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Towards a microstructural model of bitumen aging behavior

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DOI: 10.1080/10298436.2014.993192

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Towards a microstructural model of bitumen ageing

behaviour
a b a c a
Lukas Eberhardsteiner , Josef Füssl , Bernhard Hofko , Florian Handle , Markus Hospodka ,
a c
Ronald Blab & Hinrich Grothe
a
Institute of Transportation, Vienna University of Technology, Gusshausstraße 28/230/3,
A-1040 Vienna, Austria
b
Institute for Mechanics of Materials and Structures, Vienna University of Technology,
Karlsplatz 13/202, A-1040 Vienna, Austria
c
Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01,
A-1060 Vienna, Austria
Published online: 10 Jul 2015.
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To cite this article: Lukas Eberhardsteiner, Josef Füssl, Bernhard Hofko, Florian Handle, Markus Hospodka, Ronald Blab &
Hinrich Grothe (2015) Towards a microstructural model of bitumen ageing behaviour, International Journal of Pavement
Engineering, 16:10, 939-949
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 International Journal of Pavement Engineering, 2015
Vol. 16, No. 10, 939–949, http://dx.doi.org/10.1080/10298436.2014.993192

Towards a microstructural model of bitumen ageing behaviour

Lukas Eberhardsteinera*, Josef Füsslb, Bernhard Hofkoa, Florian Handlec, Markus Hospodkaa, Ronald Blaba and
Hinrich Grothec
a
Institute of Transportation, Vienna University of Technology, Gusshausstraße 28/230/3, A-1040 Vienna, Austria; bInstitute for
Mechanics of Materials and Structures, Vienna University of Technology, Karlsplatz 13/202, A-1040 Vienna, Austria; cInstitute of
Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, A-1060 Vienna, Austria
(Received 27 February 2014; accepted 19 October 2014)

When it comes to describe the mechanical behaviour of hot mix asphalt (HMA), the change of the mechanical properties
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015

over time due to environmental impacts known as ageing has to be considered. Hardening and embrittlement of bitumen lead
to a reduced resistance against cryogenic cracks and premature formation of fatigue cracks in bituminous layers. Within this
work, the microstructure of bitumen is investigated by conducting static shear creep tests on artificially composed bitumen
with asphaltene contents varying between 0 vol-% and 26.71 vol-% as well as on a paving grade bitumen 70/100. Both are
considered in unaged and laboratory-aged (rolling thin-film oven test þ pressure ageing vessel) conditions to be able to
identify and describe ageing effects. While the properties of the considered material phases of bitumen (identical to
saturates, aromatics, resins and asphaltenes (SARA) fractions) seem to remain unaffected, an increase of the asphaltene
content due to ageing can be observed. A micromechanical model is proposed that allows a prediction of the consequences
of these microstructural changes on the mechanical behaviour of bitumen. Atomic force microscopy and environmental
scanning electron microscopy images confirm a composition consisting of a micelle-like structure in a contiguous matrix, a
structural representative volume element concept based on SARA fractions is suggested, extending an existing multiscale
model for HMA. A very good accordance between model predictions and experimental results indicates the model’s ability
to reproduce as well as to describe the effects related to ageing.
Keywords: bitumen; ageing; microstructure; SARA fractions; viscoelasticity; DSR

1. Introduction
The mechanical properties of hot mix asphalt (HMA),
which is used in flexible road pavements, change
significantly over time due to impacts of the environment.
Increasing age, hardening and embrittlement of the
bitumen (binder agent) lead to a decrease of the elasticity
and ductility of the pavement structure, resulting in
reduced resistance against cryogenic cracks and premature
formation of fatigue cracks. The mechanisms behind this
phenomenon, called ageing, are subject of ongoing
debates in the scientific community.
Basically, two ageing levels can be distinguished: (i)
Short-term ageing, which occurs during the production
and compaction of HMA, when bitumen is mixed with
aggregate at temperatures of around 1608C. Within this
process, thin layers of bitumen are formed leading to a
large reactive surface, which is susceptible for ageing-
promoting thermal effects such as the distillation of
volatile fractions and chemical processes such as oxidation
or polymerisation (Traxler 1961, Bell 1989, Read and
Whiteoak 2003, Lesueur 2009). In addition, there is (ii)
long-term ageing, which occurs during service life of the
pavement construction and takes much longer (decades).
Besides local climate and air void content of the built-in
material, especially the position of the bitumen inside the
pavement plays an important role. As the exposure to
reactive gases or water-soluble reactants and UV radiation
in top layers exceeds the exposure in base layers, ageing
effects near the surface prevail (Lesueur 2009).
In times of scarce crude oil resources, recycling and
use of reclaimed asphalt pavements in new pavement
constructions on the one hand, and the development of
more sustainable and renewable alternatives to bitumen on
the other hand, are becoming increasingly important.
In both cases, the change of material characteristics of
bituminous mixtures due to ageing is a key issue and,
therefore, a close examination of the underlying effects is
not only justified but also necessary. For a complex
composite material like bitumen, examining the material’s
microstructure is a reliable way to a better understanding
of the mechanical behaviour and, moreover, a phenom-
enon like ageing. Thereby, SARA fractionation separating
bitumen into saturates, aromatics, resins and asphaltenes
(Corbett 1969, Lesueur 2009) is the most common way to
identify the constituents of bitumen. Imaging methods
such as atomic force microscopy (AFM) or environmental
scanning electron microscopy (ESEM) enable to visualise

