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Laboratory Investigation of Polymer Modified Bitumens

Ulf lsacsson and Xiaohu Lu

Roya! Institute ofTechnology, Division of Highway Engineering,


S100 44 Stockholm, Sweden

ABSTRACT

This paper deals with laboratory characterization of various pure and polymer
modified bitumens, in which five bitumens from four sources and six polymers of different
types were used. The effects of base bitumen and polymer type and content on compatibility,
storage stability, rheology and aging were investigated. The results indicated that

compatibility and storage stability of polymer modified binders were largely dependent on
polymer content and were influenced by the charncteristics of base bitumens and polymers.
Polymer modification increased the elastic responses and dynamic moduli of bitumens
at intermediate and high temperatures, and influenced complex and stiffness moduli at low
temperatures. It also reduced the temperature susceptibility and the glass transition and
limiting stiffness temperatures of birumens. The degree of the improvement generally
increased with polymer content, but varied with bitumen sourceJgrade and polymer type.
Artificial aging may cause oxidation of bitumen and degradation of polymer, and
consequently, change the microstructure and rheological properties of the modified binders.
These changes were largely influenced by polymer nature and content. Due to temperature
and frequency dependence, aging index is not a suitable parameter for characterization of
aging susceptibility of polymer modified binders.
The effectiveness of polymer modification as reflected by different testing parameters
may vary considerably. The usefulness of empirical test methods (e.g. penetration, softening
point and Fraass breaking point) for characterizing polymer modified bilwnens is discussed.
To predict significant benefit from polymer modification in practice, it is necessary to use
appropriate and fundamental pararnetm .

Keywords: polymer modified birumens, compatibility, storage stability, temperature


susceptibility, rheology, low-temperature creep, aging

INTRODUCTION

The behaviour of bitumens in service is governed by their initial engineering


properties as well as by the mechanical and environmental conditions to whieh they are
subjected. To enable pavements to accommodate increasing traffic intensity and axle loads in
varying climatic environments, high quality bilwnens are required. Special binders are also
needed for other applications, such as bridges, runways and slurry seals. These examples
suggest a potential area for bitumen modification.
The use of polymers as bitumen modifim is not a new phenomenon. As early as
1823, an English cork manufacturer was granted a patent for a binder containing natural
rubber. After the Second World War, synthetic polymer began to compete with natural rubber
as an additive in road bitumen. Over the years, an increased interest in bitumen modification
using different types of synlhelic polymers has been obselVed in many countries (1-5).

Despite numerous investigations in this area, polymer modified bitumens have not yet been
characterized unambiguously, because of the complex nature of bitumen and the complex
interaction between bitumen and polymer (1 , 6, 7).
This paper presents a laboratory investigation of a number of pure and polymer
modified bitumens. Five bitumens from four sources and six polymers of different types were
used. The main objective of the work is to study fundamental properties of the binders, which
include rheology, temperature susceptibility, compatibility, storage stability, low-temperature
creep responses and aging characteristics. The effects of bitumen source/grade and polymer
type and content on these properties are evaluated. Relationships between parameters of
dynamic mechanical analysis, creep test and conventional methods are also examined.

MATERIALS AND TEST METHODS


Materials
Five base bitumens, denoted A, B, C, 0 and E, were used in this study. They were
obtained from Venezuela (Laguna), Mexico, Saudi Arabia and Russia, respectively. The
physical properties of the bitumens are given in Table I.
Table 1 Physical Properties of Ibe Bitumens Used in This Study
C
BISo
Mexico

_.
0
BI80

E
885
BI80
Venezuela
Russia
Soo~,
18.
149
84
Penetration 5C, dmm
'81
41.0
42.8
Softening point C "J
46.0
44.3
3S4
21.
208
236
172
Viscosity (al 1]5C, mm2fs (e)
fraus breakin~ point, C to/
11
16
17
16
22
p,
-0.10
-1.00
-0.89
-0.09
1.29
-0.53
-0.57
-0.60
-0.59
-0.85
PVN
ASTM 0 5, ASl M0 3,6' (e) ASTM 021 0, IP 80,. Penetration mdex (8), Penetration
vi5(:osity number (9).
Bitumen code
Gn'"

8
BISo
Venezuela
113
]S.S

'" '"

,.' ' '

The polymers investigated are styrene-butadiene-styrene (SBS), styrene-ethylenebutylene-styrene (SEBS), ethylene vinyl acetate (EVA) and ethylene butyl acrylate (EBA)
copolymers. The SSS polyme~ used are powdered ](raton D-1I01 and Kraton D-1184,
supplied by the Shell Chemical Company. Kraton 0-1101 is a linear SBS polymer containing
31 percent styrene, and Kralon-1184 a branched polymer containing 30 percent styrene. The
SEBS polymer is Kralon G 1650 (Shell), which contains 29 percent styrene. The two EVA
copolymers used are Elvax 260 (EVA I) and EJvax 420 (EVA2), supplied by DuPont. Melt
indices (MI) of Elvax 260 and Elvax 420 are 6 and ISS, and their vinyl acetate contents are 2S
and IS percent, respectively. The EBA polymer was produced by Neste and supplied by
Nynas Petroiewn.
Polymer modified bitwnens (totally 36) were prepared using a low shear mixer (RW
20 DZM-P4, Janke & Kunkel) at ISOC and a speed of 125 rpm. The polymer contents used
were ], 6 and 9 percent by weight of blend. In preparation, 600 g of the bitumen was heated to
fluid condition and poured into a 2000 ml spherical flask . Upon reaching 175C, a preweighed
amount of polymer was added to the bitumen. Mixing was then continued at ISDe for two
hour.;. After completion, the polymer-bitumen was removed from the flask and divided into

