Road Materials and Pavement Design

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Atomic force microscopy to investigate asphalt

binders: a state-of-the-art review

Prabir Kumar Das, Hassan Baaj, Susan Tighe & Niki Kringos

To cite this article: Prabir Kumar Das, Hassan Baaj, Susan Tighe & Niki Kringos (2016) Atomic
force microscopy to investigate asphalt binders: a state-of-the-art review, Road Materials and
Pavement Design, 17:3, 693-718, DOI: 10.1080/14680629.2015.1114012

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Road Materials and Pavement Design, 2016
Vol. 17, No. 3, 693–718, http://dx.doi.org/10.1080/14680629.2015.1114012

Atomic force microscopy to investigate asphalt binders: a state-of-the-art

review
Prabir Kumar Dasa∗, , Hassan Baaja , Susan Tighea and Niki Kringosb
a Centre for Pavement and Transportation Technology, University of Waterloo, Waterloo, ON, Canada N2L
31; b Division of Highway and Railway Engineering, KTH Royal Institute of Technology, Stockholm SE-100
44, Sweden

(Received 18 April 2015; accepted 23 October 2015 )

Atomic force microscopy (AFM) is a non-destructive imaging tool, which is capable of qual-
itative and quantitative surface analysis with sub-nanometer resolution. Simultaneously with
the topology at the micro-scale, AFM is capable of acquiring micro-mechanical information
such as relative stiffness/Young’s modulus, stickiness/adhesion, hardness, energy loss and
sample deformation quantitatively. This paper presents an extensive review on the applica-
tions of AFM to investigate different physiochemical properties and performances of asphalt
binder. AFM techniques and principles, different sample preparation techniques and its effect
on observed micro-structures, chemical origin, surface or bulk phenomenon and temperature
sensitivity of these micro-structures are also discussed in this paper. All of the studies con-
ducted on this topic clearly indicated that AFM can successfully be utilised as a tool to better
understand how the surface morphology and its physicochemical properties are interlinked
and related to the binder performances.
Keywords: asphalt; binder; atomic force microscopy; micro-structure; micro-mechanical
properties

1. Introduction
Asphalt binder is the residue obtained from the vacuum distillation of petroleum oil, which is
a complex mixture of organic molecules of different sizes and polarities. It is widely used as a
binder material in flexible asphalt pavements. Even though the asphalt binder is only one com-
ponent in an asphalt mixture, it is the component that provides the material with the desired
viscoelastic properties. In addition to increasing driving comfort and flexible maintenance, this
viscoelastic behaviour plays a prominent role in many aspects of mixture durability, such as
resistance towards thermally or traffic-induced cracking and ravelling.
It is now widely accepted that asphalt binder is neither a homogeneous nor a single phase
system, but contains micro-structures with a size of several microns to tenth of microns with
different micro-mechanical properties, as noted in Figure 1. The thermo-rheological behaviour
of asphalt binder depends largely on its chemical structure and intermolecular micro-structures.
The mechanical behaviour of the material due to its micro-structures may be responsible for the
physical properties of asphalt binder such as stiffness, elasticity and plasticity, adhesion, surface
energy and healing (Allen, Little, Bhasin, & Glover, 2014; Lesueur, 1996; Loeber, Muller, Morel,

*Corresponding author. Email: prabir.das@uwaterloo.ca

© 2015 Informa UK Limited, trading as Taylor & Francis Group

694 P.K. Das et al.

Figure 1. Typical AFM images of asphalt binder: (a) topographic 2D, (b) 3D, (c) line profile along
‘bee-shaped’ micro-structure and (d) relative stiffness, which indicates evidence of micro-structures.

& Sutton, 1998). Thus, knowledge of micro-scale performance will help to optimise the binder
in its production stage.
One of the nanotechnology techniques that have received increasing attention for examin-
ing the physiochemical behaviour of micro-structures of bituminous materials is the atomic
force microscopy (AFM). AFM is a non-destructive imaging tool that can deliver the surface
topography, stiffness, tackiness information and molecular interaction at micro-level of mate-
rials (Bellitto, 2012). The advantages of AFM is that the sample preparation is rather simple,
time efficient and does not induce any artefacts, and can operate under ambient conditions or
at any specific temperatures. Moreover, the observed micro-structures under AFM have earlier
been proven to be a unique and reproducible property of any specific asphalt binder (Nahar
et al., 2013a; Soenen et al., 2014), which makes AFM a versatile research tool for a mate-
rial as complex as asphalt. Recently, a literature review has been conducted by Yu, Burnham,
and Tao (2015) on using AFM to characterise surface micro-structure of asphalt binder. The
study was mainly focused on the origin of these micro-structures, without addressing any appli-
cation of AFM. However, in this current study, the authors expanded the area of interest by
summarising the application of AFM as a tool to investigate asphalt binders. This will provide
to the community a unique collection of literature reviews on different applications of AFM
in the asphalt field and also developing the fundamental understanding on observed surface
micro-structures.
This paper presents an extensive review on the applications of AFM to investigate different
physiochemical properties and performances of asphalt binder. In that process, AFM techniques
and principles, different sample preparation techniques and their effects on observed micro-
structures, chemical origin, surface or bulk phenomenon and temperature sensitivity of these
micro-structures are also discussed in this paper. Furthermore, recommendation for future work
and application are proposed.
 Road Materials and Pavement Design 695

