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Construction
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MATERIALS
www.elsevier.com/locate/conbuildmat
Abstract
Bituminous binders are known to have simple rheological properties. Natural asphalts, such as Trinidad Lake Asphalt (TLA) and
Uintaite, are often used for bitumen modication in order to obtain improved performance of the respective asphalt mixture (such as
stiness and deformation resistance). This paper presents the results from a series of assessments of empirical and rheological properties
of bituminous binders, which incorporate natural asphalts (specically TLA and Uintaite) and/or polymer modiers. Binder empirical
properties, measured by penetration and Ring and Ball softening point tests, showed that natural asphalts reduce or increase these
respective empirical values at the level anticipated by conventional blending formulas. However, rheological analysis showed that
the stiening eect caused by addition of natural asphalts, which is normally anticipated in the case of asphalt incorporating unmodied bitumen, took place in a dierent way if a polymer modier was also used.
2006 Elsevier Ltd. All rights reserved.
Keywords: Rheology; Viscoelastic response; Complex modulus; Black curve; Polymer; Lake asphalt; Asphaltite; Uintaite
1. Introduction
Bitumen is understood to be A viscous liquid, or a
solid, consisting essentially of hydrocarbons and their
derivatives, which is soluble in trichloroethylene and is substantially non-volatile and softens gradually when heated.
It is black or brown in colour and possesses waterproong
and adhesive properties. It is obtained by renery processes
from petroleum, and is also found as a natural deposit or
as a component of naturally occurring asphalt, in which
it is associated with mineral matter [1]. In addition, bitumen is known to be a colloidal system, where the highest
molecular weight components, i.e. the asphaltene micelles,
are dispersed and the lower molecular weight maltenes (i.e.
aromatics, saturates, resins) are dissolved in the saturated
hydrocarbon mixture [2]. Depending on the degree of aromaticity of the maltenes and the nature and the concentration of the asphaltenes, the micelles in the bitumen may
*
0950-0618/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2005.12.025
240
bituminous materials, and that bitumen rheology can provide preliminary indications of the resulting bituminous
mixture performance. For unmodied bitumens, elastic
behaviour (lower phase angle) is generally associated with
high stiness and increased brittleness; while the viscous
response (higher phase angle) reects high ductility and
low stiness.
2. Natural asphalts
Natural asphalts can be found in dierent forms, such as
bitumen deposits, lake asphalt or rock asphalt, and in different degrees of purity (i.e. the proportions of bitumen
and other mineral matter).
Naturally occurring bitumen deposits, generically
termed asphaltite, are reported to be found in Argentina,
Barbados and Utah; the most extensively utilised asphaltite
is well known as Uintaite [5]. Uintaite is a pure natural
hydrocarbon (with a purity in excess of 99%) and 70%
asphaltene content [6], which is found in this form only
in the Uintah Basin in Eastern Utah, USA, and is also
known as Gilsonite [7]. It was rst used commercially in
1974 in Oslo, and has since been used in the USA (notably
on the New Jersey Turnpike) and in Germany. Uintaite is a
hard natural bitumen with zero penetration at 25 C and
softening point between 129 and 204 C (typically 176 C
for asphalt paving modication) [6]. It is claimed that its
high nitrogen content gives better adhesion between binder
and aggregate, thus improving stripping and oxidation
resistance. The high asphaltene content and high molecular
weight are thought to function mainly as a solution thickener, giving improved stiness and deformation resistance.
It is claimed that other than increasing the mixing and
compaction temperatures by 1015 C, little alteration to
conventional manufacturing and laying processes are
required for Uintaite modied asphalts.