small containers. The blend was cooled to room temperature, sealed with aluminium foil and
stored for further tesling. The process for preparing the modified binders exposed the bitumen
to high temperature and air for an cxtended lime, which led to hardening of the bitumen. For
the accurate evaluation of polymer effects, the base bitumens were also subjected to the same
treatment as the polymer-bitumen blends.
ConvtntionQ/ Bindu Tuts
The standard methods used include softening point (ASTM D 36), penetration (ASTM
D 5), kinematic viscosity (ASTM D 2170) and Fraass breaking point (IP 80).
Dynllmic Mechanical Analysis (DMA)
DMA with frequency sweeps (0. 1 to 100 radls) and temperature sweeps (-30 10 13Sq
was carried out using a Rheometries rheometer (RDA II). Parallel plates, gap 1.5 mm for l 8
mm and I mm for CD 25 nun, were used in a temperature range of )0 to SOC and 40 to 135C.
respectively. In temperature sweeps, when reducing the temperature, the nonnal force is kept
at zero by slightly reducing the gap. The gap was calibrated at the starling temperature. The
effect of the thennal expansion of the instrument is deducted during the increase of the
temperature. A sinusoidal strain was then applied by an actuator. The actual strain and torque
were measured and input to a computer for calculating various viscoelastic parameters such as
storage modulus (G,), loss modulus (G~), complex modulus (G') and phase angle (0).
Creep Tests Using a Bending Beam Rheometer (BBR)
Creep tests were carried out at four different temperatures (-35, 25, -15 and -IOC)
using a bending beam rheometer (BBR), Cannon Instrument Company. In tests, the binder
was heated to fluid condition, poured into the mold and then allowed to cool at room
temperature for about 90 minutes. The sample was cooled to approximately -SC for I minute
and demolded. After demolding, the sample beam (125 mm long, 12.5 mm wide and 6.25 mm
thick) was submerged in a constant temperature bath and kept at each test temperature
(starting at -35C) for 30 minutes. A constant load of 100 g was then applied to the rectangular
beam of the binder which was supported at both ends by stainless sleel half-rounds (102 mm
apart), and the deflection of center point was measured continuously. Creep stiffness (5') and
creep rate (m) of the binders were detennined at several loading times ranging from 8 to 240
seconds.
Thin Layer Chromatography with Flame Ionization Detector (TLC-FID)
In TLCFID, the sample to be analyzed is dissolved in a solvent and SPOiled at one end
of a chromarod (quartz rod coated with a thin layer of sintered silica or alumina). The rods are
then developed with suitable solvents, after which the solvents are removed by heating. The
rods are scanned at a chosen speed through a hydrogen flame, and the separated fractions
successively vaporizedipyrolYled. The FlO signals from each fraction are amplified and
recorded as separate peaks. In this study, 8 commercial equipment, an latroscan MK5
analyzer (latron Laboratories Inc., Tokyo, Japan), was used. 2 percent (w/v) solutions of
bitumens were prepared in dichloromethane, and [ IJI sample solution spotted on chrnmarods
using a spotter. The separation of bitumen into four generic fractions (saturates, aromatics,
resins and asphaltenes) was perfonned by a three-stage development using n-heptane, toluene
and dichloromethanelmethanol (9515 by volume), respectively.
Gel Permeation Chromatography (GPC)
[n GPC, molecules that differ in size are separated by passing the sample through a
stationary phase consisting of porous cross-linked polymeric get. The pores of the gel exclude

,
molecules larger than a certain critical size, while smaller molecules can permeate the gel
slruCtun~ by diffusion. The sample components art eluted in order of decreasing size or
molecular weight. The GPC systems used were three ultra-styrage! columns arranged in the
order of pore size (100, 500 and 500A) with a refractive index detector (Water 410). In the
analysis, 5 percent binder solutions were prepared in tetrahydrofuran (THF). A broad
molecular weight polystyrene standard was used 10 calibrate the instrument.

Fluorescence Microscopy
Fluorescence microscopy was used to study morphology (compatibility) of polymer
modified binders. The modified binder was illuminated using a blue light for excitation and
the fluorescent yellow light re-<:mitted by the swollen polymer phase was observed using an
optical microscope. The instrument (Leitz, LABORLUX II) was equipped with a Polaroid
camera and a blue filter system. The wavelength of excitation is in the range 390 to 490 MI.
Squashed slides of modified binders were prepared using very small amounts of the heated
sample and viewed under the microscope with a magnification of250 at room temperature.
EXPERIMENTAL RESULTS AND ANALYSIS
Cht mical Characluization of Btut BitumtllS
The generic fractions of the base bitwnens were detennined using TLC-FlD. The
typical TLC-FID chromatograms of bitumens art shown in Figure I. Four peaks are
recognized as saturates, aromatics, resins and asphaJtenes, respectively. The percent generic
fractions of the bitumens are detennined by area normalization. The results obtained (Table 2)
indicate that the five base bitumens vary in their chemic.aJ composition. There is little
difference between the four generic fractions of bitumens C (Mexico 8180) and D (Saudi
Arabia 81 80), resulting in the same value of the colloidal instability index I,. Bitumens A and
8 show the same It value in spite of their differences in generic fractions. This similarity may
be attributable to the same source for bitumens A and B. Bitumen E (Russian) possesses the
highest saturates and the lowest aromatics, and consequently, the highest Ie value.

_.

"' _ f

!
;

.... /

ru:

Figurt 1 Chromatographic Analysis or Base BitumeDs Bind E

GPC

,
The weight average (M... ) and number average (M.) molecular weights as well as
polydispmity (MJM.) of the base bitumens were detennined by means of OPC. Figure I
gives examples of bitumen GPe chromatograms. A small difference was observed between
the ope data of bitumens C and 0, which correlates well with the results obtained using
TLC-FID. Compared to other bitumens, bitumen E contains more of the larger molecular
species; the fraction of molecules with M... over 2500 glmole is 18 percent. This bitumen
also shows the widest molecular weight distribution (polydispersity 2.49) of the five
bitumens.
Table 2 Chemieal Charad eristits of Bue Bitumens
Bitumen Code
Saturates %
Aromatics %
Resins %
Asphahenes (%
Molecular weight, M.
Molccular weight. M.
Polydispmiry (MJM.)
l

Fraction with Mw >2.Sxl0 (%)

11.3
54.7
18.7
J 5.4
650
])00

13.0
56.4
17.3

1.1l6
IJ

C
10.4
64.8
III
11.1

750

10.9
63.6
14.8
10.7
140

E
16.9
51.1
18.3
J]J
720

])00

1400

1300

1800

2.08

1.84
11

1.80

2.49

II

18

III
600

11

Conventional Hindu ruts


The test results obtained using conventional methods are presented in Table 3. As
expected. polymer modification caused an increase in binder consistency (decrease in
penetration and increase in kinematic viscosity and softening point). The consistency changes
may increase with polymer content, but vary with bitumen source/grade and polymer type.
For a given polymer content, the bitumens were observed to be less susceptible to EVA
addition compared to the other polymers. However, in some cases, changes in the consistency
as measured by those conventional parameters were not consistent.
Polymer modification also reduced Fraass breaking point of the binders. The reduction
was comparably small (a few degree). For most of the modified binders, Fraass breaking point
did not decrease proportionally with increasing polymer content. Since the Fraass test applies
a high strain rate to binder samples, the actual differeoce in the fracture properties of the base
and modified bitumens may be reduced by this test. This means that Fraass breaking point
probably cannot accurately relate polymer perfonnance to low temperature properties of
binders.