2. AFM techniques and principles

In an effort to understand and characterise the asphalt binder micro-structure, optical microscopy
techniques and especially polarised light microscopy have been used in the asphalt field (Lu,
Langton, Olofsson, & Redelius, 2005). This investigation reported the presence of wax-induced
micro-structures in some of the specific binders. However, because of the opacity limitation and
adhesive properties of binder, researchers have also used scanning probe microscopy such as
AFM to investigate these micro-structures (Jäger, Lackner, Eisenmenger-Sittner, & Blab, 2004;
Loeber, Sutton, Morel, Valleton, & Muller, 1996). AFM is capable of measuring almost any type
of surfaces at atomic and molecular resolutions as compared with the resolution limit of optical
microscopy of about 200 nm. This has clearly opened the window for further investigations of
the micro-mechanical behaviour of binder micro-structures.
In the 1980s, the scanning tunnelling microscope was developed by Binnig, Rohrer, Gerber,
and Weibel (1982). This invention, which led to the Nobel Prize in Physics in 1986, was a
precursor to the AFM, which was developed by Binnig, Quate, and Gerber (1986). The principle
of the AFM set-up, illustrated in Figure 2, is composed of a cantilever carrying a colloidal probe
in contact with a sample surface, the laser path and the piezo transducer. The cantilever with
either a sharp tip or a colloidal probe interacts with the surface of a sample which is moved in
the x, y and z directions by piezo actuators. A laser beam focused at the end of the cantilever is
reflected into a detector and when the cantilever experiences a force, by a topographical, chemical
or electrical feature on the sample, the cantilever is deflected leading to a deviation of the laser
beam from its original position on the detector. This deviation is measured as a voltage, which
can be translated into a force or a relative height.
Classical AFM imaging is obtained either in contact mode, where the tip is in contact with
the sample at constant load while the surface is moving in the x–y direction, or in tapping mode,
where the cantilever oscillating at its resonance frequency is gently tapped on the surface which

Figure 2. Schematic illustration of general components of AFM and their functions.

Source: MIT.
696 P.K. Das et al.

is moving in the z-direction to reach contact and then in the x–y directions when the tip is lifted
away from contact. Topographic data are obtained from both techniques, but contact mode pro-
vides frictional data and tapping mode provides phase data, which reflect the damping of the
oscillation as the tip and the surface are in contact. The ‘phase’ image can be interpreted as a
material property map reflecting the elasticity of the sample (Fischer, Poulikakos, Planche, Das,
& Grenfell, 2013a).
Nowadays, force measurements have been an AFM technique apart from imaging where only
one interaction spot is chosen to obtain detailed force–distance curves for the specific interac-
tion between the sample surface and either a tip or colloidal probe mounted at the end of a
tip-less cantilever. The calibration (Cleveland, Manne, Bocek, & Hansma, 1993) and data eval-
uation of this system were manual and slow, and normally the chemical interactions are not
mechanical properties in focus (Wallqvist, Claesson, Swerin, Schoelkopf, & Gane, 2006). The
two-dimensional force mapping of a surface using this method is rather time consuming and the
graphical representation of a given property obtained from the force curve is often low-resolved.
Recent development of the AFM technique has married imaging with force measurements giv-
ing access to high-resolved 2D force mapping. In this method, the sample is similar to classical
force measurements moved in and out of contact with the calibrated cantilever (Sader, Chon, &
Mulvaney, 1999). However, the movement is now automated and rather quick, typically 2 kHz,
which is about 1000 times faster than for classical force measurements. The obtained force curve
data are evaluated online and selected regions plotted separately in 2D property maps.

3. Investigation on phase separation utilising AFM

In the asphalt binder research domain, Loeber et al. (1996, 1998) were the first research group
to conduct a comprehensive study on the asphalt binder surface utilising AFM as a tool. In their
study, ripple micro-structures with several micrometers in diameter and tens of nanometers in
height were reported and nicknamed bumble-bees due to their resemblance to the black and
yellow strips, which is now commonly known as ‘bee-shaped’ micro-structures, as shown in
Figure 1. Other shapes and textures including networks and spherical clusters were also observed.
These micro-structures mainly cause phase separation in the binder matrix; later on, different
researchers investigated on what are these micro-structures, how they evolve with time and the
temperature, is it a surface or bulk phenomenon, how are these related to the binder performance
and so on. In this section, the sample preparation techniques, reasons behind the bee-shaped
micro-structuring and whether these micro-structures are only present on the surface or also in
the bulk will be discussed in detail.

