

Table 2. Superpave heat resistance of bitumen samples

Sample T, °C Sample T, °C

60/90 59 Bituway 60P/CNT/MPB + 1.6% MK 80

50/70 60 Bituway 60P/CNT/MPB + 3.2% MK 80
22/5555A 71 Bituway 60P/CNT/MPB + 10% MK 80
60/90 + 15% APDDR 83 Bituway 40R 95
60/90 + 20% APDDR 108 100/130 73
60/90 + 25% APDDR >150 100/130 + CNT/MPB + 3.5% SBS + 10% APDDR 126
Bituway 60P 81 100/130 + CNT/MPB + 3.5% SBS + 10% MK 102
Bituway 60P/CNT/MPB 80

The superposition of the data listed in Table 2 with Mechanics of Disperse Structures: Collected Works),
the results of measuring the softening temperature Moscow: Nauka, 1966.
according to GOST (State Standard) is presented in 4. Gorshenina, G.I., Kuperman, M.E., and
Fig. 16. The following linear correlation can be seen Mikhailov, N.V., Kolloidn. Zh., 1964, vol. 26, p. 165.
between these values: 5. Kolbanovskaya, A.S., Davydova, A.R., and Shemo
naeva, D.S., Kolloidn. Zh., 1967, vol. 29, p. 509.
TGOST = 12 + 0.5TSuperpave.
6. Shemonaeva, D.S. and Kolbanovskaya, A.S., Kolloidn.
Zh., 1973, vol. 35, p. 401.
ACKNOWLEDGMENTS 7. Kotlyarskii, E.V., Finashin, V.N., Uriev, N.B., and
Chernomaz, V.E., Kolloidn. Zh., 1987, vol. 49, p. 72.
This work was supported by the federal targeted 8. Gokhman, L.M., in Puti uluchsheniya svoistv
program “Research and Development of HighPrior asfal’tobetonnykh i drugikh bitumomineral’nykh smesei
ity Directions of the Scientific and Technological (Methods for Improvement of the Properties of Asphalt
Complex of Russia for 2007–2013 (state contract Concrete and Other Bituminous Mineral Mixes), Mos
no. 14.513.11.0113 of July 1, 2013). cow: SoyuzdorNII, 1971.
9. Gokhman, L.M. and Davydova, K.I., in Polimernye
materialy v stroitel’stve pokrytii avtomobil’nykh dorog
REFERENCES (Polymer Materials in Automobile Road Pavements),
Moscow: SoyuzdorNII, 1981.
1. Lesueur, D., Adv. Colloid Interface Sci., 2009, vol. 145,
p. 42. 10. Rudenskaya, I.M. and Rudenskii, A.V., Reologicheskie
svoistva bitumov (Rheological Properties of Bitumen),
2. Rehbinder, P.A., Zh. Vses. Khim. Ova im D.I. Mendele Moscow: Vysshaya Shkola, 1967.
eva, 1963, vol. 8, no. 2, p. 162. 11. Malkin, A.Ya., Sabsai, O.Yu., Verebskaya, E.A., Zolo
3. Rehbinder, P.A., Fizikokhimicheskaya mekhanika dis tarev, V.A., and Vinogradov, G.V., Kolloidn. Zh., 1976,
persnykh struktur: sbornik statei (Physicochemical vol. 38, p. 181.