*Corresponding author. Email: lukas.eberhardsteiner@tuwien.ac.at

q 2015 Taylor & Francis
 940 L. Eberhardsteiner et al.
the (micro)structures built up by these constituents (Bodan
1982, Yen 1992, Espinat et al. 1998, Forbes et al. 2001,
Pauli et al. 2003, Bearsley et al. 2004, Jäger 2004, Masson
et al. 2006, Stangl et al. 2006, Lesueur 2009, Schmets
et al. 2010, Nahar et al. 2013a, 2013b, 2014) and, hence,
allow for the development of models predicting the
mechanical behaviour.
In recent years, Lackner et al. introduced a multiscale
model to predict the viscoelastic material behaviour of
HMA (Lackner et al. 2004, 2005, Aigner et al. 2009,
Pichler and Lackner 2009, Pichler et al. 2012). This model
is able to describe the macroscopic behaviour as a function
of microstructural characteristics down to the so-called
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015
mastic-scale, consisting of bitumen and filler, where,
however, bitumen is considered as homogeneous phase.
An extension of the existing model by taking the
microstructure of bitumen into account was recently
published in Eberhardsteiner et al. (2014). On the basis of
continuum micromechanics, a representative volume
element (RVE) of bitumen describing the complicated
microstructure as simply as possible is introduced to
predict the viscoelastic behaviour of bitumen.
Within this paper, identification experiments on aged
and unaged artificially composed bitumen with varying
asphaltene content were conducted and evaluated, first.
After a reaffirmation of model assumptions by AFM and
ESEM results, the process of bitumen ageing is explained
chemically by a micelle model and the thereby identified
main effects are described by the micromechanical model
for bitumen according to Eberhardsteiner et al. (2014).
Then, model predictions and test results for aged and
unaged bitumen are compared to validate the developed
model approach, before, finally, conclusions are drawn.
2. Experiments
In order to investigate possible changes in microstructure
due to ageing effects, aged and unaged artificial bitumens
with varying asphaltene contents were produced from an
unmodified bitumen pen 70/100. While this bitumen has
an asphaltene content of 7.79 vol-% naturally, when it is
unaged, the asphaltene content increases to 13.36 vol-%
after laboratory long-term ageing (rolling thin-film oven
test (RTFOT) þ pressure ageing vessel (PAV)-ageing –
see below).
Bitumen can be separated into two major fractions: (i)
an n-heptane soluble phase, which is generally called
maltenes, appearing as a viscous liquid at room
temperature and (ii) an n-heptane insoluble phase, called
asphaltenes, which exhibit solid or almost solid properties.
The extraction was conducted based on the procedure
proposed by ASTM Standard 4124 (ASTM D4124-01
2010). Hereby, a dispersion of approximately 10 g of
bitumen and 300 ml of n-heptane was assembled and
heated to 908C for around 90 min. After cooling and
sedimentation over night, particles were filtered and
further extraction for 72 h using a Soxhlet extractor was
conducted to obtain the asphaltene phase. After mixing the
liquid phase of the Soxhlet extraction with the filtrate of
the n-heptane extraction, the solvent n-heptane was
evaporated to obtain the maltene phase, and asphaltenes
and maltenes were dissolved in toluene and mixed again
with different proportions. By evaporating toluene,
asphaltenes can be ’re-dispersed’ in the maltene phase.
This extraction and ’reassembly’ is a quite time-expensive
task – it requires approximately one week for 10 g of
bitumen. Nevertheless, in this way, 30 g of artificially
composed bitumen with varying asphaltene content from
0 vol-% to 17.36 vol-% (in the following, only % is used)
could be produced.
Ageing effects are reproduced in the laboratory using
standardised methods, namely the RTFOT to simulate
short-term ageing, and the PAV method to describe long-
term ageing. Within the RTFOT method, bitumen is filled
in constantly rotating glasses to form a thin bitumen film,
which is exposed to a constant airflow for 75 min at 1638C
(Huang et al. 1996, Nicholls 2007). To perform PAV
ageing, a static bitumen film is kept at 1008C and under a
pressure of 21 bar for 20 h. This test is only conducted in
connection with RTFOT ageing (Huang et al. 1996,
Nicholls 2007).
Static shear creep tests – so called creep-recovery
(CR) tests – performed on the experimental set-up of a
dynamic shear rheometer (DSR) (see Figure 1) were
conducted to obtain the material behaviour of aged and
unaged mixtures. While a constant torque M is applied
statically for 1800 s on a bitumen film (diameter
d ¼ 25 mm, height h ¼ 1 mm), deflection wðtÞ is
measured. From t ¼ 2M=pr 3 , with r ¼ d=2 and
gðtÞ ¼ r%wðtÞ=p, the creep compliance
gðtÞ
J exp ðtÞ ¼ ð1Þ
t
Torque M
DSR spindle
Cover Bitumen sample
constant height
(1mm)
DSR base plate
Figure 1. CR test using DSR experimental equipment.
 International Journal of Pavement Engineering 941

Table 1. Experimental programme for CR tests on aged and to be the only, or at least most important, consequence of
unaged artificially mixed bitumen. ageing on the microstructure of bitumen.
Test temperature
Asphaltene content – 58C þ58C þ158C 3. Modelling bitumen behaviour
0% †/+ †/+ †/+ 3.1. Micromechanical modelling
4.18% †/+ †/+ †/+
7.77% + †/+ +
Obviously, the microstructure of a composite like HMA
12.32% † † or, moreover, bitumen plays a crucial role when it comes
17.36% + †/+ + to describe its material behaviour. A modelling technique
26.71% † capable of considering the composition of a material is
Note: †, Tests on unaged bitumen; +, tests on aged bitumen. multiscale modelling. Within the framework of continuum
micromechanics (Hill 1963, 1965, Suquet 1997, Zaoui
1997, 2002, Scheiner and Hellmich 2009), a material is
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seen as a micro-heterogeneous body filling a macro-