3.1. Sample preparation techniques

AFM has been widely used to provide insight into the micro-structures that can be observed on
the surface of binders. Special attention is needed in sample preparation as surface topography
can be highly influenced by the preparation process itself. For adhesive and viscoelastic material
like asphalt binder, surface preparation becomes an even more important factor for avoiding any
artefacts. Moreover, binder shows ageing due to oxidation and also collects dust or other airborne
particles with time if not stored in a dust-free environment. These particle contaminations may
collect, especially at the surface and will hence disturb/alter the surface pattern as observable
by AFM. Thus, the sample preparation techniques had always been a concern while conducting
AFM scanning of binders. From the studied literature, it can be observed that spin casting and
heat casting are the two most commonly practiced methods used for sample preparation.
In the spin casting method, the sample is produced by dissolving asphalt binder in a solvent
and after that the solution is cast on a spinning plate. The centrifugal forces of the spinning plate
 Road Materials and Pavement Design 697

(a) (b) (c)

Figure 3. AFM topography images (40 μm × 40 μm) of same asphalt binder as a function of film
thickness (Pauli et al., 2011).

spread the solution evenly and after evaporation of the solvent the resulting film thickness is in
the nano- to micrometer range depending on the binder concentration in the solvent. In addition,
to eliminate residual solvent that was used during the sample preparation, some researchers pro-
posed to keep the specimen in an airtight heated vacuum desiccator followed by ultra-high purity
dry nitrogen to pass through a purifier (Allen, Little, & Bhasin, 2012). Annealing is also impor-
tant to enable the micro-structure of the asphalt binder to return to its original form and eliminate
any artefacts that may be attributable to the solvent cast spin-coating process. It was shown by
Pauli, Grimes, Beemer, Turner, and Branthaver (2011) that the number and size of the micro-
structural phases can change with respect to film thickness when the thickness is decreased to a
few nanometers, as shown in Figure 3. It can be seen in Figure 3(a)–(c) that the size and shape of
the micro-structures change significantly with the relative film thickness. It was also reported by
the same research group that the structuring becomes essentially constant for films thicker than
10 μm.
In the heat casting method, using material from the top of a can is not recommended as ageing
occurs mainly at the surface. Therefore, the asphalt binder needs to be mixed properly by stirring
around 120 ± 10°C (depending on the types of binder) to avoid such biases. A heat conductive
sample holder can be used to place approximately 20–30 mg of hot liquid binder and keeping
it on a hot plate for 5 min at the same temperature. This will allow the binder to spread out by
creating a smooth surface. Afterwards, the specimens need to be left horizontally and be covered
to prevent dust pick up for at least 24 h at 25°C prior to test. Since all specimens generally go
through the same preparation process, it can be assumed that oxidation during sample prepara-
tion can be ignored or is at least constant amongst all specimens (Das, Kringos, Wallqvist, &
Birgisson, 2013; Fischer et al., 2013a; Soenen et al., 2014).

3.2. Origin of the bee-shaped micro-structures

It has always been a challenge to identify the key driving force behind the appearance of the
bee-shaped micro-structures. Several research projects have been conducted to identify the phe-
nomenon behind the causing of these micro-structures. The research conducted by Loeber et al.
(1998) reported that the bee-shaped micro-structures are unstable and time dependent. One of
their conclusions was that the bee-shaped micro-structures probably correspond to oscillation of
the oil phase during sample preparation and thus with time it disappears. After a couple of years,
Pauli, Branthaver, Robertson, Grimes, and Eggleston (2001) investigated the Strategic Highway
698 P.K. Das et al.

Research Program (SHRP) binders utilising AFM and attributed the asphatenes for these micro-
structuring. The difference between asphaltene molecules and other molecules in asphalt binder is
their insolubility in n-heptane (Redelius, 2006). Asphaltenes are very heterogeneous compounds,
basically made up of polycyclic aromatic constituents, n-alkanes with a chain length larger than
40 carbons and metal-containing polyphorines. To investigate the asphaltene aggregation, Pauli
et al. (2001) doped binder samples with extra asphaltenes and reported observing an increase in
the density of bee-shaped micro-structures on the binder surface.
Later on, in order to assess the chemical composition of the bee-shaped micro-structures, Jäger
et al. (2004) precipitated asphaltenes from the binder matrix by the addition of n-heptane and the
so-obtained material is known as maltane. In contrast to the AFM image of asphalt binder, where
the micro-structures were present, maltane showed no such bees on the surface. Thus, based on
investigation of five different types of binder, in agreement with the previous study by Pauli et al.
(2001), they also concluded that the formation of bee-shaped micro-structures can be related to
the presence of asphaltenes.
Since Loeber et al. (1996) investigated a single binder and Pauli et al. (2001) investigated the
spin casting method, Masson, Leblond, and Margeson (2006) carried out an extensive AFM study
on 13 different types of binder to further investigate the structuring phenomenon by eliminating
the limitations of the previous studies. They had reported on finding four phases, which were
named catanaphase (bee-shaped), periphase (around catanaphase), paraphrase (solvent regions)
and salphase (high phase contrast spots), as shown in Figure 4. Interestingly, they found a very
poor correlation between the asphaltene aggregations and the bee-shaped structures. However,
that was the conclusion in the previous investigations by Pauli and Jäger. Interestingly, it was
reported by Masson et al. (2006) that the mass per cent of vanadium and nickel metals did
correlate well with the observed structuring.
Also, to investigate the structuring phenomenon, De Moraes, Pereira, SimãO, and Leite (2010)
studied the micro-structure behaviour as a function of temperature and Zhang, Wang, and Yu
(2011) investigated the evolution of the micro-structures due to lab ageing. Both of the research
groups had mentioned the possibility that the bee-shaped structuring may be related to paraf-
fin wax crystallisation; however, neither of the studies was able to show any strong evidence.
Schmets, Kringos, Pauli, Redelius, and Scarpas (2010) studied the existence of wax-induced
phase separation in asphalt binder, where they have investigated the formation of wax phases
within the continuum of this material. In this study, the highly magnified bees showed a resem-
blance to the crystalline micro-structures, that is, ledge and terrace assemblages, which leads
to the hypothesis that the observed bee-structures consist mainly of waxes. Further, Pauli et al.