The most famous source of lake asphalt is the Trinidad
Lake Asphalt (TLA), which occurs naturally in the form of
a 100 acre lake located on the island of Trinidad in the
West Indies, and comprises a mixture of bitumen, water
and very ne mineral matter. Typically, TLA consists of
a mixture of bitumen and minerals of the following composition: soluble bitumen (5355%), mineral matter (3637%)
and other (910%). The bitumen component is made up of
maltenes (6366%) and asphaltenes (3437%). Typically,
rened TLA has a penetration at 25 C of 2 dmm and a
softening point between 93 and 99 C [8]. TLA is well
known for its consistent properties, stability and durability,
and is widely used for bridge and airport applications
where high stability surfacings are required. Typically, a
50:50 blend of TLA and bitumen is adopted in the production of TLA modied mastic asphalt, although this ratio
can be varied to meet particular design specications.
Natural rock asphalts have a completely dierent nature, being formed by the impregnation of oil into limestone, which over time is transformed into bitumen
within the rock. The bitumen content is typically about
241
Table 1
Composition and properties of mastic bindersa
Sample ID
Composition
Properties
Base binder
Added TLA
Added Uintaite
Pen at 25 C (dmm)
RBSP (C)
A
C
E
B
D
K
S
L
M
N
O
R
U
W
70%
50%
60%
70%
50%
60%
25%
15%
10%
71
31
11
41
15
51
12
14
88
32
19
15
11
15
48.0
59.8
70.0
111.0
88.0
112.0
103.4
105.0
105.0
101.4
98.0
103.4
99.4
101.4
Note: Pen and RBSP denote penetration (BS EN 1426) and R&B softening point (BS EN1427) tests, respectively.
a
the term mastic binder denote bituminous binder used in the mastic asphalt mixture, either with or without natural asphalt, but prior to the addition
of ne and coarse aggregates.
100
90
60/80 Pen
80
Elastomeric B
Elastomeric H
Penetration (dmm)
70
Elastomeric M
60
Plastomeric R
50
40
30
20
10
0
0
10
20
30
40
50
60
% Soluble Bitumen in Natural Asphalt by Total Weight of Soluble Bitumen in the Blend
Fig. 1. Eect of per cent natural asphalt on the penetration (at 25 C) of mastic binders.
242
130
60/80 Pen
Elastomeric B
Elastomeric H
Elastomeric M
Plastomeric R
120
110
100
90
80
70
60
50
40
0
10
20
30
40
50
60
% Soluble Bitumen in Natural Asphalt by Total Weight of Soluble Bitumen in the Blend
Fig. 2. Eect of per cent natural asphalt on the R&B softening point of mastic binders.
where,
Pen New is the calculated penetration value of the new
binder.
SP New is the calculated softening point value of the
new binder.
Pen A and Pen B is the measured penetration value of
binders A and B respectively.
SP A and SP B is the measured softening point value of
binders A and B respectively.
a and b is the proportion of binders A and B in the blend
respectively; in this case a + b = 1.
The above equations imply that:
for a base binder (A) which has a softening point value
lower than that of the natural asphalt (B), the addition
of natural asphalt (B) will result in a new blend (New)
with a softening point value higher than that of the base
binder (A), and vice versa;
for a base binder (A) which has a penetration value
higher than that of the natural asphalt (B), the addition
of natural asphalt (B) will result in a new blend (New)
with a penetration value lower than the base binder
(A), and vice versa;
the rate of change in the penetration or the softening
point of the new blend (New) will be in proportion to
the level of modication (b).
Figs. 3 and 4 compare the calculated and measured penetration and softening point values of the mastic binder
blends (Eqs. (1) and (2) were used for the calculation). In
this case, the natural asphalts (Uintaite (in 60/80pen blend
only) and TLA) were assumed to have a typical penetration
value of 1 dmm and R&B softening point values of 176 and
96 C for the Uintaite and TLA, respectively.
Fig. 3 shows that Eq. (1) tends to over-estimate the calculated penetration values of the new blend, resulting in a
dierence in the calculated penetration values of at least
4 dmm from the measured values, whilst Fig. 4 demonstrates that the dierence between the calculated and the
measured softening point values was relatively small. Overall, however, the observed trends in the calculated penetration and R&B softening point values after addition of
natural asphalts were considered to be consistent with
those observed in the measured values, implying the applicability of these formulas for predicting the empirical properties for these blends.