can be obtained. These tests were performed at a homogeneous RVE at different scales of observation. The
predefined temperature in the range of 2 58C to þ 158C. complex microstructure within such an RVE can be
The full experimental programme is given in Table 1. described by the so-called material phases, quasi-
Figure 2 shows the results of the CR tests for aged homogeneous subdomains with known physical charac-
artificial bitumen samples with varying asphaltene teristics such as volume fractions or mechanical properties
contents at þ 58C in comparison to the respective results (Suquet 1997, Zaoui 1997, 2002). The size of the
from tests on unaged samples. While increasing asphaltene inhomogeneities defined by the material phases has to be
content causes a decrease in creep compliance and hence significantly smaller than the characteristic length of the
stiffer material behaviour, the creep rate dJ=dt decreases RVE, and the size of the RVE again has to be smaller than
with increasing asphaltene content, until almost elastic the characteristic dimension of the structure built up by the
behaviour is reached at an asphaltene content of 17.36%. material. At each length scale, the homogenised
Adding only low amounts of asphaltenes (4.18%) to the mechanical behaviour of the overall material can be
maltene phase leads to an abrupt increase in stiffness (see described as correlation between homogeneous defor-
Figure 2). This already indicates that by adding mations acting on the boundary of the RVE and resulting
asphaltenes, a structure in bitumen is introduced, which (average) stresses. Within these considerations, the elastic/
strongly affects the mechanical behaviour. viscoelastic behaviour of the material phases, and the
A key finding is that aged and unaged samples with the volume fractions, their characteristic shapes and their
same asphaltene content show no significant difference in interactions play an important role.
their creep curves. This in turn means that the material If a single phase has a heterogeneous microstructure
behaviour of maltenes and asphaltenes remains unaffected itself, its mechanical behaviour can be estimated through
due to ageing. So, the detected increase of asphaltene introducing RVEs within this phase. Thus, the dimensions
content (from 7.79 vol-% to 13.36 vol-%) – also of these RVEs have to be significantly smaller than the
mentioned amongst others in Lesueur (2009), Read and RVE built up by the phase itself, and imply again smaller
Whiteoak (2003) and Grover Allen et al. (2012) – appears inhomogeneities with smaller characteristic lengths, and

100
0% Asphaltene 102 0% Asphaltene
0% Asphaltene − aged
80 4.18% Asphaltene
4.18% Asphaltene − aged 0% Asphaltene
100
7.77% Asphaltene 7.77% Asphaltene
60
7.77% Asphaltene − aged
17.36% Asphaltene
J[1/MPa]

J[1/MPa]

17.36% Asphaltene
40 17.36% Asphaltene − aged 0% Asphaltene
10–2
0% Asphaltene − aged
4.18% Asphaltene
4.18% Asphaltene
20 4.18% Asphaltene − aged
10–4 7.77% Asphaltene
7.77% Asphaltene − aged
0 17.36% Asphaltene
17.36% Asphaltene
17.36% Asphaltene − aged
−20 10–6
0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000 1200 1400 1600 1800
t [s] t [s]

Figure 2. Results from CR tests on aged artificial bitumen at þ58C compared to the respective results from unaged bitumen. Creep
compliance is shown on a linear scale (left) and on a logarithmic scale (right) for a better representation of creep curves with high
asphaltene content.
 942 L. Eberhardsteiner et al.
stone (d > 2 mm)
mortar
asphalt-scale
air voids
sand (d ≤2 mm)
mastic mortar-scale
filler (d ≤125 µm)
~1000 µm bitumen mastic-scale
~100 µm ? bitumen-scale
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015
Figure 3. Multiscale model for HMA according to Lackner
et al. (2004, 2005), Aigner et al. (2009), Pichler and Lackner
(2009) and Pichler et al. (2012), in which the microstructure of
bitumen is not considered.
so on. This approach leads to a multistep homogenisation
scheme.
As mentioned before, such a homogenisation scheme
considering five scales of observations to predict the
material behaviour of HMA was introduced by Lackner
et al. (see Figure 3) (Lackner et al. 2004, 2005, Aigner
et al. 2009, Pichler and Lackner 2009, Pichler et al. 2012).
Within this model, bitumen is considered as a homo-
geneous material, for which the material behaviour can be
identified directly from rheological experiments, like CR
tests.
In order to be able to describe phenomenons such as
ageing, a detailed micromechanical description of the bitumen
scale is needed. For these reasons, an RVE of bitumen was
derived by taking the following aspects into account:
. The most important material phases and structural
effects are described as good as possible, but only as
accurate that the available physical properties
(volume fractions, material behaviour, etc.) of the
components of bitumen from identification exper-
iments are sufficient for characterisation.
. The characteristic dimension of the material phases
building up the RVE of bitumen must obey the laws
of multiscale modelling, meaning that it has to be
significantly smaller than the RVE itself (signifi-
cantly smaller than about 100 mm – see Figure 3).
. As indicated by the CR test results presented before,
with respect to mechanical properties, the main
effect of ageing seems to be an increase of the
asphaltene content. It therefore seems essential to
consider this material phase explicitly within
micromechanical modelling.
SARA fractionation is the most common procedure to
separate the constituents of bitumen chemically. At first, a
low-viscous phase called maltenes can be isolated from
highly viscous asphaltenes by n-heptane extraction.
Cromatographic methods according to ASTM standards
(Corbett 1969, Lesueur 2009, ASTM D4124-01 2010) can
be applied for further separation of the maltene phase into
saturates, aromatics and resins. As the volume fractions of
the constituents can be determined from fractionation and
the material behaviour of the maltene phase can be
identified from CR tests, these fractions seem to be a
reasonable choice as material phases within an RVE of
bitumen.
Imaging methods such as ESEM are capable of giving
access to the complex microstructure of composite
materials. While a sample is scanned by a focused electron
beam, the signal arising from the interactions between the
surfaces of the constituents of the sample and the electrons
can be intensified by a gas within the testing chamber and,
thus, the microstructure is made visible. When bitumen is
tested by ESEM, results suggest a string-like structure
embedded in a matrix (Stangl et al. 2006) (see Figure 4),
while the top film of the matrix is removed by the electron
beam. Taking a closer look at the strings, spherical centres
can be identified, which are connected by strings.
AFM is another imaging method used to analyse
bitumen. Within the experimental set-up, a sharp tip
(radius about 8 nm) attached to a cantilever is moved over
a sample of the examined material leading to changes of
the interaction between the tip and the surface of the
sample. Consequently, deflections of the cantilever occur,
which are detected by a laser scanning system. Within the
bitumen, a heterogeneous composition, consisting of
micelle (‘bee’)-like structures embedded into a matrix, can
be identified (Bodan 1982, Yen 1992, Espinat et al. 1998,
Forbes et al. 2001, Pauli et al. 2003, Bearsley et al. 2004,
Jäger 2004, Masson et al. 2006, Stangl et al. 2006, Lesueur
2009, Schmets et al. 2010, Nahar et al. 2013a, 2013b,
2014) (see Figure 4). The less pronounced visible string-
structure, compared to the ESEM pictures, is assumed to
be a result of the matrix phase forming a veil on the
surface. Nevertheless, since the cells and strings exhibit
similar dimensions, these micelle-like structures seem to
correlate with the spherical structures as seen from ESEM
results. As AFM images indicate that the number of
‘bee’-like inclusions increases with increasing asphaltene
content, asphaltenes are supposed to be responsible for
these structures. In addition, experimental results from CR
tests show that stiffness increases with increasing
asphaltene content and decreasing saturate content for
artificially composed binders, which exhibit the same
microstructural features as natural bitumen. Within this
work, AFM and ESEM results are only used to confirm the
microstructural concept of bitumen, as well as to identify
the characteristic dimension of asphaltene inclusions to
ensure that the structure chosen is an appropriate
observation scale under the mastic scale.
With a length between 1 and 10 mm (see Figure 4), the
characteristic dimension of these (asphaltene) inclusions is
 International Journal of Pavement Engineering 943