(a) (b) (c)

Figure 4. AFM image of an asphalt binder surface with four different types of phases (Masson et al.,
2006).
 Road Materials and Pavement Design 699

(2011) had scanned different fractions of asphalt binders and found bee-shaped structures even
in the ‘pure’ maltene phase, which contained no asphaltenes, while the de-waxed binder frac-
tions did not show any micro-structures. Based on the findings, in agreement with Schmets, they
had hypothesised that the interaction between crystallising paraffin waxes and the remaining
asphalt fractions is responsible for much of the structuring, which made them refer to this spe-
cific behaviour as ‘wax-induced phase separation’. It was also concluded that the measured wax
fractions did not correlate well with the observed percentage of bees.
The research done by De Moraes et al. (2010), Schmets et al. (2010) and Zhang et al. (2011)
only hypothesised wax-induced micro-structure, but no investigation was conducted on exper-
imental evidence or validation. Since AFM measurement is highly sensitive to the surface
preparation, conclusions from the experimental evidence by Pauli et al. (2011) on solvent cast
films were becoming an issue. Hence, Das et al. (2013) used the heat casting method to avoid
any bias during sample preparation. In their study, AFM was utilised at different temperatures to
investigate the phase separation behaviour for four different types of binders and it was co-related
to the differential scanning calorimetry (DSC) measurements. Each of the binder specimens was
subjected to a heating cycle from 30°C to 60°C, where AFM force mapping was conducted at
every 10°C interval. To understand the crystallisation effect, if any, these specimens went through
a cooling cycle from 60°C to 30°C and, consequently, were scanned under AFM at every 10°C
interval. Finally, the DSC test results were used to understand the AFM phase separation dur-
ing the heating–cooling cycle. Based on evidences found (cf. Figure 5), the authors relate the
observed phase separation to the wax fraction of the asphalt binder, and not to the ‘asphaltene’
phase as was concluded by some earlier researchers.

Figure 5. Correlation of reduced modulus obtained from AFM scanning for (a) B2 and (b) B4 binder with
(c) DSC heating scan (Das, 2014).
700 P.K. Das et al.

Currently, as explained earlier, several researchers have conducted work to identify the origin
of bee-shaped micro-structures, where each of the studies differs to others because of different
sample preparation techniques, different binder types, samples with or without solvents, tested
at different temperatures and so on. As it is well known, AFM itself is an extremely sensitive
tool and combined with all of these uncertainties makes it even more difficult to compare differ-
ent results from different research projects. Keeping this in mind, to investigate the fundamental
mechanisms behind the micro-structural phase appearance, the RILEM technical committee on
nano bituminous materials 231-NBM had conducted a round robin study combining DSC and
AFM, in which eight laboratories (seven from Europe and one from the USA) had participated
(Fischer et al., 2013a; Soenen et al., 2014). In that round robin study, all the labs were using
the same binder samples and a specific procedure to avoid any bias during sample collection and
preparation. The obtained results confirmed the reproducibility and repeatability of the conducted
tests. The observed changes in the phases with both increase and decrease in temperature were
correlated with the DSC curves and from this it was concluded that the behaviour and appear-
ance of the micro-structure was very much related to the wax behaviour, as shown in Figure 6.
Therefore, in agreement with Das et al. (2013), the study conducted by RILEM technical com-
mittee hypothesised that the so-called ‘Bee’ structures are indeed wax induced. In other words,
the interaction between crystallising waxes and the remaining non-wax chemical components in
the asphalt binder matrix is the key reason behind the bee-shaped micro-structure.
Moreover, recently Pauli, Grimes, Cookman, and Huang (2014) investigated the surface struc-
turing of wax in complex media like asphalt binder. In that work, a theory was presented on the
physicochemical nature of surface structuring in binders and its fractions, based on investiga-
tions of simpler material systems reported in the literature pertaining to paraffin and polymer
crystallisation. The key conclusion of this study was that the interactions between crystallising

