Construction and Building Materials 64 (2014) 316–323

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Construction and Building Materials

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Rheological property investigations for polymer and polyphosphoric acid

modified asphalt binders at high temperatures
Feipeng Xiao a,⇑, Serji Amirkhanian b, Hainian Wang c, Peiwen Hao c
a
Key Laboratory of Road and Traffic Engineering of the Ministry of Education, Tongji University, Shanghai, 201804, China
b
Department of Civil, Construction, and Environmental Engineering, University of Alabama, Tuscaloosa, AL 35487, USA
c
School of Highway, Chang’an University, Xi’an, China

h i g h l i g h t s

 Rheology on SBS and three alternative binders with/without PPA was studied.
 Two base asphalt binders, four polymers, and one PPA were used to produce binders.

 Viscosity, G /sin d, amplitude and frequency sweep, creep recovery, etc. were tested.
 0.5% PPA could reduce by 1.0% the polymer needed to produce the PG 76-22 binder.
 Rheology of binders is dependent on polymer type, asphalt source and test temperature.

a r t i c l e i n f o a b s t r a c t

Article history: Polymer modified asphalt binders have been used with success in mitigating many major causes of
Received 17 February 2014 asphalt pavement failures (e.g., permanent deformation, moisture induced damage, fatigue, etc.). The sty-
Received in revised form 3 April 2014 rene butadiene styrene (SBS) is commonly used for producing PG 76-22 binder, but the market was hit
Accepted 4 April 2014
with a shortage of butadiene back in late 2009, which affected both supply and cost of PG 76-22 through-
out the entire United States. Therefore, some alternative modifiers such as elastomers, plastomers, recy-
cled ground tire rubber, sulfur additives, and polyphosphoric acid (PPA) to substitute for SBS in PG 76-22
Keywords:
asphalt binders have been investigated for future applications in the industry. The objective of this study
Polymerized asphalt binder
Crumb rubber
was to investigate the high temperature rheological properties of SBS and three alternative polymer mod-
Polyphosphoric acid ified binders with/without PPA. Two base asphalt binders (PG 64-22), four polymers, and one PPA were
Viscosity used to produce the modified binders. The tested rheological properties include rotational viscosity, fail
Fail temperature temperature, G/sin d, phase angle, viscometry, amplitude sweep, frequency sweep, creep and creep
Amplitude and frequency sweep recovery, and relaxation. The test results indicated that the PG 76-22 binders with two alternative poly-
Relaxation mers had noticeably lower viscosity values compared to SBS modified binders and thus need lower
energy for mixing and compaction. In addition, for the binders used in this research work, the utilization
of 0.5% PPA could reduce by 1.0% of additional polymer needed to produce the PG 76-22 binder. More-
over, the characteristics of viscometry, amplitude sweep, frequency sweep, creep and creep recovery,
and relaxation spectrums of all modified binders were generally dependent upon polymer type, asphalt
source, and test temperature.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction pavement failures, including permanent deformation at high tem-

In many cases, heavy traffic loading and severe weather condi-
tions will result in some serious functional damage of asphalt
pavements. Therefore, polymers have been incorporated into
asphalt binders as a way to mitigate many major causes of asphalt
⇑ Corresponding author. Tel.: +1 864 6504821.
E-mail address: fpxiao@gmail.com (F. Xiao).
peratures and cracking at low temperatures, as well as some other
failures such as fatigue, raveling, and stripping damage for many
years [1–3]. These polymer modified asphalt (PMA) binders also
have been used with success at many locations of high stress such
as interstates, intersections, and airports [4]. The PMA has been
commonly used materials in high quality asphalt pavement indus-
try in many parts of the United States (US). PMA has proven itself
to be an essential element in the paving process.