5. Rheology
Rheological testing was carried out in accordance with
Clause 928 of the Manual of Contract Documents for
Highway Works [13], which is currently an assessment
requirement for PMBs for use in UK highways. The
rheological testing involved determination of complex
shear modulus (G*) and phase angle (d) of the studied
PMB materials over a range of test temperatures
(between 0 and 80 C) and frequencies (between 0.01
and 10 Hz). The rheological testing was carried out by
243
100
90
Measured
Calculated
80
Penetration (dmm)
70
60
50
40
30
20
10
0
A
60/80pen
Elastomeric B
Elastomeric K
Elastomeric M
Plastomeric R
Fig. 3. Measured and calculated penetration values (at 25 C) of mastic binders.
120
Measured
Calculated
100
80
60
40
20
0
A
60/80pen
Elastomeric B
Elastomeric K
Elastomeric M
Plastomeric R
244
Table 2
Selected of rheological data (at 0.4 Hz)
Sample ID
Base binder
25 C
80 C
5 C
25 C
80 C
A
C
E
B
D
K
S
L
M
N
O
R
W
U
1.32 107
2.96 107
1.70 108
1.35 107
7.17 107
4.22 105
1.98 107
4.92 107
1.40 105
8.20 106
1.06 107
9.10 106
4.11 106
1.84 107
4.33 105
1.70 106
1.26 107
4.85 105
4.78 106
1.43 105
3.26 106
6.49 106
3.12 104
6.54 105
1.32 106
1.58 106
1.25 106
2.80 106
3.09 102
1.50 103
11.30 102
37.70 102
3.51 104
1.23 105
2.33 104
1.15 104
6.55 103
9.81 103
6.63 104
2.31 104
1.31 104
41.4
32.6
26.9
37.7
27.3
20.6
25.7
24.0
40.8
39.3
31.5
27.3
17.7
26.0
64.5
54.5
55.7
55.9
54.3
20.2
38.6
41.7
21.6
48.8
42.5
35.5
24.9
38.5
84.8
89.9
16.9
66.4
24.6
43.7
55.9
28.6
43.9
47.5
38.4
52.4
54.6
9.9%
55.9%
35.1%
44.4%
55.9%
35.1
44.4%
8.6%
15.3%
90
1.E+09
Softer
80
More
Viscous
1.E+07
70
1.E+06
1.E+05
60
1.E+04
50
1.E+03
40
1.E+02
A (60/80 Pen) - G*
A (60/80Pen) - PA
C (60/80Pen + 10%Uintaite) - PA
E (60/80Pen + 70%TLA) - PA
30
1.E+01
1.E+00
Stiffer
1.E+08
More
Elastic
20
10
20
30
40
50
60
70
Temperature ( C)
Fig. 5. Rheology of 60/80 pen based mastic binders (at 0.4 Hz).
1.0.E+09
80
1.0.E+08
70
1.0.E+07
90
60
50
40
30
245
5E
25 E
60 E
80 E
5C
25 C
60 C
80 C
5A
25 A
60 A
80 A
1.0.E+06
1.0.E+05
1.0.E+04
1.0.E+03
1.0.E+02
20
10
5E
25 E
60 E
80 E
5C
25 C
60 C
80 C
5A
25 A
60 A
80 A
0
0.01
0.1
1.0.E+01
10
1.0.E+00
0.01
0.1
Frequency (Hz)
10
Frequency (Hz)
Note: A, C and E denote sample I.D. 5, 25, 60 and 80 denote test temperatures in degree
Celsius.
Fig. 6. Isothermal curves of 60/80 pen based mastic binders containing natural asphalts.