Figure 6. AFM phase contrast mode images as a function of temperature and corresponding DSC heating
curve (Fischer et al., 2013a).
 Road Materials and Pavement Design 701

n-paraffin waxes and the remaining non-wax asphalt molecules are responsible for much of the
structuring, including bee-structures.
It was also observed that the dominant bee structuring asphalt binders exhibited a much higher
chemical polarity at the surface compared to the minimal bee structuring asphalt, despite the
dominant bee structuring asphalt having a much higher saturates content (Allen et al., 2014). It
was concluded that saturates content of binder is the primary dominant factor causing such bee-
shaped micro-structures. Interestingly, in the binder matrix, the crystalline wax molecules fall in
the saturates group, thus confirming the findings of previous studies by Das, Soenen, Fischer and
Pauli.
It can be seen from above-listed studies that mostly all of the research findings are based on
the chemical compositions of asphalt binders. Lyne, Wallqvist, Rutland, Claesson, and Birgisson
(2013b) were the first research group to investigate the physical mechanisms for the bee-shaped
micro-structure formation adapting surface wrinkling theory (Chung, Nolte, & Stafford, 2011).
It was concluded that the bees observed on the surface of the asphalt binder may be caused by
surface wrinkling due to buckling of the bee laminate; since this phase is stiffer and does not
contract as much as the continuous matrix phase during cooling from melting temperatures. The
authors believed that the bee laminate phase wrinkles due to a differential in stiffness (elastic
modulus) between it and the less stiff underlying matrix phase. Also, it was mentioned that the
bee laminate phase may consist of crystalline wax.
As explained in the above paragraphs, several researchers proposed and validated different
hypothesis to identify the reason behind the formation of micro-structures on asphalt binder sur-
faces. In general, these micro-structures are dependent on three major factors, such as binder
origins (crude sources), sample preparation method and thermal history. The concept of the
interaction between crystallising waxes and the remaining non-wax chemical components in
binder is the key reason behind the bee-shaped micro-structure getting much attention. Further-
more, the effects of asphaltene and metal traces on binder micro-structures cannot be excluded
because of the complicated intermolecular associations in binder matrix. Likewise, the ‘Surface
wrinkling’ theory has some merit to explain the formation of bee-structures on thin-film sur-
faces of asphalt binder. Hence, the evidence from all the studies is contrary to the ones from
the others (wax-induced vs. asphaltene); yet in all the cases, the evidences were indirect and
limited.

3.3. Micro-structuring: a surface or the bulk phenomenon

As discussed above, depending on the source of crude oil, types of asphalt binders, sample prepa-
ration and temperature, micro-structures can be observed on the surface of the binder. However,
uncertainty still remains whether these micro-structures are just present at free surfaces or sim-
ilar structures exist in the bulk of the material. To investigate this issue, Schmets et al. (2010)
performed small-angle neutron scattering (SANS) experiments, which can indicate any phase
separation throughout the bulk of a material. Based on the experimental results, the authors had
observed that binders exhibited a two-phase morphology and the two phases are chemically dis-
tinct in nature. By comparing SANS signals of binders with and without micro-structures, they
had concluded that the micro-structuring is a bulk phenomenon.
Since the SANS experiment is a very complex experiment to conduct and has a limitation
on visualisation, Fischer, Dillingh, and Hermse (2014) investigated the surface versus bulk phe-
nomenon using AFM and also concluded that these micro-structures present on the surface of an
asphalt binder are also available in the bulk. In that study, the bulk-side of a freshly mechanically
extracted bead of binder was inspected by turning the bead after extraction upside down and then
performing the AFM scan. Though this study provides visual proof of bulk phenomenon, it has
702 P.K. Das et al.

certain limitations during sample preparation. In order to obtain a sufficiently flat surface suitable
for performing AFM experiments, the specimens were subjected to a short and mild thermal
treatment. Thus, one can examine whether or not the seen surface features do resemble at least
some of the bulk features as well, originated during the heat treatment. By addressing this limita-
tion, later on Fischer and Dillingh (2014) conducted AFM scanning on a freeze-fracture surface
by eliminating the surface mobility and surface tension issues. Moreover, acoustic microscopy
was used to scan the binder’s interior micro-structures by ruling out preparation disturbances
as well. The new AFM and scanning acoustic microscopy results furthermore supported pre-
vious findings that similar micro-structures are present in the bulk as can be observed on the
surface.
However, Lyne et al. (2013b) hypothesised that the bee-shaped micro-structuring observed by
AFM on the surface of the asphalt binder is believed to be caused by surface wrinkling, since
this phase is stiffer and does not contract as much as the continuous matrix phase during cooling
from melt temperatures. According to the authors, there are two phases that make up the bees
and its surrounding. It was concluded that the bee laminate phase wrinkles due to a differential
in stiffness (elastic modulus) between it and the less stiff underlying matrix phase and, thus, it is
a surface phenomenon.

4. Applications of AFM to better understand asphalt binder

Although the characterisation of observed micro-structures is important, how these micro-
structures affect due to binder modification, evolve due to ageing and influence the long-term
performances also need to be evaluated. Since the asphalt binder rheology is related to its micro-
scopic phase separation, in the last decade, AFM has been utilised to investigate the binder
micro-mechanical and micro-rheological properties. Different transport agencies require a modi-
fied asphalt binder to resolve different environmental and traffic loading challenges. The blending
mechanism and effect of these modifiers are still unclear; thus to enhance the understanding,
AFM has been used as a tool to study these modifications at the micro-level. So far, several
research projects were conducted to evaluate different applications of AFM in the asphalt domain.
This section focuses on the different applications of AFM to identify asphalt binder properties
and performances.