COLLOID JOURNAL Vol. 76 No. 4 2014

434 ILYIN et al.

12. Vinogradov, G.V., Zolotarev, V.A., and 36. Navarro, F.J., Partal, P., GarciaMorales, M., Mar
Verebskaya, E.A., Kolloidn. Zh., 1979, vol. 41, p. 409. tinezBoza, F.J., and Gallegos, C., Fuel, 2007, vol. 86,
13. Kolbanovskaya, A.C. and Mikhailov, V.V., Dorozhnye p. 2291.
bitumy (Road Bitumen), Moscow: Transport, 1973. 37. Cuadri, A.A., GarciaMorales, M., Navarro, F.J.,
14. Luksha, O.V., Opanasenko, O.N., Krut’ko, N.P., and Airey, G.D., and Partal, P., Rheol. Acta, 2013, vol. 52,
Loboda, Yu.V., Russ. J. Appl. Chem. 2006, vol. 79, p. 145.
p. 1021. 38. Navarro, F.J., Partal, P., GarciaMorales, M., Martin
Alonso, M.J., MartinezBoza, F., Gallegos, C., Bor
15. Rozental’, D.A., Kutsenko, V.I., and Miroshnikov, E.P., dado, J.S.M., and Diogo, A.C., J. Ind. Chem. Eng.,
Stroit. Mater., 1995, no. 9, p. 23. 2009, vol. 15, p. 458.
16. Gokhman, L.M., Gurarii, E.M., Davydova, A.R., and 39. Martinez, M., Paez, A., and Martin, M., Fuel, 2008,
Davydova, K.I., Polimernobitumnye vyazhushchie vol. 87, p. 1148.
materialy na osnove SBS dlya dorozhnogo stroitel’stva.
Vyp. 4 (SBBased Polymer Bitumen Binders for Road 40. Masson, J.F., Energy Fuels, 2008, vol. 22, p. 2637.
Building), Moscow: Inforavtodor, 2002, no. 4. 41. VasiljevicShikalevska, A., PopovskaPavlovska, F.,
17. Pechenyi, B.G., Bitumy i bitumnye kompozitsii (Bitu Cimmino, S., Duraccio, D., and Silvestre, C., J. Appl.
men and Bituminous Compositions), Moscow: Polym. Sci., 2010, vol. 118, p. 1320.
Khimiya, 1990. 42. Ghasemi, M., Marandi, S.M., Tahmoores, M., Kama
18. Rudenskii, A.V., Nikonova, O.N., and Kaziev, M.G., lia, R.J., and Taherzade, R., J. Basic Appl. Sci. Res.,
Stroit. Mater., 2011, no. 10, p. 10. 2012, vol. 2, p. 1338.
43. Gutierrez, L. and Pawlik, M., J. Rheol. (N. Y.), 2012,
19. Ivan’ski, M. and Uriev, N.B., Asfal’tobeton kak vol. 56, p. 687.
kompozitsionnyi material (s nanodispersnym i
polimernym komponentami) (Asphalt Concrete as Com 44. Gutierrez, L., PhD Thesis (The University of British
posite Material (with Nanodisperse and Polymer Com Columbia, Vancouver, Canada, 2009).
ponents)), Moscow: Tekhpoligraftsentr, 2007. 45. Parviz, A., Austr. J. Basic Appl. Sci., 2011, vol. 5,
20. Yousefi, A.A., Prog. Color Colorants Coat., 2009, vol. 2, p. 3270.
p. 53. 46. Hassan, Z., Hassan, D., Rezvan, B., and Ali, A., World
21. Huang, S.C., J. Mater. Civil Eng., 2008, vol. 30, p. 221. Acad. Sci. Eng. Technol., 2012, vol. 68, p. 1534.
22. Mashaan, N.S. and Karim, M.R., Int. J. Nano Mater. 47. Shokuhfar, A. and EbrahimiNejad, S., Constr. Build.
Sci., 2012, vol. 1, p. 68. Mater., 2010, vol. 24, p. 1239.
48. Jahromi, S.Gh. and Khodaii, A., Constr. Build. Mater.,
23. Fu, H.Y., Xie, L.D., Dou, D.Y., Li, L.F., Yu, M., and
2009, vol. 23, p. 2894.