Tahle 3 Binder Test Re.sults Obtained Using Conventional Methods


Binder

Viscosity

@mc.
mm 1/s

Bitumen A
A + 3Y, linearSBS
A + W. linear SBS
A + 9% linear SSS
A + 6!-', branched SSS
A + 6Y. SEBS
A + 6Y. EVAI
A "'6% EVA2
A +6% EBA
Bitumen B
B + 3% linear SBS
B + 6Y, linear SBS
B+9Y. linearSBS
B + 6Y, branched SSS
B+ J!/tSE8S
8 + 6Y, SE8S
B +9Y. SEBS
8+3%EVA I
8 +6%EVAI
B+ 9%EVAI
B+3% EVA2
B+6%EVA2
B+9%EVA2
B+)%EBA
8 +6%EBA
8 +9'hIEBA

Bitumen C

C + )% linear SSS
C + 6% linear SBS
C + 9% linear SBS
C + 6% branched SBS
C+6%SEBS
C+6%EVAI
C+6%EVA2
C + 6Y. ESA
Bitumen D
D + 6% linear SBS
D + 6% branched SBS
Bimmen E
E+ 6% linear SBS
E + 6Y. branched SSS

Penelrati()l'l Softening
poin!, C

370

77

64

1080
2020
224

PI

PVN

47.3
52.1
71.5
84.0
82.3
71.8

."
."."

59.5

1'
12

-0.86
-0.1 1
3.25
4.08
459
2.55
1.12

-0.64
0.32
1.23
2.00
2. 12
1.38
1.24
0.49

dmm

821
2020
4780
3830
2740

1860

Fraass
breaking
I ooin!, C

@25C.

49

37
50
.0
54
54
44

63.5
74.8

165

39.5

506
1060

III

3350

70

46
141
97
76
129
96

55J
17.2
85.1
82.5
58.0
66.8
78.S
42.2
53.4
59.8
46.8
57.4

2390
577
1630
3950

469
1140
2970

342
602

84
III
61

1070
472
1180

77

64.4

121

3040
237
461

61
151
120

51.6
70.2
77.8
41.5
51.2
77.2
85J
85.4
70.5
57.7
59.8
7J.l
41 0
75.2
84.0
44.0
75.2
81.5

])50
3450

3890
1490
940
584
1080

82

.
.

67
89
67
100

250

110

1220
4360

80
77

187

166

1640
3220

70

69

."

12

16

Il

."

16

17
19
18
19
18

1.90
3.25
-1.l0
2.70
5.61
5.95
6.14
lOS
2.84

ll

3.90

20

.(l.61
1.48
2.15

."
."
."
."

19

20

20

18

16
18
20
20

."."
."

0.64
2.39
3.10
1.80
4.33
4.58
.{l.44
1.60
5.61
5.81
6.12
3.74

1.09
.Q.55
0.40
1.10
2.44
2.24
0.48
L22
2.05
0.48

IJ'
2.40
-0.16
0.35
0.9)
0.28
1.16
2.10
-0.51
0.23
1.45
2.42

3.06
1.22

2.60

1.09

21

2.62

20
1 6
19
19

4.06

0.20
0.85
-0.66
1.17
2.98
-0.85
1.4\
2.37

ll

26

-0.6 1

5.00
6.12
0.72
4.58
5.52

25
The but bitumens have been subJet!ed to the same treatment IS the polymer.bitumen blends .

Compatibility and Storage Sillbilily


Fluorescence Microscopy Studies Due to the chemical dissimilarity (e.g. differences in
molecular weight, polarity and structure) between bitumen and polymer, most of the modified
binders obtained by mechanical mixing are thermodynamically immiscible. In describing
such systems, the term ~compati bility" is often used. Compatibility can be defined as the slate
of dispersion between two dissimilar components. The property was studied using
fluorescence microscopy by characterizing the nature of the continuous phase and the fineness
of the dispersion of the discontinuous phase. At room temperature and a magnification of 250,
the modified binders may show either a continuous bitumen phase with dispersed polymer
particles or a continuous polymer phase with dispersed birumen globules, or two interlocked
continuous phases. as illustrated in Figure 2.

'

'

~.

I .
o

...

BilUmen B + 9% SEBS

'

Bitumen B + 3% EVA]

. . .. '" .
~tr .
,
iI'

8itwnen 8 + 3% SEaS

Bitumen B + 9'10 EVA]

Figure 2 Fluorescence Photomicrognilphs or Polymer Modified Bitumens

The morphology (compatibility) is the result of the mutual effect of polymer and
bitumen, and consequently is influenced by bitumen composition and polymer nature and
content. In general, at a low polymer content, the small polymer spheres swollen by bitumen
compatible fractions (e.g. aromatic oils) are spread homogeneously in a continuous bitumen
phase. Compared with 3 percent elastomer (SBS and SEBS) modified binders, those
containing thermoplastics (EVA and EBA) of the same polymer conlent revealed much finer
dispersion of the polymer. Belter dispersion of the polymers was also observed for the
modified binders prepared from the bitumens with higher aromatic and lower asphaJtenc
contents. By increasing polymer content, a continuous polymer phase may be obtained
(Figure 2). The minimum pcrcentagl! of polymer to ensure the fonnation of its continuous
phasc depends to a great extent on the base bitumen and the polymer itself. In most cases,


appearance of a continuous polymer structure was observed to begin a\ a polymer content of
about 6 percent.
The morphology should also be influenced by testing temperature, This means that the
morphology of polymer modified binders observed at ambient temperature does not
necessarily reflect thai at high temperatures.
Phase Separalion Polymer modified binders may separate inlo JXllymcNich and
asphaltenerich pbases during hot storage. The phase separation has been CQnfirmcd by
tluorescence micrographs and Fourier Transform Infrared Spectroscopy (FTJR) of the
modified binders before and after lube storage al 180C for three days (\ 0). The two phases
differ widely in their rheological properties and chemical constitutions. In this study, the
logarithm of the ratio of complex modulus (DMA al 25C) of the asphaltenerich phase to that
of the JXI1ymer-rich phase is defined as the separation index, I" and is used to evaluate the
slorage stability of the modified binders (Figure 3),
\.ooE+09 r - - - - - - - - - - - - - - - - ,
, l.ooE+08

--Bilumen A + 6% lOB'" bc:fln stonge

- . _. Top sroion iIfIa storage


Bottom sectiOll after $Iorage

l.ooE+07

.. . .. .. -. ..