http://dx.doi.org/10.1016/j.conbuildmat.2014.04.082
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323
Of all the polymer modifiers, styrene butadiene styrene (SBS),
which was originally developed by Shell Chemical Co., is widely
used in the majority of the modified asphalt binders in the US
[5–7]. SBS creates a three dimensional network within the virgin
asphalt phase, resulting in an excellent bonding strength to aggre-
gates that leads to a durable and long-lasting pavement [8,9]. Cur-
rently, in the United States, the most commonly used polymer for
asphalt modification is the SBS followed by other polymers such as
GTR (ground tire rubber), SBR (styrene butadiene rubber), EVA
(ethylene vinyl acetate) and polyethylene [10–12]. According to a
modified asphalt market survey in 2005–2006, 80% of states,
including South Carolina, across the US used SBS as a modifier [13].
Although they cost more than conventional binders, SBS-modi-
fied PG 76-22 asphalt binders have been utilized for many years by
many state DOTs on interstate projects in order to increase the life
of asphalt pavements. The high cost associated with the SBS mod-
ification process is mostly due to the SBS material. The SBS market
was hit with a shortage of Butadiene back in late 2009, which
affected both supply and cost of PG 76-22 throughout the entire
US. Due to many reasons, it is important to have some alternative
modifiers such elastomers, plastomers, other polymers, GTR (from
recycled passenger and truck tires), sulfur additive, and PPA (poly-
phosphoric acid) to substitute for SBS in PG 76-22 asphalt binders.
Polymers, having long-chain molecules of very high-molecular
weight, used by the binder industry are classified based on differ-
ent criteria including two general categories: elastomers and plas-
tomers. An elastomer may be defined as an amorphous, cross-
linked polymer above its glass transition temperature [14–16].
The load–deformation behavior of elastomers is similar to that of
a rubber band such as increasing tensile strength with increased
elongation, which may reach 1300% of the original length, and abil-
ity to recover to the initial state after removal of load. Plastomers
exhibit high early strength but are less flexible and more prone
to fracture under high strains than elastomers [17–19].
In an attempt to change its rheological characteristics and
improve its performance properties, asphalt is often modified with
an elastomer [20,21], a plastomer [22,23], a thermoset [24,25], sul-
fur [26], or a mineral acid [27]. The interest in using polyphospho-
ric acid (PPA) as a modifier to change asphalt features has
increased in recent years [28]. It has been reported, by itself or in
combination with a polymer, PPA provides a means of asphalt
modification usually produced cheaper than one with a polymer
alone [28].
PPA is an oligomer of H3PO4. High-purity material is produced
either from the dehydration of H3PO4 at high temperatures or by
heating P2O5 dispersed in H3PO4 [29–31]. The dehydration method
tends to produce short chains, whereas the dispersion method usu-
ally produces chains with more than 10 repeat units [32]. The lit-
erature indicates that the PPA has found increasing use as a
straight additive without the need for air blowing to improve the
grade range. Typical results are high-temperature grade improve-
ments of less than 6 °C [31]. The increase in grade is thought to
occur because of a reaction between the asphaltenes and acid
[31,32].
Table 1
Rheology of base binders A and B.
Binder type Source Aging states
Unaged Unaged
Viscosity (135 °C) Fail temp. G/sin d (64 °C)
(cP) (°C) (kPa)
PG 64-22 A 645 68.8 2.03
PG 64-22 B 465 66.4 1.28
317
Kodrat et al. reported the effect of PPA on the Superpave grading
properties was found to be significant, with the high-temperature