Yao, S.D., Constr. Build. Mater., 2007, vol. 21, p. 1528.
49. You, Zh. and MillsBeale, J., Constr. Build. Mater.,
24. Wang, Q., Liao, M.Y., and Wang, Y.R., J. Appl. Polym. 2011, vol. 25, p. 1072.
Sci., 2007, vol. 103, p. 8.
50. Fu, Y., Wu, Sh., Han, J., and Yu, J., Abstracts of
25. Krut’ko, N.P., Opanasenko, O.N., Luksha, O.V., and Papers, Int. Conf. on Mech. Automat. Control Eng.
Loboda, Yu.V., Russ. J. Appl. Chem., 2009, vol. 82, (MACE), Wuhan, 2010, p. 1382.
p. 1301. ˆ
51. Liu, T.G., Wu, S.P., and Han, J., Key Eng. Mater., 2011,
26. Polacco, G., Kri z , P., Filippi, S., Stastna, J., Biondi, D., vol. 467.
and Zanzotto, L., Eur. Polym. J., 2008, vol. 44, p. 3512.
52. Hooshar, A., Uhlok, H., Kaminsky, H.W., Shinbine, A.,
27. Zhang, B., Xi, M., Zhang, D., Zhang, H., and Zhang, B., Omotoso, O., Liu, Q., Ivey, D.G., and Etsel, T.H.,
Constr. Build. Mater., 2009, vol. 23, p. 3112. Appl. Clay Sci., 2010, vol. 48, p. 466.
28. Navarro, F.J., Partal, P., and MartinezBoza, F., Polym. 53. Yartsev, V.P., Polezhaeva, E.S., and Buchnev, A.Yu.,
Test., 2010, vol. 29, p. 588. Vestn. TGTU, Materialoved. Nanotekhnol., 2011,
29. Sureshkumar, M.S., Filippi, S., Polacco, G., Kazatch vol. 17, no. 4, p. 1053.
kov, I., Stastna, J., and Zanzotto, L., Eur. Polym. J., 54. Hasan, Z., Kamran, R., Mohammad, F., Ahmad, G.,
2010, vol. 46, p. 621. and Hosein, F., Int. J. Civil Environ. Eng., 2012, vol. 12,
30. Sengoz, B. and Isikyakar, G., Constr. Build. Mater., p. 53.
2007, vol. 22, p. 1897. 55. Motlagh, A.A., Kiasat, A., Mirzaei, I.E., and Birgani, F.O.,
31. Garrera, V., Partal, P., GarciaMorales, M., Gallegos, C., World Appl. Sci. J., 2012, vol. 18, p. 594.
and PerezLope, F., Fuel Process. Technol., 2010, 56. Amirkhanian, A.R., Xiao, F., and Amirkhanian, S.N.,
vol. 91, p. 1139. Int. J. Pavement Res. Technol., 2011, vol. 4, p. 81.
32. Guardi, A.A., Partal, P., Navarro, F.J., Garcia 57. Yao, H., You, Z., Li, L., Goh, S.W., Lee, C.H.,
Morales, M., and Gallegos, C., Energy Fuels, 2011, Yap, Y.K., and Shi, X., Constr. Build. Mater., 2013,
vol. 25, p. 4055. vol. 38, p. 327.
33. Guardi, A.A., GarciaMorales, M., Navarro, F.J., and 58. Karbushev, V.V., Semakov, A.V., and Kulichikhin, V.G.,
Partal, P., Fuel, 2012, vol. 96, p. 862. Polym. Sci., Ser. A, 2011, vol. 53, p. 1513.
34. MartinAlfonso, M.I., Partal, P., Navarro, F.J., Garcia 59. Cominsky, R.J., Huber, G.A., Kennedy, T.W., and
Morales, M., and Gallegos, C., Eur. Polym. J., 2008, Anderson, M., The Superpave Mix Design Manual for
vol. 44, p. 1451. New Construction and Overlays, Washington, DC: Stra
35. Garrera, V., GarciaMorales, M., Partal, P., and Gal tegic Highway Research Program, 1994.
legos, C., Rheol. Acta, 2010, vol. 49, p. 563. Translated by A. Kirilin

COLLOID JOURNAL Vol. 76 No. 4 2014