4.1. Micro-mechanical properties of asphalt binder

Simultaneously with the topographical image at the micro-scale, AFM is capable of acquiring
micro-mechanical information such as relative stiffness/Young’s modulus, stickiness/adhesion,
hardness, energy loss and sample deformation quantitatively, as described in Section 2. Back in
2004, Jäger et al. (2004) were the first research group to investigate the relative stiffness of differ-
ent phases present in asphalt binder surfaces, as can be seen in Figure 7. It can be seen in the figure
that the micro-structure and its surrounding matrix showed different relative stiffnesses, which
might play a significant role in stress concentration. This work showed the potential to perform
creep and relaxation tests with pre-specified load history over a wide range of temperatures.
AFM was further utilised to evaluate micro-rheological properties of asphalt binders by nano-
indentation creep measurements (Allen et al. 2012). The creep test settings were designed to
bring the tip into contact with the surface of the binder at a pre-determined location of the spec-
imen, and a constant force for 4 s was applied, while vertical deflection (change in topography)
versus time was measured. The creep measurements were conducted on three different SHRP
binders from materials reference library. Ten creep measurements were conducted in both of the
bee-shaped micro-structure phase and surrounding matrix phase for each asphalt binder. Results
 Road Materials and Pavement Design 703

(a) (b)

Figure 7. Relative stiffness of different phases measured by pulse-force mode AFM (Jäger et al., 2004).

from the creep measurements exhibited a significant difference in the mechanical response
of these two phases within each asphalt binder. Bee-shaped micro-structure phase exhibited
40–50% higher stiffness than the surrounding matrix phase, as indicated by a smaller creep defor-
mation under constant load. Later on, using the same asphalt binders, Allen, Little, Bhasin, and
Lytton (2013) extended their experimental window and obtained the relaxation moduli of the
asphalt micro-phases, which yielded more practically significant information for modelling and
predicting asphalt behaviour. Furthermore, the same research group investigated the impact of
asphalt chemical composition on the micro-structure and performance characteristics of asphalt
binder. To do so, the methods implemented in this study include adsorption–desorption chro-
matography analysis and a range of AFM and chemical force microscopy techniques. It was
revealed through the study that certain asphalt chemical parameters have a consistent and mea-
surable effect on the asphalt micro-structure that can be observed with AFM (Allen et al.,
2014).
A similar kind of investigation was conducted by Dourado, Simao, and Leite (2012), where
AFM was employed in order to relate the features observed on the surface of a 50/70 asphalt
binder according to its local stiffness and elastic recovery. Indentations were performed at dif-
ferent points on the surface and a significant variation of elasticity was observed between the
points on the bee-shaped micro-structures and the matrix. In this work, the so-called bee struc-
ture presented distances between sequential maxima of approximately 400 nm, similar to the
ones observed before for a 30/45 asphalt (De Moraes et al., 2010). It was observed that the elas-
tic recovery is very much dependent on the colloidal structure of the bee-shaped micro-structures
and surface hardening was also observed surrounding this phase.
Recently in Europe, the AFM PeakForce QNM (Quantitative Nanomechanical property Map-
ping) imaging technique was used to investigate the micro-mechanical properties of asphalt
binder (Das et al., 2013; Fischer, Stadler, & Erina, 2013b; Lyne, Wallqvist, & Birgisson, 2013a).
Compared to the other AFM techniques, this allowed the concurrent capture of topography
with a suite of micro-mechanical maps (Young’s modulus, adhesion and energy of dissipation).
This method is based on the acquisition of force curves recorded at each moment of the tip-
sample interaction to calculate mechanical properties, thus allowing simultaneous capture of
704 P.K. Das et al.

(a) (b)

(c) (d) (e)

Figure 8. AFM PeakForce QNM imaging of Q8 70–100 PEN grade asphalt binder (25 μm × 25 μm),
where micro-mechanical properties (a)–(e) can be obtained simultaneously (Fischer et al., 2013b).

the topography and maps of micro-mechanical properties by an instantaneous force curve treat-
ment. Therefore, QNM is a different technique compared to the above-mentioned techniques.
The QNM gets the “elastic” modulus or the modulus at the high rate of loading over the entire
specimen. So, the QNM gives an approximate map of relative stiffness whereas the previous
technique exposes the relative time-dependent response. However, the other techniques (Allen
et al., 2012, 2013, 2014; De Moraes et al., 2010; Jäger et al., 2004) acquire more time-dependent
properties, but over few selected spots. Each has its advantage and produces slightly different
pieces of information.
A quantitative determination of the mechanical properties of the different constituents within
the asphalt binder with a high spatial resolution and in the temperature range of application is now
accessible for the first time using advanced scanning probe microscopy, which was not possible
using a macroscopic indenter (Fischer et al., 2013b). A typical result of AFM QNM is shown
in Figure 8, where topography (‘height sensor’), elasticity (‘DMT modulus’), stickiness (‘Adhe-
sion’), hardness (‘Deformation’) and energy loss (‘Dissipation’) were acquired simultaneously.
Different phases were observed such as a stiffer phase (peri) and a softer phase (perpetua), and
a more viscous phase (perpetua) and less viscous phase (peri). The resolution was good enough
to resolve the individual temperature behaviour of the mechanical properties modulus of both
phases. The modulus behaviour for both phases was very similar at different temperatures. Using
a similar technique, in spite of different objectives of the studies, similar findings were reported
by Das et al. (2013) and Lyne et al. (2013a).