grade increasing by varying amounts depending on the crude
source and the low-temperature grade [33]. King et al. found that
contained asphalt binders modified with both PPA and anti-strip-
ping agent and tested using a Hamburg Wheel Tracking Device
and an Asphalt Pavement Analyzer and found poor performance
in these mixtures with acid–amine binders [34]. Ajideh et al. indi-
cated that the resistance to moisture damage of asphalt mixtures
modified with only PPA was not as good as that of those modified
with other polymers [35]. In addition, they also found that asphalt
mixtures modified with only PPA exhibited significantly improved
resistance to rutting and fatigue. Baumgardner et al. studied the
mechanism of how PPA interacts with asphalt binder and found
that the interaction depends on the base (virgin) asphalt [32,36].
The objective of this study is to investigate the high tempera-
ture rheological properties of SBS and three alternative polymer
modified binders with/without PPA. Two base asphalt binders, four
polymers, and one PPA are used to produce the modified binders.
The tested rheological properties in this study include viscosity, fail
temperature, G/sin d, phase angle, amplitude sweep, frequency
sweep, creep and creep recovery, and relaxation.
2. Materials and experimental procedures
2.1. Materials
The bitumen materials used in this study included two asphalt base binders,
which were from southeast area of USA. Both asphalt binders are PG 64-22 from dif-
ferent sources, commonly used by various state departments of transportation
(DOTs). The basic rheological properties of two base binders are shown in Table 1.
It can be noted that binder A generally has a higher viscosity, fail temperature, and
G/sin d at unaged and rolling thin film oven (RTFO) states compared to binder B, but
has a lower G sin d and stiffness after a long term aging process. Therefore, it could
be concluded that binder A has a better aging resistance.
Four polymers used in this research were SBS, oxidized polyethylene, Propyl-
ene–maleic anhydride, and 40 mesh ambient produced recycled crumb rubber
and are referred to as 1–4, respectively. The main physical and chemical properties
of these materials are shown in Table 2. Polymer 1, SBS, is commonly used for pro-
ducing PG 76-22 binders (AP1 and BP1) with a concentration of 3.0% (by weight of
base binder). Polymer 2 generally has a lower melting point and is often used for
reducing the mixing and compaction temperature of asphalt mixtures. Approxi-
mately 3.0% (by weight of base binder) of polymer 2 was blended with base binders
A and B to produce PG 76-22 binders (AP2 and BP2). Similarly, 3.0% of polymer 3
was used to produce the modified binders AP3 and BP3. When using recycled
crumb rubber, approximately 10% 40 mesh crumb rubber was blended with base
binders A and B and the produced binders were referred to AP4 and BP4.
The blending time and temperature to produce these PG 76-22 binders in this
study were 30 min and 165 °C, respectively. However, when blended with 0.5%
PPA, only 2% of polymers 1–3 and 10% crumb rubber were blended with the base
binders for 30 min first and then PPA was added to the modified binders and
blended another 30 min as recommended by the manufacture. The produced mate-
rials were designated as shown in Table 3.
2.2. Experimental procedure
The base binders and produced modified binders were tested according to
Superpave binder specifications. Brookfield rotational viscometer was employed
to measure the viscosity of these binders per AASHTO T316. Approximately 10.5 g
base binders were tested to obtain the viscosity value by using a spindle of #21
RTFO PAV
G/sin d (64 °C) G sin d (25 °C) Stiffness ( 12 °C) m-Value ( 12 °C)
(kPa) (kPa) (MPa)
4.94 1429 103 0.376
2.87 3229 257 0.312
318 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323