Interaction between Micelle mantles

Asphaltene Micelles

0 10 50 µm
~100 µm

162
~1-10 µm

0 nm Interaction between Micelle mantles

Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015

Asphaltenes
Resins and Aromatics
Saturates

Figure 4. ESEM image (Stangl et al. 2006) (upper), AFM topography scan (Jäger 2004) (left) and microstructural concept of bitumen
based on SARA fractions (right).

significantly smaller than filler particles (d#125 mm) at
the mastic scale and, therefore, is also smaller than the
selected RVE size. Hence, an important precondition of
continuum micromechanics is fulfilled and a strong
indicator is given that an RVE of bitumen based on
SARA fractions can be a logic and reasonable extension of
the multiscale model for HMA presented in Figure 3.
Based on this, a concept of the microstructure of
bitumen is proposed in Figure 4 (right), consisting of a
contiguous matrix of aromatics and resins with embedded
saturate and asphaltene inclusions, and a structural concept
of an RVE is implemented into a homogenisation scheme
predicting the overall mechanical behaviour of bitumen
(see Figure 5). An RVE of bitumen is built up by a
contiguous matrix of aromatics and resins with spherical
saturate and asphaltene (labelled by suffix ’aspha’)
inclusions (see Figure 5). The network-like structure
built up by the micelle mantles is represented by an
interaction phase (suffix ’ip’) appearing as needles, being
oriented in all directions.
For this work, identification experiments are available
for maltenes (saturates, aromatics and resins). While in a
first step aromatics– resin matrix and saturate inclusions
are assumed to exhibit the same viscoelastic behaviour, the
determination of the material properties of saturates is a
task of ongoing investigation. Furthermore, asphaltenes
and their mantles are considered as different phases with
respect to volume content and morphology, but assumed to
show the same viscoelastic response because of acting
together in the micelle structure.
To be able to compare model predictions with
experimental results, the overall bitumen behaviour has
to be given in terms of the homogenised shear compliance
J bit ðtÞ, which could be determined following a five-step
procedure:
(1) Due to the viscoelastic characteristics of bitumen
and its constituents, the homogenisation is
conducted in the Laplace Carson (LC) domain
defined through frequency variable p with the LC
transformation according to Donolato (2002),
resulting in formally linear elastic behaviour.
(2) The properties of the material phases are
represented through a defined material model,

Interaction between Micelle mantles

Asphaltenes
Resins and Aromatics
Saturates

Figure 5. Derived structural RVE concept for micromechanical model.

 944
namely the power-law model, consisting of a
linear spring element and a nonlinear dashpot in
series. The material behaviour can be described in
a LC domain reading
*
J i ¼ J 0;i þ J a;i ðpt!Þ2ki Gð1 þ ki Þ;
where J 0;i is the elastic shear compliance of phase
i, and J a;i and ki are viscous parameters.
(3) Considering constitutive equations in the LC
domain together with the viscoelastic correspon-
dence principle (Read 1950, Sips 1951, Laws and
McLaughlin 1978, Beurthey and Zaoui 2000) and
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015
L. Eberhardsteiner et al.
*
from which component J 4444 ðpÞ can be back-
transformed into the time domain employing the
Gaver – Stehfest algorithm as outlined in Stehfest
(1970).
(5) The so obtained shear creep compliance J bit ðtÞ
ð2Þ allowes a comparison with the measured exper-
imental result J exp ðtÞ according to Equation (1).
For the theoretical background and validation of the
presented multiscale approach, please refer to Eberhard-
steiner et al. (2014).
3.2. Ageing effects