1.E+09
1.E+08
+ 70% TLA
1.E+07
60/80 Pen
1.E+06
TS 0-80C - Sample E (60/80Pen + 70% TLA)
1.E+05
FS @5C - Sample E
FS @25C - Sample E
FS @60C - Sample E
1.E+04
+ 10% Uintaite
1.E+03
FS @60C - Sample C
FS @80C - Sample C
1.E+02
1.E+01
FS @60C - Sample A
FS @80C - Sample A
1.E+00
20
30
40
50
60
70
80
90
246
60
more
viscous
Sample S (K + 60%TLA)
Sample R
Sample U (R + 25%TLA)
Sample L (K + 70%TLA)
55
Phase Angle (degree)
more
elastic
Sample K
50
45
40
35
30
25
20
15
10
10
20
30
40
50
o
Temperature ( C)
60
70
80
1.E+08
Sample K
Sample S (K + 60%TLA)
Sample R
Sample U (R + 25%TLA)
Sample L (K + 70%TLA)
1.E+07
1.E+06
1.E+05
1.E+04
10
20
30
40
50
60
70
Temperature ( C)
Fig. 9. Eect of TLA addition on the complex modulus (G*) of PMBs.
80
247
5K
25 K
80 K
5S
25 S
80 S
5L
5S
5K
5L
25 L
80 L
25 L
25 S
25 K
80 L
80 S
80 K
1.0E+09
60
1.0E+08
50
40
30
1.0E+07
1.0E+06
1.0E+05
20
1.0E+04
10
1.0E+03
0
0.01
0.1
10
0.01
0.1
Frequency (Hz)
10
Frequency (Hz)
Note: K, L and S denote sample I.D. 5, 25 and 80 denote test temperatures in degree Celsius.
Fig. 10. Isothermal curves of elastomeric mastic binders K.
the 60/80 pen based mastic binders, and that in any test/
loading condition, the d values of Elastomeric K binders
never exceeded 60 as opposed to those of the 60/80 pen
based mastic binders which reached 90 (completely viscous) at 80 C.
1.E+08
+ 70% TLA
1.E+07
Sample K
1.E+06
+ 60% TLA
TS 0-80C - Sample K
FS @ 5C - Sample K
FS @ 25C - Sample K
FS @60C - Sample K
FS @ 80C - Sample K
TS 0-80C - Sample S (K + 60%TLA)
FS @ 5C - Sample S
FS @ 25C - Sample S
FS @60C - Sample S
FS @ 80C - Sample S
TS 0-80C - Sample L (K + 70%TLA)
FS@5C - Sample L
FS @ 25C - Sample L
FS @60C - Sample L
FS @ 80C - Sample L
1.E+05
1.E+04
1.E+03
10
20
30
40
50
60
70
80
248
changes in the shape of the black curve from a very narrow S-like curve (typical for heavily modied elastomeric
binders) to a broader S-like curve after TLA addition;
Fig. 11 shows that the shape of the black curve of Sample K had been stretched out by the addition of TLA,
resulting in:
90
1.0E+08
5R
25 R
60 R
80 R
5U
25 U
60 U
80 U
80
1.0E+07
70
60
50
40
30
1.0E+06
1.0E+05
1.0E+04
20
1.0E+03
10
5R
25 R
60 R
80 R
5U
25 U
60 U
80 U
1.0E+02
0.01
0.1
10
0.01
0.1
10
Frequency (Hz)
Frequency (Hz)
Note: R and U denote sample I.D. 5, 25, 60 and 80 denote test temperatures in degree Celsius
Fig. 12. Isothermal curves of plastomeric mastic binders R.
1.E+08
1.E+07
+ 25% TLA
1.E+06
TS 0-80C - Sample R
FS @5C - Sample R
FS @25C - Sample R
FS @60C - Sample R
FS @80C - Sample R
TS 0-80C - Sample U (R + 25%TLA)
FS @5C - Sample U
FS @25C - Sample U
FS @60C - Sample U
FS @80C - Sample U
Sample R
1.E+05
1.E+04
1.E+03
10
20
30
40
50
60
70
80
249