Table 2
Physical and chemical components of three polymers, recycled crumb rubber, and PPA.

Properties 1 2 3 4 PPA
Ingredients Styrene–butadiene–styrene Oxidized polyethylene Propylene–maleic anhydride Processed rubber Polyphosphoric acid
Block copolymers Maleic anhydride Carbon, sulfur Tetraphosphoric acid
Physical state Solid Wax like solid powder Solid Solid Liquid
Color White White Light yellow pellets Dark Amber. (dark grey)
Odor Odorless Wax like mild Characteristic waxy odor Mild rubber Odorless
Specific Gravity 0.94–0.96 0.9 (25 °C) 0.93–0.94 1.10–1.15 2.02
Bulk density 0.20–0.45 g/cm3 0.85–1.00 g/cm3 1.03 g/cm3 0.34–0.35 g/cm3 –
Ph values N/A N/A N/A N/A 2-Jan
Boiling point – – – – 282 °C
Melting point 160–200 °C 88–140 °C 143–148 °C >200 °C –
Flashpoint – >255 °C (closed up) – – –
Solubility in water Insoluble Negligible Negligible Insoluble Water soluble

Notes: 1–4: polymer types, PPA: polyphosphoric acid.

Table 3
Test sample names of modified asphalt binders.

Binder type Base binder Polymer type (PG 76-22) Polymer type + PPA (PG 76-22)
1 2 3 4 1 2 3 4
PG 64-22 A0 AP1 AP2 AP3 AP4 APP1 APP2 APP3 APP4
PG 64-22 B0 BP1 BP2 BP3 BP4 BPP1 BPP2 BPP3 BPP4

Notes: 0: no polymer, 1–4: polymer types, A and B: binder types, P: polymerized, PP: polymerized binder with PPA.

with a rotational speed of 20 rpm while 8.5 g polymerized binders were tested by
using a #27 spindle. Three test temperatures of 135 °C, 150 °C and 165 °C were used
to investigate the variability of all modified binders in this study.
Dynamic shear rheometer (DSR) was used to test the complex shear modulus
(G*), phase angle (d), and other rheological properties in term of AASHTO T315.
These binders were tested with a 25 mm diameter plate and a 1000 lm gap except
that the rubberized asphalt binders were tested with a 2000 lm gap as has been
suggested by many researchers. The DSR binder tests were performed at a fre-
quency of 10 radians per second, 1.59 Hz. The shear stress and shear strain were
measured during each cycle and then were used to characterize both viscous and
elastic behavior. All binders (PG 64-22 and PG 76-22) were tested at a starting tem-
perature of 64 °C and continued until reached a fail temperature, G*/sin d value less
than 1.0 kPa for an unaged binder.
3. Test results and discussions
3.1. Viscosity
The viscosity is the flow characteristics of the asphalt binder to
provide some assurance that it can be pumped and handled at the
hot mix facility. It is also used to develop temperature–viscosity
charts for estimating mixing and compaction temperature for use
in mix design as a reference [37]. Generally, a higher viscosity
value results in higher mixing and compaction temperatures and
may increase the energy consumption.
As shown in Fig. 1, it can be observed that the viscosity values
reduce as the test temperature increases regardless of polymer
type and binder source. Fig. 1 indicates that the base binders have
the lowest viscosity values at three test temperatures while the
rubberized asphalt binders have the highest viscosity. Comparing
Figs. 1(a) and (b), it can be noted that the modified binders pro-
duced from binder A have greater viscosity values due to higher
viscosity from the base binder A. In addition, polymerized binders
AP2, AP3, BP2, and BP3 generally have slightly higher viscosity val-
ues than the base binders A0 and B0, but noticeably lower viscosity
values compared to SBS and rubberized binders (AP1, AP4, BP1, and
BP4). Therefore, as using polymers 2 and 3, a lower mixing and
compaction temperature can be employed to produce the asphalt
mixture in the laboratory and at the asphalt plant, same as recom-
mended by manufactures.
In addition, Fig. 2 shows that, as blended with 0.5% PPA, these
modified asphalt binders (2% polymers 1–3 or 10% crumb rubber)
have higher viscosity values compared to those modified binders
containing 3.0% polymers of 1–3 or 10% crumb rubber (Fig. 1). In

10000 10000
A0 AP1 AP2 AP3 AP4 B0 BP1 BP2 BP3 BP4
Viscosity (cp)

Viscosity (cp)

1000 1000

100 100
120 135 150 165 180 120 135 150 165 180
Temperature (°C) Temperature (°C)
(a) (b)
Fig. 1. Viscosity values of polymerized binders for binder sources. (a) A and (b) B.