formally elastic matrix-inclusion problems of the

Eshelby –Laws type (Eshelby 1957, Laws 1977)
results in a Mori – Tanaka-homogenisation scheme
(Mori and Tanaka 1973, Wakashima and Tsuka-
moto 1991), typical for composite materials
consisting of a contiguous matrix with inclusions.
Within this scheme, the physical material proper-
ties (through the fourth-order relaxation tensor
*
ri ðpÞ related to Equation (2)), the volume fractions
f i and the morphologies (through the fourth-order
* ;arom * ;arom
Hill tensors Psph ðpÞ and Pcyl ðpÞ for spherical
and cylindrical inclusions, respectively) of all
material phases i are taken into account to estimate
*
the creep relaxation tensor of bitumen Rbit ðpÞ
(Eberhardsteiner et al. 2014), yielding
!
* *
Rbit ðpÞ ¼ ð1 2 f aspha 2 f ip 2 f sat Þrarom ðpÞ
h * ;arom
* *
þ f aspha raspha ðpÞ : I þ Psph
As described before, during the exposure of bitumen to
environmental impacts, its material characteristics change
due to ageing effects. A significant increase of the
asphaltene content is mainly responsible for structural
changes, while the material behaviour of the constituents
do not alter considerably.
These effects can be explained from a chemical point of
view, by considering the polarity distribution between the
different material phases (chromatographic methods as used
for the separation in SARA fractions are based on the fact that
chemically different constituents differ in polarity – see
Figure 6). When adding asphaltenes to the contiguous matrix
seen in Figure 5, differences in polarity lead to an
agglomeration of aromatics and resins to the asphaltenes,
" #i21
*
ðpÞ : raspha ðpÞ 2 rarom ðpÞ

* Ð 2p Ð p h * ;arom
"
* *
#i21
sin qdqdw
þ f ip rip ðpÞ : w¼0 q¼0 I þ Pcyl ðq; w; pÞ : rip ðpÞ 2 rarom ðpÞ 4p
h i '
* * ;arom % * *
& 21
þ f sat rsat ðpÞ : I þ Psph ðpÞ : rsat ðpÞ 2 rarom ðpÞ
! ð3Þ
: ð1 2 f aspha 2 f ip 2 f sat ÞI
h * ;arom
" #i21
* *
þf aspha I þ Psph ðpÞ : raspha ðpÞ 2 rarom ðpÞ
Ð 2p Ð p h * ;arom
"
* *
#i21
sin qdqdw
þ f ip w¼0 q¼0 I þ Pcyl ðq; w; pÞ : rip ðpÞ 2 rarom ðpÞ 4p

h i '21
* ;arom % * *
& 21
þ f sat I þ Psph ðpÞ : rsat ðpÞ 2 rarom ðpÞ :

(4) In order to describe the creep response of bitumen
in a physically relevant format, the LC-trans-
formed creep tensor has to be determined, using
* *
Jbit ¼ ½Rbit &21 ;
resulting in the formation of a solvation layer (mantle), which
helps to stabilise the asphaltenes within the maltene matrix.
These mantles interact with each other dependent on the
volume fraction of asphaltenes and, thus, form a network-like
micelle structure, which could serve as a reasonable
ð4Þ explanation for the abrupt stiffness gain seen in Figure 2.
 International Journal of Pavement Engineering 945
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015

Figure 6. Model for the polarity distribution in material phases, for unaged (black line) and aged (blue line) bitumen.