. ...

e... LOOE+06 I~~~.~~.q~._.;. ~. -.~._.::::::l


_.- "
~ l.ooE+05
~

LooE+il4

.. I,

_.-'

- .-

l.ooE+{I3

I, " Jog/O(bonom section),IG' {top section)]

I.OOE+{I2
I.00E+{I1 L_~~=_~~~~~~~....J

l.ooE-01

l.ooE+OO

I.(IOE+OI

l.ooE+{I2

Figure J Complex Modulus as a Function of Frequency for a EBA Modified Bitumen


berore and after Storage atl80C ror Three Days

The investigation indicates that the storage stability decreases with increasing polymer
content. For the modified binders with a low content of polymer (3 percent), almost no phase
separation (I, close to 0) was observed. The storage stability is also influenced by
characteristics of the base bitumen and the polymer. Higher content of aromatics and/or lower
content of asphaltenes are observed to be favourable with regard to storage stability, as
illustrated in Figure 4. Among all the modified binders prepared, the modified binders with
EBA display the lowest storage stability. For the elastomer (SBS and SEBS) modified
binders, those containing branched SBS show the lowest storage stability, For the EVA
modified binders, better storage stability is observed for those containing the polymer with
lower VA content and higher Mr.
The storage stability wa~ also assessed by softening point. Unfortunately, the
conventional evaluation did not show any correlation with DMA method. This implies that
different conclusions could be drawn from the storage stability if using different evaluation
methods.

Since many polymer modified bitumens display a tendency towards phase separation,
some agitation is recommended during the storage of hoI blends. However, such a measure
should not be taken wilhoullimil and at the expense of the oxidative degradation of polymers.

2' ,-----__________,

2' ,-------~~~-.
O''IIINIrSES

,.

2.'

,
o!

;
!
!

L~

H O

__~~__~____'

50.0

SSO

600

6S 0

" ''''_sas

5 LO

'.o
,
00

O' nlftMS8S

. n~SBS

700


., o ,o

"..

...

'---~-----------'

LO.O

,,.

CMI..L" ",.",,"II..n 1% . , ",

Figure 4 Relationship between the SeparttioD Index (at 1 radls) orSBS Modifi ed
Binder! lod Bitumen Composition

Comparison oj Storage Stability and CompatibiUry In general, storage stability of


polymer modified binders may be associated with the compatibility between bilwnen and
polymer. A quaJitalive comparison between separation index and fluorescence
photomicrograph indicates that, at a given polymer conlenl, the modified binders showing a
finer polymer dispersion generally exhibit less phase separation during static hot storage. In
this case, the separation index (storage stability) can be regarded as a measurement of the
compatibility of polymer modified binders. However, high phase separation was observed in
modified binders with high polymer content showing a continuous polymer phase in their
microstructures; the modified binders with such desirable microstructures cannot be judged as
incompatible systems. Obviously, the compatibility of polymer modified binders defined in
different ways or evaluated by different methods is not necessarily consistent. This also
suggests that using only one method for determination of the degree of compatibility of
polymer modified binders could be misleading.
DynIJmic Rhe%gic4/ Propertiu
Dynamic rheological properties refer to responses of a material to periodically varying
strains or stresses (11). ln DMA, the ratio of the peak: stress to the peak strain is defined as the
complex modulus (G ), which is a measure of the overall resistance to deformation of a
material. lbe in-phase and out-Qf-phase components of G are defined as the storage modulus
(G' ) and the loss modulus (G-), respectively. Storage modulus is proportional to the stress
in-phase with the strain and provides information on the elastic responses of a material, while
loss modulus is proportional to the stress out-of-phase with the strain and is associated with
viscous effects. The phase difference between the stress and strain in an oscillatory
deformation is defined as phase angle (li). This parameter is a measure of the viscoelastic
character of the material. A purely viscous liquid and an ideal elastic solid demonstrate li of
90" and 0, respectively. The viscoelastic parameters of bitumens are functions of temperature
and frequency, which may be modified by the addition of polymers.

Phase Angle and Viscoelastic Properties Phase angle as a function of temperature was
detennined at I radfs over a temperature range from 30 to 135C. Examples are gh'en in
Figure 5. It is evident that polymer modification increases the elastic response (decreased
phase angle) of bitumens. The effectiveness of polymer modification is largely dependent on
temperature, and is innuenced by bitumen source/grade and polymer type and content. As the
temperature exceeds about 2OC, the polymers begin significantly to improve the elasticity of
the modified binders. This can be attributed to the viscosity of the mobile bitumen
components, which is low enough to allow the elastic network of the polymer to innuence the
mechanical properties of the modified binders. With increasing temperature, the phase angle
may pass through a maximum and then through a minimum, or show a smoothly increasing
function of temperature, depending on base bitumen and polymer nature and content (Figure
5). The phase angle maximum and minimum correspond to the transition and plateau regions
of storage modulus, respectively, which may be indicative of a continuoll5 IX'lymer network.

--,......
------'
........ -

I .. . . . .

I ......

_ _ c .. _ _

I
I

~-

I." ' "

'.01(...
I .

'"

I .

'"

--,-- .

!"
j"

,."

,-~

l.,M

, " ,. ,

'-"'

-_....__ _ c . .. _ _

--,

. , " ,.

ON

,.

' -'"

'.oK ...
l.oK"
I. " "

1 c.....

,i,

--<... _-

"
,!
,

UK'"
uK'"
uK.f)

...

i, ,
,-,

' ....M

I .. . . . .

_....-

...._ _ c ... _

.,

" ra
T...... __

,.

ON

,.

.,
~

_ _ c ...
_ _ c .. ",-

.,

" '" ,
ra
T..... ~ ....

Figure 5 Storage Modulus and Phase Angle as a Function ofTemperatun at 1 radls

In this investigation, the contribution of storage modulus (G') to complex modulus


(G-) is arbitrarily considered to be negligible as a> 75~, since in this case, G' is less than 27%
of G", and JG 1'" J G G-' '" G- . The temperature above which the phase angle is greater
than 75 is denoted T11' , and used to quantitatively compare the clastic response of the
binders. II was observed thai polymer modification increased T15' of the binders. and the
improvement may increase with polymer content. The improvement is also dependent on the
base bitumen and polymer Iype. The innuence of the polymers tested may be ranked as
branched SBS, SEBS/linear sas. EBA, EV A2 and EVA I, branched sas being the most
t

II

effective. This temperature is observed 10 statistically correlate with the softening point, as
illustrated in Figw-e 6. For all the binders studied, the correlation coefficient obtaioed is 0.95.
However, al the softening point, all the base bitumens are purely viscous, as indicated by
phase angles of 90, while the modified binders still display considerable elasticity. This
observation suggests that the softening point is related to dilTerent properties when applied to
pun: and polymer modified bitumens.

" "

JO

.,
Soflnln~

70

80

90

100

Point [OC1

Figure 6 T7S. as a FUDdioD of Softening Point

Polymer modification also influences the frequency dependence of phase angle, as


illustrated in Figure 7. The improved viscoelastic properties of polymer modified binders can
be observed over a wide frequency range. Although the frequency dependence of phase angle
is similar for the base bitumens, significant differences can be observed among the modified
binders. This may result from different degrees of molecular interactions between base
bitumens and polymers.

.,..