10000
Viscosity (cp)
1000
100
120
addition, the viscosity values shown in Fig. 2(a) are greater than
those values from Fig. 2(b) because the base binder A has a higher
viscosity than the base binder B. Similarly, APP2 and APP3, BPP2
and BPP3 have noticeably lower viscosity values than SBS and rub-
ber modified binders. Additionally, APP4 and BPP4 (rubberized
binders) have the greatest viscosity values. So, it can be concluded
that the polymerized binders made with polymers 2 and 3 have the
potential of reducing the energy demand during mixing and com-
paction of the mixtures.
3.2. Fail temperature
The fail temperature, a factor of G*/sin d less than 1.0 kPa, is
often used to determine the performance grade of an asphalt bin-
der. According to Superpave binder grade specifications, the south-
east area in USA uses PG 64-22 binder as a base binder for
secondary and local road pavements. The test results shown in
Fig. 3 illustrate that the base binders A and B have fail tempera-
tures greater than 64 °C and less than 70 °C, meanwhile, the base
binder A has a high fail temperature than the base binder B.
As shown in Fig. 3, it can be found that the modified binders
such as AP1-AP3 and BP1-BP3 have fail temperatures greater than
76 °C and less than 82 °C, but the fail temperature of rubberized
binder AP4 is just over 76 °C and the value of BP4 does not reach
76 °C. Thus, it seems that for the binders used the addition of
10% crumb rubber may not able to increase the fail temperature
by 6 °C. However, as shown in Fig. 3, as adding 0.5% PPA to AP4
and BP4, these modified binders (APP4 and BPP4) have fail temper-
ature greater than 82 °C and close to 82 °C, respectively. In addi-
tion, the modified binders produced from 2% polymers 1–3,
reduced from 3.0%, blended with 0.5% PPA (e. g. APP1-APP3 and
88
A B
Fail temperature (C)
82
76
70
64
58
52
0 P1 P2
Fig. 3. Fail temperatures of various polymerized binders.
F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323 319
10000
APP1 APP2 APP3 APP4 BPP1 BPP2 BPP3 BPP4
Viscosity (cp)
1000
100
135 150 165 180 120 135 150 165 180
Temperature (°C) Temperature (°C)
(a) (b)
Fig. 2. Viscosity values of polymerized binders with PPA for binder sources. (a) A and (b) B.
BPP1-BPP3) have fail temperatures greater than 76 °C. It can be
concluded that the reduced 1.0% polymer can be offset by an
increased 0.5% PPA. Meanwhile, the modified binders from the
base binder A have slightly higher fail temperatures due to the nat-
ure of the base binder A.
3.3. G*/sin d
The G*/sin d is often used to characterize the rutting resistance
of an asphalt pavement at a high performance temperature. A
greater G*/sin d value indicates having a pavement with a better
permanent deformation resistance. Fig. 4(a) and (b) show the G*/
sin d values of the modified asphalt binders from the base binders
A and B at a temperature from 64 °C to 82 °C, respectively. In
Fig. 4(a), it can be observed that all binders have G*/sin d values
greater than 1.0 kPa at 64 °C, but the G*/sin d value of the base bin-
der (A0) is 1.0 kPa as the test temperature reaches 68.8 °C. Other
modified binders have G*/sin d values greater than 1.0 kPa at
76 °C. The lowest test temperature found was 77.6 °C when the
G*/sin d is 1.0 kPa, which is the modified binder made with 10%
crumb rubber. Additionally, as shown in Fig. 4(a), APP4 (10% crumb
rubber with 0.5% PPA) have the greatest G*/sin d values at all test
temperatures and its G*/sin d value is greater than 1.0 kPa at
82 °C. Moreover, the modified binders with PPA generally have
slightly higher G*/sin d values.
Similar trends for those modified binders can be found in
Fig. 4(b), even though all modified binders have lower G*/sin d val-
ues at various test temperatures since the base binder A has a
higher G*/sin d value compared to the base binder B. For instance,
the temperature is only 66.4 °C, less than 68.8 °C, when the G*/sin d
value of the base binder B is 1.0 kPa. Therefore, the effects of alter-
native polymers and PPA on the G*/sin d values of the binders
tested are mainly based on the base binder source.
3.4. Phase angle
The time lag between the applied stress and the resulting strain
or the applied strain and corresponding stress is related to the
phase angle, d. In general, for a perfectly elastic material, an applied
load causes an immediate response, thus, the time lag is zero.
Reversely, a viscous material has a relatively large time lag
between load and response; its phase angle approaches 90° [37].
However, this property can be influenced by the nature of the poly-
mer such as visco-elastic, visco-plastic, and elastic–plastic at a high
performance temperature.
P3 P4 PP1 PP2 PP3 PP4
Biner types As shown in Fig. 5(a), phase angles of various modified binders
from the base binder A increase as the test temperature increased
except that the phase angles of modified binders containing
320 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323