As saturates can be considered almost inert and As outlined in Aigner et al. (2009), the power-law
asphaltenes only exhibit low reactivity at ambient model, used to describe the mechanical behaviour of
conditions due to their solid state, the significant bitumen and its constituents, is able to desrcibe the
susceptibility of highly polar aromatics and resins to experimentally obtained viscoelastic response very well,
oxidative species makes the micelle mantles likely to be implying a physically relevant form of Equation (2)
responsible for decreasing elasticity and ductility of according to Füssl et al. (2013), reading
bitumen, especially due to long-term ageing. The degree of ! t "k
the associated state of the constituents – and thus the J mod ðtÞ ¼ J 0 þ J a : ð5Þ
t!
polarity – decreases qualitatively with increasing distance
to an asphaltene micelle (see Figure 6) and, hence, To identify parameters J 0;malt , J a;malt and kmalt of the
oxidation takes place mainly at the surface of the micelle maltene phase, the error between experimentally obtained
mantles. Consequently, a highly polar layer is formed creep compliances J exp from CR identification tests and
persisting at the outside of the mantle as a consequence of predicted creep compliances J mod is minimised through
the low mobility of molecules at ambient conditions and, nonlinear least square fitting. The obtained power-law
therefore, the ’effective’ volume content of asphaltenes parameters for the maltene phase at 2 58C, þ 58C and
increases (see blue line in Figure 6) (Handle et al. 2013). þ 158C are given in Table 2, describing almost perfect fits.
As the substances considered as material phases in the As the material behaviour of asphaltenes and the
structural RVE concept in Figure 5 do not transform within interaction phase cannot be determined from identification
this process, their material properties do not change, which experiments, the power-law parameters are back-calcu-
can be confirmed by experimental observations seen in lated from experimental results from samples of artificially
Section 2. composed bitumen with an asphaltene content of 4.18% at
a temperature of þ 58C using the coefficient of
determination R 2 as an indicator for the degree of
accordance. Thereby, parameters J 0;aspha , J a;aspha and kaspha
4. Comparison of model predictions and test results – appropriate for asphaltenes as well as for the interaction
With the micromechanical model proposed in Section 3.1, phase – lie within a range, where they influence the
the viscoelastic behaviour of bitumen can be predicted,
considering the ageing-induced change of the material Table 2. Power-law parameters for maltene phase at 258C,
response due to increasing asphaltene content. Thereby, þ58C and þ 158C.
the identification of the model input parameters is a crucial – 58C þ58C þ 158C
task. While the material properties of the maltene phase
can be characterised by CR tests, the material behaviour of J 0;malt [1/MPa] 0:0980 0:2652 2:433
asphaltenes and the volume fraction of the interaction J a;malt [1/MPa] 0:0076 0:0766 1:205
kmalt [ – ] 0:8124 0:9386 1:027
phase have to be back-calculated from CR test results from R2 0:99 0:99 0:99
artificially composed bitumen.
 946
45
40
Interaction phase content [%] 35
30
25
20
15
10
5
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015
0
0 2
Figure 7. Exponential relationship between asphaltene and needle content (representing the interaction between micelle mantles).
predicted material response only insignificantly (Eber-
hardsteiner et al. 2014).
Since the needle-shaped interaction phase describes the
structural influence of the asphaltene micelle network, its
volume fraction f ip is directly related to the asphaltene
content. Similar to the power-law parameters, the volume
fraction of the interaction phase f ip is determined on a best-
fit basis also employing R 2 to evaluate the degree of
accordance. When correlating asphaltene and back-
calculated needle content, an exponential relation can be
found for (realistic) asphaltene contents up to 17.36% (see
Figure 7), typically for molecular agglomeration processes
in nature.
With all input parameters available, model predictions
are compared to experimental results from aged artificially
composed bitumen with asphaltene contents of 4.18%,
7.77%, 12.32% and 17.36% shown in Figure 8. Besides the
known volume fraction of the asphaltenes, the content of
the interaction phase was the only parameter varied.
Figure 8 shows a remarkable accordance between test
results and viscoelastic response predicted by the derived
micromechanical model. Analogously, very good accord-
ance can be found for temperatures of 2 58C and þ 158C
using asphaltene properties estimated from the change of
temperature-dependent behaviour of the maltene phase.
To validate the proposed model not only on artificially
composed but also on natural bitumens, CR tests were
conducted on unaged, laboratory-short-term aged (using
RTFOT equipment) and laboratory-long-term aged (using
RTFOT and PAV equipment) unmodified bitumen pen
70/100 samples with known asphaltene content. The
results can be seen in Figure 9.
The experimental results were related to model
predictions, taking the actual asphaltene contents into
account. As can be seen in Figure 9, predictions of long-
term ageing (13.36% asphaltene content) fit experimental
L. Eberhardsteiner et al.
y=0.4037*exp(0.2559*x)
4 6 8 10 12 14 16 18
Asphaltene content [%]
results very well. As described in Section 2, bitumen has to
be heated for the identification of the asphaltene content
through n-heptane extraction. As the asphaltene content
(n-heptane-soluble phase) is strongly affected by heating
due to ageing, its determination is a challenging task.
Especially for unaged and short-term aged samples, which
are more susceptible to ageing effects than already long-
term aged samples, the reliable specification of the amount
of asphaltenes is difficult. However, model predictions
considering a realistic asphaltene content for unaged and
short-term aged samples between 4% and 9% cover
experimental results very well.
5. Conclusion
In this paper, ageing effects of bitumen and their
microstructural nature were investigated by examining
bitumen chemically and rheologically. In addition, a
micromechanical model is presented providing a first
approach to predict the viscoelastic behaviour of bitumen
on the basis of its microstructure, as well as to describe the
effects of ageing on its mechanical behaviour.
The obtained results can be summarised as follows:
. Artificially composed bitumens with varying
asphaltene contents were examined in CR tests –
a static shear creep experimental set-up – in unaged
condition as well as after laboratory long-term
ageing (RTFOT þ PAV ageing). While an increase
in asphaltene content resulted in an expected
decrease of the measured creep compliance, the
addition of only low amounts of asphaltenes (from
0 vol-% to 4.18 vol-%) caused a surprisingly abrupt
increase in stiffness (the creep compliance decreases
from approximately 90 1/MPa to 20 1/MPa),
indicating a structural effect which acts hardening.
 International Journal of Pavement Engineering 947

100
102
0% Asphaltene
0% Asphaltene − aged
80 4.18% Asphaltene
4.18% Asphaltene − aged 0% Asphaltene
100
7.77% Asphaltene
60
7.77% Asphaltene − aged

J[1/MPa]
17.36% Asphaltene
J[1/MPa]

0% Asphaltene
40 17.36% Asphaltene − aged 10–2 0% Asphaltene − aged
micromechanical model
4.18% Asphaltene 4.18% Asphaltene
4.18% Asphaltene − aged
20
7.77% Asphaltene
10–4
7.77% Asphaltene − aged
0 17.36% Asphaltene
17.36% Asphaltene 17.36% Asphaltene − aged
10–6 micromechanical model
−20
0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000 1200 1400 1600 1800
t [s] t [s]
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Figure 8. Comparison of experimental results and micomechanical model predictions for aged artificial bitumen with asphaltene
contents of 4.18%, 7.77%, 12.32% and 17.36% at þ58C. Creep compliance is shown on a linear scale (left) and on a logarithmic scale
(right) for a better representation of creep curves with high asphaltene content.