"

-_-_.
.... -_.......

io

L.

~_I

._10"

.....

,
"

--.
.._c ... ..
..._ c ... ....

~- <

.... ....

~_ c

... _

._."oM!

, oK...

Figure 7 Effect of Polymer Modification on .'requeney Dependenee of Phase Angle at


60C

Dynamic Moduli and High Temperature Properties As indicated in Figure 5, polymer


modified binders exhibit four regions in the plots of storage modulus versus temperature:
glassy, transition, plateau, and terminal or flow, similar to those for polymer materials. These
regions can be associated qual itatively with different kinds of molecular responses (12).
Different degrees of prominence may be observed in the four regions, depending on the
chemical and physical nature (e.g. molecular weight, microstructure and network density) of
the binders. Of these regions, the plateau corresponds to the phase angle minimum and may
indicate the presence of polymer networks (cross-links and entanglements) and/or polymer
crystallinity in the modified binders. For the base bitumens and modified binders with a low
content of polymer, the plots display only three regions but not the plateau. In this case, the
transition goes directly from the glassy region to the terminal region, and correspondingly, no
phase angle maximum and minimum occur.
For optimal performance at elevated temperatures, the selected polymer should be able
to form a continuous elastic network when dissolved/dispersed in the bitumen. This is
determined by several factors such as the chemical and physical properties of the polymer and
the bitumen, polymer content and the thermal/mechanical history of the blend. For example,
for the modified binders containing a low content of polymer (e.g. 3 percent) and the
modified binders with bitumen E, no apparent phase angle minima are observed (Figure 5).
Correspondingly, the plateau region of these modified binders is not easily recognized,
indicating that there is no, or a very weak, polymer network. Compared with thermoplastics
(EVA and EBA), elastomers (SBS and SEBS) may result in a more pronounced plateau
region. Due to the increased elastic response (increased storage modulus and decreased phase
angle) and increased complex modulus, the SHRP rutting parameter, Gt/sinS, is improved.
The magnitude of the increase is dependent on the bitumen source/grade and polymer content
and type. It is also highly dependent on testing conditions (e.g. frequency and temperature), as
ilhlslrated in Figure 8.
I.fllt..,

r - - -- - - -- -,

-_.

"I~[WI.,

... _
..... f'/>J
_ _ A ... ..

I.t_ t!

~IO n~---------

u N:>ti

T UtE ...

_ _ A ........

_ _

I .

I.M'"

, [ '"
1 [ '"

1.['"
1.1IK41

, __"

1.101;'"

f,..,._,I"....)