10 10
A0 B0
AP1 BP1

G*/sin δ (kPa)
G*/sin δ (kPa)

AP2 BP2
AP3 BP3
1 AP4 1 BP4
APP1 BPP1
APP2 BPP2
APP3 BPP3
APP4 BPP4
68.8C 77.6C 66.4C 75.7C
0.1 0.1
58 64 70 76 82 88 58 64 70 76 82 88
Test temperature (C) Test temperature (C)
(a) (b)
Fig. 4. G*/sin d values of various polymerized binders made with binder sources. (a) A and (b) B.

90 90
B0
Phase angle (degress)

A0

Phase angle (degree)

AP1 BP1
80 80
AP2 BP2
AP3 BP3
70 AP4 70 BP4
APP1 BPP1
decreased decreased
APP2 BPP2
60 60
APP3 BPP3
APP4 BPP4
50 50
58 64 70 76 82 88 58 64 70 76 82 88
Test temperature (C) Test temperature (C)
(a) (b)
Fig. 5. Phase angle values of various polymerized binders made with binder sources. (a) A and (b) B.

polymer 3 were reduced when the test temperature increased from
70 °C to 82 °C. In addition, the phase angles of the other modified
binders produced similar trends as the test temperature increased.
Moreover, the results indicated that the base binder has a greater
phase angle than other modified binders, and exhibits a more vis-
cous behavior. Therefore, for the binders tested, it could be con-
cluded that the polymer type has an impact on the viscoelastic
characteristics of the modified binders at a high performance
temperature.
Similarly as shown in Fig. 5(b), the modified binders made with
the base binder B have the increased phase angles, showing higher
viscous characteristics, except that BP2, BP3, and BPP3 have the
reduced phase angles at a starting temperature of 70–82 °C. There-
fore, it is necessary to do some further research to identify the
visco-plastic behavior of these polymer materials at high test
temperatures.
3.5. Viscometry
The modified binders were performed viscometry test at 64 °C.
The setting controlled stress from 0.1 kPa to 100 kPa was used to
run the test. The obtained shear rate and viscosity value can be
used to characterize how a material is likely to flow under an
imposed constant shear stress [38].
The shear rate and viscosity values in terms of a reduced shear
stress are shown in Fig. 6. It can be found that an increased stress
results in an increase of the corresponding shear rate but the vis-
cosity values reduce at the same time. As expected, the lowest
shear rates of the modified binders result in the greatest viscosity
values regardless of the stress value. Same trend was noticed by all
the modified binders. However, no obvious conclusions can be
made that which polymerized binders show the greatest or the
lowest shear rate and viscosity values in this study. Additionally,
in Fig. 6, it can be observed that the shear rate and viscosity values
are generally affected by the polymer type, asphalt source, and the
reduced stress.
3.6. Amplitude sweep
The amplitude test is to perform an amplitude sweep at a single
frequency (1 Hz was used for this study). It is used mainly for
defining the linear region of the material under test for a subse-
quent frequency sweep. During an amplitude sweep, the amplitude
of the deformation or alternatively the amplitude of the shear
stress is varied while the frequency is kept constant [38].
As shown in Fig. 7, when 1 Hz frequency was used, a reduced
shear stress from 0.5 Pa to 10 Pa and a temperature of 64 °C, the
complex modulus values and phase angle values of all modified
binders generally were constant regardless of the binder source
and polymer type. Additionally the results shown in Fig. 7(a) indi-
cates that there are only slight differences in the complex modulus
and phase angle between any two of the modified binders, but
these values are noticeably different for the modified binders made
with the base binder B (Fig. 7(b)). Furthermore, no obvious trends
in complex modulus and phase angle values can be noted in terms
of the polymer type in this study. Consequently, it could be
 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323 321