A comparison between results from aged and which is able to predict the viscoelastic behaviour of
unaged samples shows that the material properties bitumen on the basis of its composition. Based on
of the constituents remain unaffected and, hence, SARA fractions, a homogenisation scheme is
only the remarkable increase in asphaltene content proposed, where the RVE of bitumen consists of a
observed (from 7.79 vol-% to 13.36 vol-%) appears contiguous matrix of aromatics and resins with
to be responsible for the ageing-induced increase of spherical saturate and asphaltene inclusions. Asphalt-
stiffness and decrease of creep rate dJ=dt and enes and a mantle around them, built up by highly
ductility of the bituminous layers. polar aromatics and resins, form network-like micelle
. ESEM and AFM images give insight into the structures, which are represented by a needle-shaped
microstructure of bitumen, confirming a compo- interaction phase within the homogenisation scheme.
sition consisting of a micelle-like structure As AFM and ESEM images confirm that the
embedded in a contiguous matrix. From CR test characteristic lengths of the inclusions (assumed
results, conducted on artificially composed bitumen, asphaltenes) to be significantly smaller than filler
it can be assumed that asphaltenes are responsible particles at the mastic scale, this model can be used to
for these micelle structures. extend an existing multiscale model for HMA.
. In order to take the microstructure of bitumen into . This micromechanical model was used to predict the
account, a micromechanical model was developed, viscoelastic behaviour of bitumen, showing very good

16
70/100 unaged
14 70/100 short−term aged
70/100 long−term aged
12 micromechanical model

10
J[1/MPa]

8 Hardening due to
short−term aging
6
model
4 (asphaltene content
range from 4% to 9%)
model long−term aged
2 (13.36% asphaltenes)

0
0 200 400 600 800 1000 1200 1400 1600 1800
t[s]