UOE" ,

L~~

.H

_ _

~~~

1.
"
"
T . .,.....

"

_ _~
,.

1H

'"

"1'Cl

Figure 8 C/sinS as a Fundion of Frequency (at 60C) and Temperature (It 1 rad/s)

Since in European countries, the contribution of the bitumen to the susceptibility of


permanent deformation is usually assessed by testing the softening point, a comparison has
been made between the SHRP rulling parameter and softening point (13). It was observed that
no significant linear relationship existed between those two parameters if all the binders tested
were analyzed together. However, such linear relationships could be established if modified
bindern produced from one and the same bitumen were examined, as indicated in Figure 9.
The correlation coefficients of the three regression lines are in the range 0.84 to 0.95.

13

15

r---------------------,

10

R'" O.U

R" o.as

R " O.93

35

75

65

55

95

85

105

Sobnln" Poin t reI

Figure 9 Relationship between G"sino (at 10 radls and 60C) and Softening Point

BLACK Diagram Polymer modification of bitumen rheology is also identified in


Figure 10, where BLACK diagrams (complex modulus as a function of phase angle) are
displayed. These diagrams were generated with temperature sweeps (from )0 to 135C) al 1
radfs. Evidenliy, al a low polymer conlent (3 percent in this study), the effect of polymer
modification appears insignificant, and the behaviour of the modified binders remains close to
thaI of the base bitumens. After modification with a sufficiently high polymer content (t?: 6
percent), the binders change fundamentally in their rheological behaviour, as indicated by a
substantial decrease in phase angle (8 substantial increase in the elastic response) with
decreasing complex modulus. In these cases, the rheological response of the modified binders
is mainly imposed by the viscoelastic properties of the polymers, and those of the bitumens
waning considerably. These observations imply that the rheological properties of polymer
modified binders are governed by their continuous phase.
,~~

,--,
,-~

~ 1:- '

ltllK>M

.i

k
~

UII[~

it. ..., r-

{I.."

At...,f--

,-

1.l1li;"

:=

'f--

1.l1li;...

,
I.

,.II1II:'"

"

-~

iR

f .. _oM

i '..

'\

U H

-_.

l: UIK....

{ '.111:'"

1.lII:olII

I -

"' ......

'.ME

,,,&4,

..... 1...

"

-_..
-......
... _
..... \1...
_ _ ..."tv ...

1.11('"

,.

Figure 10 Complex Modulus as a Function of Ph an Angle

"

"

"

"
The rheological changes are also influenced by the characteristics of the bitumens and
the polymers. For the modified binders with SEBS or SSS, complex modulus deviales from
that of the base bitumens a\ phase angles as low as lit' (corresponding to binder glassy slale
al low temperatures). However. the curves of the modified binders with EVA and EBA are
almost the same as those of the base bitumens at points where 0 5 500 and Gt ~ 10 MPa.
These differences suggest that SEBS and sas may improve bitumen rheology over a wide

temperature range, while EVA and EBA show their effect mainly at high temperatures.
Low-Tempuafure Propertits
For a flexible pavement, one of the failure modes is low-temperature cracking. This
occurs when the Ulenna] stress induced at low temperatures exceeds the tensile strength of the
asphalt pavement. Low-temperature cracking can be a serious problem in cold areas. To
reduce the risk of crack.ing, the binder should have good flexibility (low stiffness and complex
modulus and high ability of stress relaxation) at the lowest pavement temperature. In this
paper, the influence of polymer modification on the low.temperature properties of bitumens is
studied using DMA and BBR.
DMA CharaclerizaliQn The DMA observations indicate that, in low temperature
regions (below OC), all the modified binders show a lower complex modulus titan the
corresponding base bitumens. However, the glassy modulus G, of the binders is close to I
GPa and insignificantly influenced by polymer modification. This value of glassy modulus
reflects the rigidity of the carbon hydrogen bonds as the bitwnens reach their minimum
thennodynamic equilibrium voiwne {i4}.
B tllalllU Codt

-j

..

iJ JO
-15

":

20

..<

-30

;; 25

-35
-40

.bo.sc ~il"",."
O~6%SEBS

9 6% Ii,",,,, sas
Q '6%EVAI

6% br,"ciltd SBS
1I'!I' 6%EVA2

1iI ~6%EBA

-45

Figurt II Erreet of Polymer Type on tbe DMA Glau Transition Temperature

In quantitatively characterizing the low temperature properties of bitumen, one of the


parameters often used is the glass transition temperature, T,. In this study, detennination ofT,
of the binders was initially perfonned using differential scanning calorimetry (OSC).
Unfortunately, relevant results were not obtained. Most of the binders displayed a wide
transition region in DSC, and T, was difficult to recognize. The glass transition temperature
was then determined from peak loss modulus at I radls using DMA. In general, the modified
hinders demonstrate lower T, compared to the base bitumens. However, the effect of 3

"
percent polymer on binder TI is very small, If 6 or 9 percent polymer is added, the range of
reduction in T, is between 10 and 20C for the elastomer (SSS and SEBS) modifi ed binders,
but only a few degree for those containing lhennoplaslics (EVA and EBA), ils illustrated in
Figure 11. It should be noted that values of the DMA TI art frequency dependent and will
also be affected by heating rate at the temperature sweep. To allow meaningful comparisons,

careful control of lest conditions is necessary.


Low-Tempera/ure Creep Response In the SHRP binder speeification, a limited creep
stiffuess (S) and logarithmic creep rate (m-value, which is related to binder stress relaxation
ability) have been used as performancebased criteria at low temperatures (15). The

measurements of low-temperatUIC creep responses are conducted at JOe above the minimum
pavement design temperature. In this study, the SHRP bending beam rheometer was
employed to detennine binder low-temperature creep responses at six different loading times
(8, 15, 30, 60, 120 and 240 sec) and four different temperatures (-35, -25, -15 and -IOC). The
stiffiless of the binder is calculated from the dimensions of the beam, the applied load and the
measured deflection. Typical examples of creep response are shown in Figure 12, in which
the influence of polymer modification is clearly illustrated .

_
--_

...,..._.
..... .. "'...
.........-

r:-c:---,----- ---,
i
1'"

...

_ _ 1 .... -

_---- -

--_
-_ ".--

",,--------,
...,..._.........
........

..II
A

L_~_~~~~_---'

51

100

151

LoM,..T I-!

180

150

Figure 12 Creep Responses orthe Base Ind SEOS Modified Bitumen 0 at -2SC

Table 4 indicates that polymer modified binders generally display a lower creep
stiffness than the corresponding base bitumen, especially at temperatures lower than 15e.
The improvement increases with polymer content, but varies with the base bitumen and
polymer type. At 35C and for a given polymer content, the modified binders containing
elastomers (SSS and SEBS) show a higher reduction in creep stiffness than those with
thermoplastics (EVA and EBA). However, al the other three low temperatures, varying
changes are observed in the creep stiffness. Some modified binders (e.g. bitumens A and B
modified with SEBS) even show an increased creep stiffness at 15C. Moreover, the usc of a
softer bitumen seems favourable for reducing creep stiffness (cf. B85 and BI80). As a result
of the reduced creep stiffness, the modified binders exhibit a lower limiting temperature (by
definition, the temperature at 300 MPa creep stiffiless) than the base bitumens. However,
degree of the improvement is comparatively low. As regards the effect of polymer
modification on binder stress retaxation ability, both increased and decreased mvalues are
observed, depending on the testing temperature and loading time. Therefore, no definite
conclusions could be drawn on this mailer.

Table 4 Cmp Stiffness and m-value of the Binders at a Loading Time of 60 sec anti
Dirrerent Temperatures
Binder
Bitumen A
A + W.linear sas
A+6t.linearSBS
A+9%linearSaS
A + 60/. branched SBS
A+6%SEBS
A+6%EVAI
A+6%EVA2
A+6%EBA
Bitumen B
B + 3% linear SBS
B + 6% linear sas