100 A0 AP2 AP3 APP1 APP2 APP3 APP4 100000 100 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4 100000
A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
10 10
10000 10000
1
1

Shear rate (1/s)

Shear rate (1/s)

Viscosity (Pa.s)

Viscosity (Pa.s)
1000 0.1 1000
0.1
0.01
0.01 100 100
0.001
0.001
0.0001
10 10
0.0001 0.00001

0.00001 1 0.000001 1
0.1 1 10 100 0.1 1 10 100
Reduced shear stress (Pa) Reduced shear stress (Pa)
(a) (b)
Fig. 6. Shear rate and viscosity values of various polymerized binders at a reduced shear stress for binder sources. (a) A and (b) B.

10000 100 10000 100

Complex modulus (Pa)

90 90
Complex modulus (Pa)
Phase angle (degress)

Phase angle (degress)

80 80

1000 70 1000 70

60 60

50 50
A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
100 40 100 40
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Reduced shear stress (Pa) Reduced shear stress (Pa)
(a) (b)
Fig. 7. Amplitude sweep of various polymerized binders at a reduced shear stress for binder sources. (a) A and (b) B.

concluded that the amplitude sweep test results may be dependent angle characteristics of the polymerized binders modified with or
on the binder source and polymer type tested in this study. without PPA are dependent on the base binder and polymer types
used to modify the binders.
3.7. Frequency sweep
3.8. Creep and creep recovery
A frequency sweep is a particularly useful test as it enables the
viscoelastic properties of a sample to be determined as a function The creep test is a very simple test in principle with the appli-
of timescale. During the frequency sweep, the frequency is varied cation of a constant stress value where the strain is measured accu-
while the amplitude of the deformation or alternatively the ampli- rately from the time of the application of the stress. Creep recovery
tude of the shear stress is kept constant [38]. The data at low fre- is that after the creep test, the stress can be removed and the sam-
quencies describes the behavior of the samples at slow changes ple’s recovery response is monitored with the time. Generally, if
of stress. In addition, the behavior at a fast load is expressed at high the material is ideal elastic and this elasticity has not been
frequencies. destroyed by the creep test, it may recoil back to its original posi-
The complex modulus and phase angle values regarding a tion. Otherwise, it will stay where it is [38].
reduced frequency at a temperature of 64 °C are shown in Fig. 8. In general, the polymerized asphalt binder is a temperature
The results indicate that the increased frequency results in an dependent viscoelastic material. Its creep and creep recovery
increase of complex modulus for all the modified binders. In gen- characteristics is generally based on test temperature and the
eral, approximate complex modulus values can be noted for the type of polymers used. As shown in Fig. 9, it can be shown that
binders modified with various polymers. However, Fig. 8 indicates creep compliance values of all binders rise very fast with a con-
that the phase angles were reduced as the frequency increases. In stant stress of 50 Pa at a temperature of 64 °C, but after removing
addition, obviously, the various modified binders have different the stress of 50 Pa, the creep compliance values generally keep
phase angles under a reduced frequency loading. There were no constant with some slight reductions for all binders tested in this
obvious trends could be observed regarding the phase angles of study. In Fig. 9(a), most of the modified binders have the same
the various polymers made with two base binders. It could be con- creep compliances except for AAP1 having the lowest one with
cluded, for the binders tested, the complex modulus and phase the highest elastic properties. However, in Fig. 9(b), the base
322 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323

100000 100 100000 100

90 90
Complex modulus (Pa)

Complex modulus (Pa)

Phase angle (degress)
10000 10000

Phase angle (degress)

80 80
1000 70 1000 70

100 60 60
100
50 50
10 10
A0 AP2 AP3 APP1 APP2 APP3 APP4 40 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4 40
A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
1 30 1 30
0.001 0.01 0.1 1 0.001 0.01 0.1 1
Reduced frequency (Hz) Reduced frequency (Hz)
(a) (b)
Fig. 8. Frequency sweep of various polymerized binders at reduced frequency for binder sources. (a) A and (b) B.