4.2. Investigation on binder modifications

Asphalt binder itself is very well known as a complex material, which consists of a mixture
of different hydrocarbons; therefore, different ways of modification of the binder makes it even
more complex. AFM has been utilised to investigate the phase changes due to the modifications
and correlate the micro-scale changes to the chemical, rheological and physical performances of
 Road Materials and Pavement Design 705

the modified binder. Below is a short description, where AFM is used as a tool in different kinds
of asphalt binder modifications.

• The morphology of the rubber phase and its interaction with the asphalt binder network
structure in various concentrations at different particle sizes was investigated by Huang
and Pauli (2008). Rubber-modified asphalt showed a different phase on the topography
image obtained from AFM, which leads to the findings that some fractions of the rubber
particles may be dissolved in the asphalt due to the de-vulcanisation of the rubber.
• AFM was employed for observing oil-in-water emulsions with a continuous water phase
and a dispersed binder phase (Loeber et al., 2000). For the first time, the evolution of
surface morphology from wet to dry and the subsequent film formation by coalescence on
an atomically smooth mica substrate was visualised. Thus, the micro-structural analysis of
asphalt binder emulsions by AFM enables a new understanding in emulsion research and
could be a very useful tool for future developments in this field.
• The temperature effect on morphology of asphalt binder modified with low-molecular-
weight reactive isocyanate-terminated polymer was studied by AFM (Carrera, Garcia-
Morales, Partal, & Gallegos, 2010; Navarro, Partal, Garciamorales, Martinezboza, &
Gallegos, 2007). AFM measurements showed that the reactive polymer addition leads
to bee-shaped micro-structure-rich regions with lower thermal susceptibility, which were
present even at high temperature, yielding an improved binder viscosity in this range of
in-service temperatures. It was concluded that neat asphalt binder chemical composition
and micro-structure play a relevant role in the binder modification by the reactive polymer.
• Dourado, Pizzorno, Motta, Simao, and Leite (2014), Rebelo et al. (2014a) and Yan, Zhang,
and Xu (2013) investigated the micro-mechanical properties and morphological evolu-
tion due to the binder modification by poly-phosphoric acid (PPA) and cashew nut oil.
The micro-mechanical measurements showed that both additives increased the elasticity
modulus and apparent viscosity of the modified binder. The ability of the AFM to probe
simultaneously the micro-morphology and micro-rheology of binders, providing insights
into how the micro-morphology affects the micro-rheology of the samples, was demon-
strated. This correlation may help to develop new strategies to enhance the performance
of asphalt binder.
• A comparative study was conducted on asphalt binders modified with isocyanate-
functionalised castor oil, where four preparation procedures were evaluated (Cuadri,
García-Morales, Navarro, & Partal, 2014). The preparation procedures included a com-
bination of two processing times (1 or 24 h, at 90°C) and followed by two different
post-treatments (water addition or ambient curing for up to 6 months). The obtained
AFM images are depicted in Figure 9. By comparing AFM phase images at 30°C, it was
deduced that processing and post-treatment greatly influence the observed micro-structure.
The modified binders cured for 6 months at room temperature showed much larger ellip-
soids, particularly for those samples processed for 1 h. It was found that the degree of
modification attained after post-treatment depends on the previous processing conditions.
• Nazzal, Abu-Qtaish, Kaya, and Powers (2015) successfully utilised various AFM tech-
niques to study the effects of different warm mix asphalt (WMA) additives on the
nanostructure and micro-structure as well as the adhesive and cohesive properties of an
asphalt binder. The control asphalt binder was modified with three different types of WMA
additives, which included: Advera (a synthetic zeolite), Evotherm and Sasobit (a com-
mercial wax). It was observed that while the Sasobit additive reduced the width of the
bee-shaped micro-structures, the other WMA additives did not have any significant effect
on these micro-structures. In addition, the results of the force spectroscopy experiments
706 P.K. Das et al.