B + 9010 linear SBS
B + 6% branclted SSS
B + 3% SEllS
B + 6';' SEBS
B + 9";' SEaS
S+3%EVAI
B+6%EVAI
S +9%EVAI
B+3%EVA2
B +6%EVA2
B+9%EVA2
B+3%EBA
B +6%ESA
B +9%EBA
Bitumen C
C + 3% linear sas
C + 6% linear sas
C + 9%linear SBS
C + 6% branched sas
C+6%SEBS
C+6%EVAI
C+6%EVA2
C+6%EBA
Bitumen D
D + 6% linear SSS
0+ 6% branched sas
Bitumen E
E+ 6% linear sas
E + 6% branched SBS

Cree Stiffness MPa


-2SC
-[SC

-35C
1590
1320
884
682
"'7
1140
1560
2000
1620
1560
1080
921
664

180
16 1
54
63
55

789
680
482
550
484
684
624
790
656
487
400
371

56
63

"

304

42J

1IS0

80

329
230
350
326
302
3"
366
265
J83
298
234
4J7

774
575

185
152
I2J

161
146
195
III

60
40

36
31
50
48
27

45
J8
27
99

!OS
95
91
81
97
89
94

60
144
117
117
24
40

42

J72

J7I

1360

0.64

1200

0.6[
0.58
0.56
0.54
0.59
0.58
0.52
0.54
0.49
0.45
0.42
0.40
0.43
0.42
0.47
0.44
0.35
0.46
0.42
0.38
0.49
0.39
0.34

1210
1190
1240
1140
1250
1160
1020

931
812

295

491

257

628

328

686
765
958
1040

JJJ
J57

411
167
481
l77

354
151
176
185

m-va[ue
-ISC
0.45
0.43
0.40
OJ5
0.38
0.38
0.47
0.42
0.41
0.61
0.54
0.52
0.45
0.49
0.54
0.41
0.38

875

'"

796
"4
516
366
446

-2SC
0.26
0.24
0.23
0.2 1
0.20
0.20
0.30
0.25
0.26
0.35
0.32
OJO
0.29
OJI
0.33
0.28
0.25
0.41
0.42
0.46
0.40
0.38
0.42
0.37
OJ8
0.42
0.32
0.29
0.27
0.29
0.29
0.28

OJ!
0.32
0.16
0.29
0.27
0.26
0.38
0.35
0.30

-35C
0.09
0.12
0.12
0.11
0.13
0.11
0.13
0.12
0.13
0.15
0.13
0.15
0.16
0.17
0.1 5
0.[9
0.21
0.17
0.19
0.20
0.16
0.18
0.19
0.18
0.19
0.21
0.19
0.20
0.18
0.19
0.20
0.1 8
0.19
0.19
0.20
0.16
0.17
0.18
0.30
0.27
0.26

11

CorreIa/ions between Different Low-Tempera/ure Parameters Relationships between


different low-temperature parameters were examined. It was observed thai creep stiffness may
statistically (risk level 5 percent) correlate with complex modulus at low temperatures. AI
25C, the correlation coefficient R is 0.80 for the creep stiffness at 8 sec and the tDmplex
modulus at 1 radls. In addition, for all the binders tested, statistically significant relationships
exist between the limiting stiffness temperature and Fraass breaking point (R = 0.86), and
between the limiting stiffness temperature and DMA T, (R .. 0.62). The [ow conelation
coefficient is due to the modified binders containing II high content (6 and 9 percent) of
elastomers, which show significant differences in the degree of modification with respect to
those parameters.
Tempua(ure SlISctptibility
Temperature susceptibility of the binders is one of the important parameters
detennining asphalt perfonnance in road service. Asphalt mixtures containing the binders
with lower temperature susceptibility should be more resistant to cracking and rutting at low
and high temperatures, respectively. Temperature susceptibility is usually defined as the
change in binder properties as a function of temperature. Since binder properties may be
characterized by means of various parameters, different approaches have been proposed to
evaluate temperature susceptibility. Traditionally, temperature susceptibility is quantified
through consistency measurements made at two different temperatures. Two classical
methods are the Penetration Index, PI, and Penetration Viscosity Nwnber, PYN. Lower values
of PI and PVN indicate higher temperature susceptibility. The results obtained (Table 3) show
that the classical parameters are improved by polymer modification. For all the binders, PI
may statistically correlate with PVN (R = O.S3). However, the temperature susceptibility of
binders may be ranked differently by PI and PVN. As mentioned earier, tests of penetration
and softening point are empirical and, in principle, only valid for unmodified bitwnens.
Consequently, conventional temperature susceptibility parameters such as PI and llYN are
probably not relevant indicators in the case of polymer modified binders.
In DMA, the temperature susceptibility of binders may be evaluated by measurements
of various viscous and elastic parameters at different temperatures and frequencies.
Observations described earier indicate that polymers modify the rheology of bitwnen.
Through polymer network and/or crystallinity, the modified binders become more elastic and
less temperature susceptible over the nonnal service temperature range compared 10 the base
bitumens (Figure S). AI high temperaltU"es, however, the polymer modified binders are likely
to cxhibit temperature susceptibility that is the same as, or slightly higher than, thaI of the
base bitumens. This is a result of the weakening and dissociation of the polystyrene domains
(SSS and SEBS) or the melting of Ihe crystalline portions (packed polymer segments of EVA
and EBA). To perfonn an evaluation similar 10 viscosity temperature susceptibility (VTS)
(16), the double logarithm of complex modulus, complex viscosity (,, ' .. O'/ro) and dynamic
viscosity (,,' = GM/Il) was plotted against the logarithm of temperature in K for both
unmodified and modified binders. Unfortunately, these plots were not straight lines over a
wide temperature range, and the slope (temperature susceptibility) changed with the
temperature range being considered. This means that temperature susceptibility cannot be
evaluated as a single-valued parameter such as VTS.
Aging Properties
Aging of the binders was perfonned using the Thin Film Ovcn Test (TFOT, ASTM D
1754) and the Rolling Thin Film Oven Test (RTFOT, ASTM D 2872), respectively.
Aluminium pans (TFOD and glass containers (RTFOD were heated to 160C before loading
the sample. The sample holders were kept in an oven at 160C for about IS minutes (RTFOT

"
glass containers in horizontal position) and then aged according 10 the standardized
procedures: 163C and 75 minutes for RITOr and, 163C and 5 hours for TFOT, The aged
binders were evaluated by measuring their rheological properties.
Figure I) reveals the viscoelastic changes oflhe binders after aging. AI the frequency
studied ( I radls), aging increases the complex modulus of the base bitumens. However, the
innuence of aging on polymer modified binders is temperature dependent. For the base
bitumens and modified binders with 3 percent SSS, as well as those containing
thermoplastics, the elastic response was slightly increased by aging, as indicated by a small
decrease in phase angle in a temperature range of 0 10 about 7OC. In contrast, when aging is
performed on the modified binders with 6 or 9 percent SBS and SEBS, large increases in
phase angle were observed at high temperatures, and consequently, the depth of the phase:
angle minimum is reduced, which would imply polymer network damage.

-_
-_-_.................. .._-.... .--

....

_ .1fOT -_, ,..

, -~

, . .. f!

.... "101 _ _

-- ,

f 'lIl*
; '1Il>f)

J'II(I('I)O
t ,lIlotl

,"

,,00."

"

, a~

..

, -~


0''' _ _

.... lTfOT--

,-~

_ _

'-'"

'0

'"

"~_

I&I

f '- *

!.

"Oli>f)

\ "

1 ' 00 ...

r"

i. ' .>f)

..... ,...". _ _ 0

__

-_-_..
-_..,"'. --

"'- '",..
...."'" -_A.........
......... '"

_I1IOT - - ,

' 0

UltEoO:I

I-"
111

..,-...

U II!>f)

' '
,

"

....

,~'"

10

..

'.

..

Figure 13 Effect of RTFOT Aging on Tempel'lllture


and Pbase Angle

'-'"

DependeD~e

. ,.

of Complu Modulus

In addition, the frequency dependence of the rheological parameters is innucnc.ed by


aging process (Figure 14). For the base bitumens, aging increases complex modulus and
decreases phase angle over a frequency range of 0.1 to 100 rad/s, indicating the aged bitumens
become more elastic. For the modified binders, the curves may cross, both for complex
modulus and phase angle, and changes in elasticity (phase angle) are dependent on the
frequency considered.
The rheological changes are consistent with the degradation of polymers and oxidation
of bitumens (17). An increasing content of funct ional groups may change bitumen polarity
and molecular association. As a resull, compatibility (microstructure) between thc polymer

19

and bitumen is changed, as shown in Figure 15. On the other hand, breakdown of polymer
reduces the number of large polymer molecules, and consequently, the effectiveness of the
polymer in significantly modifying bitumen rheology is reduced. Obviously, the rheological