1 1
Creep compliance (1/pa)

Creep compliance (1/pa)

0.1 0.1

0.01 0.01

0.001 0.001

A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
0.0001 0.0001
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (second) Time (second)
(a) (b)
Fig. 9. Creep and creep recovery of various polymerized binders at a reduced time for binder sources. (a) A and (b) B.

binders show the highest creep compliance values, which exhibit 3.9. Stress relaxation
a relatively higher viscous than other modified binders. Therefore,
it could be concluded that the test results for the creep and creep During the stress relaxation test, the sample is subjected to a
recovery tests of the modified binders are dependent on the rapidly applied strain which is then held for the remainder of the
binder source and polymer type. No obvious trends were test. The relaxation behavior is studied by monitoring the steadily
found which polymer produces the best viscous or elastic decreasing value of shear stress. This test is useful to obtain viscos-
characteristics. ity and initial modulus over the decay time.

1000 1000
Relaxation spectrum (Pa)
Relaxation spetrum (Pa)

100 100

10 10

1 1

A0 AP2 AP3 APP1 APP2 APP3 APP4 B0 BP2 BP3 BPP1 BPP2 BPP3 BPP4
0.1 0.1
0.01 0.1 1 10 100 0.01 0.1 1 10 100
Time (second) Time (second)
(a) (b)
Fig. 10. Relaxation spectrums of various polymerized binders a reduced time for binder sources. (a) A and (b) B.
 F. Xiao et al. / Construction and Building Materials 64 (2014) 316–323
The test results shown in Fig. 10 illustrates that the relaxation
spectrums of all the binders reduce as the decay time increases
at a controlled strain of 10% and a test temperature of 64 °C. In
addition, these relaxation spectrums generally decrease slowly
when the decay time starts from 6–7th second. In Fig. 10, it can
be noted that two base binders have the lowest relaxation spec-
trums regardless of the decay time while the binders AP2 and
BP2 generally have the greatest relaxation spectrums after the
decay time increases to 3 s. In addition, compared to the relaxation
spectrums of the modified binders from two base binders
(Fig. 10(a) and (b)), it can be concluded that the binder source
and polymer type play a key role in determining the relaxation
characteristics of the modified binders.
4. Findings and conclusions
Based on the test results in this study, the following findings
and conclusions can be obtained in terms of the application of sev-
eral modified binders containing three polymers and recycled
crumb rubber modified with/without PPA:
1. As using polymers 2 and 3, a lower mixing and compac-
tion temperature could be employed to produce the
asphalt mixture and thus reducing the energy demand
during mixing and compaction procedure. Additionally,
10% 40 mesh rubberized binders with PPA had the high-
est viscosity values.
2. For the binders and the polymers tested, the 1% reduction
in polymers could be offset by using 0.5% PPA in the
matrix. Meanwhile, all modified binders from the base
binder A had slightly higher fail temperatures compared
to the base binder B in this study.
3. The results in this study indicated that the effects of alter-
native polymers and PPA on the G*/sin d values were
mainly based on the base binder source.
4. Phase angle values reported in this research could be
influenced by the nature of the polymer such as visco-
elastic, visco-plastic, and elastic–plastic properties at a
high performance temperature. In addition, it can be
found that the polymer type had an impact on the visco-
elastic characteristics of the modified binders.
5. It can be observed that, in this study, the behaviors of vis-
cometry, amplitude sweep, frequency sweep, creep and
creep recovery, and relaxation spectrums of all modified
binders were generally affected by polymer type, asphalt
source, and test temperature.
Acknowledgements
The research is partially supported by National Natural Science
Foundation of China (NSFC) (No. 51278060) and the Special Fund
for Basic Scientific Research of Central Colleges, Chang’an Univer-
sity (2013G1502022).
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