Академический Документы
Профессиональный Документы
Культура Документы
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 .
INTRODUCTION
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.
_.
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:
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
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
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 .
'
'
~.
I .
o
...
BilUmen B + 9% SEBS
'
Bitumen B + 3% EVA]
. . .. '" .
~tr .
,
iI'
8itwnen 8 + 3% SEaS
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
l.ooE+07
.. . .. .. -. ..
. ...
LooE+il4
.. I,
_.-'
- .-
l.ooE+{I3
I.OOE+{I2
I.00E+{I1 L_~~=_~~~~~~~....J
l.ooE-01
l.ooE+OO
I.(IOE+OI
l.ooE+{I2
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
,,.
Figure 4 Relationship between the SeparttioD Index (at 1 radls) orSBS Modifi ed
Binder! lod Bitumen Composition
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
~-
'.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..... ~ ....
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
.,..
"
-_-_.
.... -_.......
io
L.
~_I
._10"
.....
,
"
--.
.._c ... ..
..._ c ... ....
~- <
.... ....
~_ c
... _
._."oM!
, oK...
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)
13
15
r---------------------,
10
R'" O.U
R" o.as
R " O.93
35
75
65
55
95
85
105
Figure 9 Relationship between G"sino (at 10 radls and 60C) and Softening Point
,--,
,-~
~ 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('"
,.
"
"
"
"
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
"
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,
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
-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
"
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.
-_
-_-_.................. .._-.... .--
....
, -~
, . .. 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
..
'.
..
'-'"
DependeD~e
. ,.
of Complu Modulus
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
f_ I'~
Bitumen
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
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.
REFERENCES
5
6
8
9
10
II
12
13
14
15
16
17
D.N. lillie, tW. Bulton, R.M. White, EK Ensley, Y. Kim and SJ. Atuned,
"Investigation of asphalt additives", Report No FHWA/RD-871OO1. U.S. Department
ofTransportation. Federal Highway Administration, 1987.
a.N. King, H.W. King, O. Harders, W. Arand and P.-P. Planche, "lnflucnceof asphalt
grade and polymer concentration on the low temperature performance of polymer
modified asphalt", J. Assoc. of Asphalt Paving Technologists, Vol. 62, 1993, pp. ]-22.
H I. Collins, M.G. Bouldin, R. Gelles. and A. Berker, "Improved performance of
paving asphalls by polymer modification", J. Assoc. of Asphalt Paving Technologists.
Vol. 60, 199I,pp. 43-79.
n . Goodrich, "Asphaltic binder rheology, asphalt concrete rheology and asphalt
concrete mix properties", J. Assoc. of Asphalt Paving Technologists, Vol. 60, pp.
1991 , pp. 80- 120.
S. Piazza, A. Arcozzi and C. Verga, "Modified bitumens containing thennoplastic
polymers~, Rubber Chemistry and Technology, Vol. 53, 1980, pp. 994- 1005.
G. Van Gooswil!igen and W.C. Vonk, "The role of bitumen in blends with
thermoplastic rubbers for roofing applications", Proceedings of the Vl lntemational
Conference "Roofing and Waterproofing, The International Waterproofing
Association, London, 1986, pp. 45-52.
B. Brule, Y. Brion and A. Tanguy, "Paving asphalt polymer blends: relationships
between composition, structure and properties~ , Pmc. Assoc. of Asphalt Paving
Technologists, Vol. 57, 1988, pp. 41-64.
D. Whiteoak, "The Shell Bitumen Handbook", Shell Bitumen UK, 1991, p.74.
N.W. Mcleod, "A 4-year survey of low temperature transverse pavement cracking on
three Ontario test roads", Proc. Assoc. of Asphalt Paving Technologists, Vol. 41 ,
1972, pp. 424-493.
X. Lu, U. lsacsson and 1. Ekblad, "Phase separation of SBS polymer modified
bitumens", Journal of Materials in Civil Engineering, ASCE. 1998, in press.
O. Kramer and J.D. Ferry, "Dynamic mechanical properties", Science and Technology
of Rubber, edited by F. R. Eirich, Academic Press, New York, 1978.
J.D. Ferry, Viscoelastic Properties of Polymers", Wiley, New York, 1980.
G.N. King, H.W. King, O. Harders, P. Chavenot and J.-P. Planche, "Influence of
asphalt grade and polymer concentration on the high temperature performance of
polymer modified asphalt". J. Assoc. of Asphalt Paving Technologists, Vol. 61, 1992,
pp. 29-66.
H.U. Bahia and DA Anderson, "The new proposed rheological properties of asphalt
binders: why are they required and how do they compare to conventional properties",
Physical Properties of Asphalt Cement Binders, ASTM STP 124\, John C. Hardin,
Ed., American Society for Testing and Materials, Philadelphia, 1995, pp. 1-27.
DA Anderson and T.W. Kennedy, "Development of SHRP binder specification", J.
Assoc. of Asphalt Paving Technologists, Vol. 62, 1993, pp. 481-507.
V.P. Puzinauskas, Properties of asphalt cements-, Pmc. Assoc. of Asphalt Paving
TechnologislS, Vol. 48, 1979, pp. 646-710.
X. Lu. and U. lsacsson, -Chemical and rheological evaluation of ageing properties of
SBS polymer modified bitumens-, Fuel, Vol. 77, 1998, pp. 961-972.