changes in aged modified binders are dependent on a combined effect of bitumen oxidation
and polymer degradation, which varies with types of bitumen and polymer, as well as
polymer content.

'*~

i ,OOl'"

I, , t:~

-. _.--_...._

I IIlIl...

,--

,-,

",,

toIioOl

. . ...........

-......

.,

"1

"

I.Ioot:'"

'.4

.... _..... .
-_
._
.....
-. ._

~---

i
A100!",

'Q'.",
f _ l--t

,_

. .... ... "' ... ""',

,'""
_ _ _ _ __ _,lOEoOO

,RoO,

-. . -_.._.... .............-."'-."'. ......""

--~-

10

I E'"

, .~

......-:.

.'0'

.-_........,......

... . _

r~~~~~~~~~-,'

- - --_
............ ""'"
_ .... p ..... .....
_

"'''..............
.....
..... ........

' *~

",,

j,00l~

..
"'.,,
.'
~

1 1.0lIIE>fJ

f_~ ""1

~100Jt: ....

' *~

..... tr .....

' *4 r-:--:-;-~~~~~~~l.

....

;:,

"1
I,j
_____ a_.""" 0'
!

JI.'"
..

,*4

,-,
'OK.o,
'*4

lODE'"

'*~

,~~

____

, OQE.II

I lOX"

"

"'
.........
"'

~~

.,.,,
.',
.,

,"'"
___
....J "

I 111(>01

''' ' ' ' ' o4IIl

f_ I'~

Figure 14 Complex ModulU5lnd Phase Angle It 60C as I Funttion or Frequenty Cor


Base and Polymer Modified Bitumen B berore Ind after RTFOT

Bitumen B + 6% EaA bcfoo RTFOT

Bitumen

a + 6% EBA after RTfOT

Figure IS Errut of RTFOT Aging on the Microstrutlure of Polymer Modified Binden


Traditionlllly, the aging sensitivity of bitumens is evaluated by means of aging index,
which is defined as the ratio of a physical/rheological parameter of the aged binder to that of
the original binder. For conventional binders, high values of the parameter indicate a high
degree of bitwnen aging (hardening). However, aging index of polymer modified binders is
largely influenced by the evaluation temperature and frequency, as illustrated in Figure 16.
The varying indices are caused by degradation of the JXllymcr and oxidation of the bitumen,
which are to some extent compensatory. Evidently, aging index is not an accurate parameter
in the case of polymer modified binders, and it does nol seem possible 10 apply a certain value
of aging index in characterizing their aging properties.

,
2.0

r
._I.!
:
~

1.0

...
.

..

. " ,,/ "


,

..

....

-_.
-_...............
.. .
, ,-,

----

'V

'

~ ... -.

Q.5

0.'

L~~~~~_~~~..J
~

10

]00 ]M

]~

OJ

1.00&-411

1.00+1

I.OOE+Gl

Tom"".. t." for Mouori"1 AItiDJ: ladn t"tl

Figure 16 Temperature and Frequency Dependence of RTFOT Agiog Iodex

CONCLUSIONS
Polymer modified bitumens exhibit a two-phase microstructure. Under the influence
of gravitational fields, a phase separation can OCCut. The phase separation may be determined
by hot storage test. The compatibility and storage stability of polymer modified binders
depend greatly on polymer content and are also influenced by the chemical composition of
base bitumens and the nature of polymers. By mixing a small amount (3 percent in this study)
of polymer, the modified binders show dispersed polymer particles in the continuous bitumeo
matrix. At an increased polymer content, a continuous polymer phase may be observed. The
minimum percentage of the polymer to ensute the formation of its continuous phase depends
on the base bitumen as well as the polymer itself. Regardless of the nature of the two phases,
the storage stability of modified binders decreases with increasing polymer content. Among
all the modified binders prepared, those containing EBA display the lowest storage stability.
For the elastomer (SBS and SEBS) modified binders, those containing branched SSS are the
most unstable. In the case of EVA modified binders, better storage stability is observed for
those containing the polymer with a lower VA content and a higher MI. Better compatibility
and higher storage stability may also be achieved by using a base bitumen with a higher
content of aromatics and/or a lower content of asphaltenes.
A Qualitative comparison between separation index and fluorescence micrograph
indicates that, at a given polymer content, the modified binders showing finer polymer
dispersion in micrographs generally exhibit less phase separation during hot storage. Such a
comparison cannot be made among modified binders with differeot polymer contents. This
means that the compatibility defined by different methods is not necessarily consistent, and
the degree of compatibility cannot be determined using only one method. Moreover,

"
compatibility and storage stability may influence the rheological properties of modified
binders; unfortunately, no definite relationships between tbese parameters were established in
this study. The complexity in such relationships increases when modified binders with
different kinds of polymer art compared.
The rheological properties of bitumens are improved by polymer modification. The
improved viscoclastic properties may be identified by various parameters obtained using
dynamic mechanical analysis, such as phase angle and storage modulus. Four regions (glassy,
transition, plateau, and tenninal or flow) are recognized in plOlS of storage modulus vrnus
temperature for polymer modified binders of sufficiently high polymer content (6 percent in
this study). In phase anglcltemperature diagrams, phase angle maximum and minimum are
observed. On the other hand, for base bitumens and modified binders with a low content of
polymer (3 percent in !his study), !he transition goes straight from the glassy 10 the flow
regions with no region of rubberlike behaviour. The degree of the modification with respect to
the increased elastic response is greatly affected by the characteristics of base bitumens and
polymers. For a given base bitumen, the influence of the six polymers tested may be ranked as
branched SBS, SEBS/linear SBS, EBA, EVA2 and EVAI, branched SBS being the most
effettive. The improved dynamic viscoelastic properties should be favourable for resistance to
rutting al high temperatures.
Polymer modification improves the low.temperature properties of bitumens, as
indicated by decreases in creep stiffness, Fraass breaking point and glass transition and
limiting stiffness temperatures. The relative improvement varies with the base bitumen,
polymer type and polymer content. Compared with thennoplastics (EVA and EBA), the
elastomers (SBS and SEBS) seem more effettive in improving bitumen low-temperature
parameters (except for the limiting stiffness temperature). For a given polymer, the BI80
bitumens may result in a relatively higher reduction in creep stiffness than the B8S bitumen.
The influences of polymer modification may also vary with testing conditions (temperature
and loading time). The improved low temperature parameters should be favourable with
respect to asphalt cracking perfonnance.
The RTFOT and TFOT aging causes oxidation of bitumen and degradation of
polymer, and consequently, change the microstructure and rheological properties of the
modified binders. These changes largely depend on the characteristics of the polymer used
and its content. For the modified binders with thennoplastics (EVA and EBA) as well as those
with a low content of elastomers (SBS and SEBS), aging increases complex modulus and
elastic response (decreased phase angle) and reduces temperature susceptibility. On the other
hand, for the modified binders with sufficiently high content of elastomers (;2: 6 percent in Ihis
study), the influence of aging on those parameters is strongly dependent on temperature and
frequency.
Aging index may be applied for evaluating !he base bitwnens and certain modified
binders with no significantly chemical changes in the polymer during aging, but it is not
suitable if the aging process causes a considerable polymer degradation. In this case, values of
aging index are largely influenced by !he temperature and frequency dependence of polymer
effect
ACKNOWLEDGEMENTS
The authors wish to thank Jonas Ekblad, Britt Wideman and Clarissa Villalobos for their
laboratory assistance. The authors also gratefully acknowledge the Swedish Transpon and
Communications Research Board (KFB) for the financial support of this study, and Nynas
Petroleum for supplying a number ofbase bitumens and polymers.

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