Figure 9. Comparison of experimental results and micromechanical model predictions for unaged, RTFOT- and RTFOT þ PAV-aged
natural bitumen 70/100.
 948 L. Eberhardsteiner et al.
accordance between predicted and experimental
results for artificially composed bitumen with a
predefined asphaltene content. In addition, model
predictions fit experimental results from unaged,
laboratory-short-term aged (using RTFOT equip-
ment) and laboratory-long-term aged (using RTFOT
and PAV equipment) unmodified bitumen pen 70/100
samples with known asphaltene content to a
remarkable extent.
Due to the complex assembling of artificially
composed bitumen, only the microstructure of one specific
unmodified bitumen pen 70/100 was studied in the course
of this work. The investigation of other bitumens to
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improve the validation of the presented micromechanical
model is a topic of further research. Moreover, a possible
rejuvenation of bitumen by adding maltenes to reduce the
asphaltene content appears as an interesting task.
In addition, a more comprehensive identification of the
mechanical properties of the material phases (e.g.
saturates) is a task of ongoing investigation.
Acknowledgements
The authors appreciate the support of Daniel Grossegger and
Thomas Riedmayer with sample preparation and execution of CR
tests.
Funding
The authors gratefully acknowledge financial support from the
Austrian Research Promotion Agency (FFG) and the sponsors
Pittel þ Brausewetter, Swietelsky and Nievelt through project
‘OEKOPHALT – Physical-chemical fundamentals on bitumen
ageing’.
References
Aigner, E., Lackner, R., and Pichler, C., 2009. Multiscale
prediction of viscoelastic properties of asphalt concrete.
Journal of Materials in Civil Engineering (ASCE), 21,
771– 780.
ASTM D4124-01, 2010. Standard test methods for separation of
asphalt into four fractions. ASTM International.
Bearsley, S., Forbes, A., and Haverkamp, R., 2004. Direct
observation of the asphaltene structure in paving-grade
bitumen using confocal laser-scaning microscopy. Journal of
Microscopy, 215 (2), 149– 155.
Bell, C., 1989. Summary report on aging of asphalt-aggregate
systems. Washington, DC: National Research Council, SHRP
Report Number (A-305).
Beurthey, S. and Zaoui, A., 2000. Structural morphology and
relaxation spectra of viscoelastic heterogeneous materials.
European Journal of Mechanics – A/Solids, 19 (1), 1– 16.
Bodan, A., 1982. Polyquasispherical structure of petroleum
asphalts. Chemistry and Technology of Fuels and Oils, 18,
614– 618.
Corbett, L., 1969. Composition of asphalt based on generic
fractionation, using solventdeasphaltening, elution-adsorp-
tion chromatography and densimetric characterization.
Analytical Chemistry, 41, 576– 579.
Donolato, C., 2002. Analytical and numerical inversion of the
Laplace – Carson transform by a differential method. Compu-
ter Physics Communications, 145, 298– 309.
Eberhardsteiner, L., et al., 2014. Influence of asphaltene content
on mechanical bitumen behavior – experimental investi-
gation and micromechanical modeling. Materials and
Structures, doi:10.1617/s11527-014-0383-7.
Eshelby, J., 1957. The determination of the elastic field of an
ellipsoidal inclusion, and related problems. Proceedings of
the Royal Society London, Series A, 241, 376– 396.
Espinat, D., Rosenberg, E., Scarsella, M., Barre, L., Fenistein, D.,
and Broseta, D., 1998. Colloidal structural evolution from
stable to flocculated state of asphaltene solutions and heavy
crudes. Structures and Dynamics of Asphaltenes, 145– 201.
Forbes, A., Haverkamo, R.G., Robertson, T., Bryant, J., and
Bearsley S., 2001. Studies of the microstructure of polymer-
modified bitumen emulsions using confocal laser scanning
microscopy. Journal of Microscopy, 204 (3), 252– 259.
Füssl, J., Lackner, R., and Eberhardsteiner, J., 2013. Creep
response of bituminous mixtures – rheological model and
microstructural interpretation. Meccanica, doi:10.1007/
s11012-013-9775-y.
Grover Allen, R., Little, D., and Bhasin, A., 2012. Structural
characterization of micromechanical properties in asphalt
using atomic force microscopy. Journals of Materials in
Civil Engineering, 24 (10), 1317– 1327.
Handle, F., et al., 2013. Understanding the microstructure of
bitumen: a CLSM and fluorescence approach to model
bitumen ageing behavior. 12th ISAP international conference
on asphalt pavements, Raleigh, USA.
Hill, R., 1963. Elastic properties of reinforced solids: some
theoretical principles. Journal of the Mechanics and Physics
of Solids, 11, 357– 362.
Hill, R., 1965. Continuum micro-mechanics of elastoplastic
polycrystals. Journal of Mechanics and Physics of Solids,
13 (2), 89 – 101.
Huang, S., Tia, M., and Ruth, B., 1996. Laboratory aging
methods for simulation of field aging of asphalts. Journal of
Materials in Civil Engineering, 8 (3), 147– 152.
Jäger, A., 2004. Microstructural identification of bitumen by
means of atomic force microscopy (AFM), modulated
differential scanning calorimetry (MDSC), and reflected
light microscopy (RLM). Master’s thesis, Vienna University
of Technology, Vienna.
Lackner, R., et al., 2004. Multiscale modeling as the basis for
reliable predictions of the behavior of multi-composed
materials. Progress in Engineering Computational Technol-
ogy, Saxe-Coburg Publications, 8, 153– 187.
Lackner, R., et al., 2005. Is the low-temperature creep of asphalt
mastic independent of filler shape and mieralogy? –
Arguments from multiscale analsysis. Journal of Materials
in Civil Engineering (ASCE), 17 (5), 485– 491.
Laws, N., 1977. The determination of stress and strain
concentrations at an ellipsoidal inclusion in an anisotropic
material. Journal of Elasticity, 7 (1), 91 – 97.
Laws, N. and McLaughlin, R., 1978. Self-consistent estimates for
the viscoelastic creep compliances of composite materials.
Proceedings of Royal Society, London, Series A, 359, 251–273.
Lesueur, D., 2009. The colloidal structure of bitumen:
consequences on the rheology and on the mechanisms of
bitumen modification. Advances in Colloid and Interface
Science, 145, 42 – 82.
 International Journal of Pavement Engineering
Masson, J., Leblond, V., and Margeson, J., 2006. Bitumen
morphologies by phase-detection atomic force microscopy.
Journal of Microscopy, 221 (1), 17 – 29.
Mori, T. and Tanaka, K., 1973. Average stress in matrix and
average elastic energy of materials with misfitting inclusions.
Acta Metallurgica, 21 (5), 571– 574.
Nahar, S., et al., 2013a. First observation of blending-zone
morphology at interface of reclaimed asphalt binder and
virgin bitumen. Transportation Research Record: Journal of
the Transportation Research Board, 2370 (1), 1 –9.
Nahar, S., et al., 2013b. Temperature and thermal history
dependence of the microstructure in bituminous materials.
European Polymer Journal, 49 (8), 1964 –1974.
Nahar, S., et al., 2014. Turning back time: rheological and
microstructural assessment of rejuvenated bitumen. TRB
93rd Annual Meeting Compendium of Papers, 1 – 17.
Downloaded by [TU Technische Universitaet Wien], [Josef Füssl] at 04:14 10 July 2015
Nicholls, J., 2007. Analysis of available data for validation of
bitumen tests. Report on Phase 1 of the BiTVal project.
Available from: http://www.bitval.fehrl.org/fileadmin/bitval/
BitVal_final_report.pdf
Pauli, A., et al., 2003. Atomic force microscopy investigation of
SHRP asphalts. Abstracts of Papers of the American
Chemical Society, 221, 104– 110.
Pichler, C. and Lackner, R., 2009. Upscaling of viscoelastic
properties of highly-filled composites: investigation of
matrix-inclusion type morphologies with power-law viscoe-
lastic material response. Composite Science and Technology,
69, 2410– 2420.
Pichler, C., Lackner, R., and Aigner, E., 2012. Generalized self-
consistent scheme for upscaling of viscoelastic properties of
highly-filled matrix-inclusion composites – application in
the context of multiscale modeling of bituminous mixtures.
Composites: Part B, 43, 457– 464.
Read, W., 1950. Stress analysis for compressible viscoelastic
media. Journal of Applied Physics, 21 (7), 671– 674.
View publication stats
949
Read, J. and Whiteoak, D., 2003. The shell bitumen handbook.
5th ed. London: Thomas Telford.
Scheiner, S. and Hellmich, C., 2009. Continuum microviscoe-
lasticity model for aging basic creep of early-age concrete.
Journal of Engineering Mechanics, 135 (4), 307– 323.
Schmets, A., et al., 2010. On the existence of wax-induced phase
separation in bitumen. International Journal of Pavement
Engineering, 11 (6), 555– 563.
Sips, R., 1951. General theory of deformation of viscoelastic
substances. Journal of Polymer Science, 7 (2 – 3),
191– 205.
Stangl, K., Jäger, A., and Lackner, R., 2006. Microstructure-based
identification of bitumen performance. International Journal of
Road Materials and Pavement Design, 7, 111–142.
Stehfest, H., 1970. Algorithm 368: numerical inversion of Laplace
transforms. Communications of the ACM, 13, 47–49.
Suquet, P., ed., 1997. Continuum micromechanics. Vienna:
Springer.
Traxler, R., 1961. Relation between asphalt composition
and hardening by volatilization and oxidation. Proceedings
of the Association of Asphalt Paving Technologists, 30,
359– 372.
Wakashima, K. and Tsukamoto, H., 1991. Mean-field
micromechanics model and its application to the analysis
of thermomechanical behaviour of composite materials.
Materials Science and Engineering A, 146 (1-2),
291– 316.
Yen, T., 1992. The colloidal aspect of a macrostructure of
petroleum asphalt. Fuel Science and Technology Inter-
national, 10, 723– 733.
Zaoui, A., 1997. Structural morphology and constitutive
behavior of microheterogeneous materials. New York:
Springer.
Zaoui, A., 2002. Continuum micromechanics: survey. Journal of
Engineering Mechanics (ASCE), 128 (8), 808–816.