Figure 9. AFM images (20 μm × 20 μm) at 30°C, for neat asphalt binder and selected (added-water and
6 months-cured) 1-h processing and 24-h processing samples (Cuadri et al., 2014).

indicated that the inclusion of the WMA additives significantly increased the adhesive
forces of the asphalt binder prior to moisture conditioning. The obtained results indicated
that the AFM is a viable device to study the moisture damage of WMA-modified binders.
Similar findings were also reported by Al-Rawashdeh and Sargand (2014) in a study on
the moisture sensitivity assessment of a WMA-modified asphalt binder. Also, Menapace,
Masad, Bhasin, and Little (2015) have conducted a study on two WMA additives, where
they reported how the binder micro-structures changed with the modification and further
related to the mobility of these micro-structures. Another study by Qin, Farrar, Pauli,
and Adams (2014) observed an interconnected network structure caused by 3% Sasobit
in asphalt binder, which was dependent on the Sasobit concentration rather than asphalt
source.

4.3. Moisture susceptibility investigation

The adhesion force of asphalt binders is one of the fundamental properties that affect asphalt
pavement’s moisture-induced damage performance. AFM is one of the few methods that are
capable of measuring adhesion of asphalt binders at the micro-scale (Lyne et al. 2013a). AFM
has been utilised to measure the force–distance curve, which is a plot of cantilever deflection as a
function of sample position (Yu, Burnham, Mallick, & Tao, 2013). By analysing this curve, one
can measure the tackiness or adhesive properties of an asphalt binder. A typical force–distance
curve is shown in Figure 10(b), in which the x-axis represents the separation or the indenta-
tion depth between the tip and sample, and y-axis is the tip-sample interaction forces. In this
curve, adhesion force is the force required to pull the tip off the sample, which is the lowest
 Road Materials and Pavement Design 707

(a) (b)

Figure 10. (a) AFM topographical image of asphalt binder (10 μm × 10 μm). (b) Force–deflection curves
during approach (dotted lines) and retraction (solid lines) (Yu et al., 2013).

point of the retraction curve. Consequently, the lowest point of the approach curve indicates
the maximum measured attractive force. In the plot (cf. Figure 10(b)), the area enclosed by the
approach and retraction curves is a hysteresis loop, which represents the energy dissipated dur-
ing the tip-sample interaction. These inherent properties of binder can be used to identify the
moisture-induced changes of tackiness, which can be furthermore utilised to relate to moisture
damage performance.
Little, Bhasin, and Hefer (2006) conducted a study on surface energy measurements of dif-
ferent asphalt binders and compared the obtained results between different methods such as the
Wilhelmy method, sessile drop method, inverse gas chromatography and AFM. In their study, the
surface energies of 11 different SHRP binders from materials reference library were measured
using AFM at 25°C. It was recommended that the AFM can be used as an advanced material
characterisation tool to characterise surface properties of asphalt binder. AFM was also utilised
to investigate the effect of liquid anti-strip additives on asphalt binder (Tayebali, Knappe, &
Mandapaka, 2008). It was reported that binder adhesive strength, measured by AFM, increases
with the addition of anti-strip additives, which correlates with the mixture of the moisture sus-
ceptibility results. To understand the adhesive/cohesive bond failures through the investigation
of chemical functional group effects on moisture sensitivity, Tarefder and Zaman (2010, 2011)
conducted a nano-scale experiment using AFM, but silicon nitride (Si3 N4 ) tips were function-
alised using –COOH, –CH3 and –OH functional groups. It was observed that the measured forces
are largely dependent upon the types of used functionalised tips. Based on the ratio of wet to dry
adhesion/cohesion forces, it was concluded that AFM can be utilised as a tool to investigate
the moisture susceptibility of the polymer-modified asphalt binder. Similarly, Allen et al. (2014)
conducted AFM investigation using non-polar (–CH3) and polar (–COOH) tips to investigate
the surface adhesive forces of different phases. It was found that the dominant ‘bee’ structuring
asphalt exhibits a much higher chemical polarity at the surface compared to the minimal ‘bee’
structuring asphalt. Later on, a neural network model to quantify adhesion from AFM data indi-
cated that an increase in the percentage of lime is very effective at reducing moisture damage in
a styrene–butadiene–styrene (SBS) polymer-modified asphalt sample (Tarefder & Ahsan, 2014).
Vasconcelos, Bhasin, and Little (2011) investigated the history dependence of water diffu-
sion in asphalt binders. In their study, by comparing the AFM topographic images of dry and wet
708 P.K. Das et al.

conditioned binders, it was concluded that the increase in moisture diffusivity is attributed mostly
to the change in the asphalt binder micro-structure. The results from the study on adherence
measured by AFM on asphalt thin films conducted by Pauli et al. (2014) showed that bitumen
adherence fracture energy is indeed a rate-temperature-dependent phenomenon. Thus, the adhe-
sion measurements with AFM might provide a new way to characterise chemical and mechanical
relationship of asphalt binders, which will promote more sustainable use of asphalt binders and
related petroleum products.
Very recently, the effect of water on the micro-structures of asphalt binder surface was inves-
tigated by submerging the binder films in water at 23°C under various experimental conditions
and measured deformation as a response to force exerted due to the presence of water (Dos San-
tos, Partl, & Poulikakos, 2014). As a result, the micro-structures were strongly affected; hence
new topographic features were observed on the bitumen film surfaces. It was proposed that ten-
sion, bending and pressure in the presence of water exposure resulted in cracking of the weakest
points of the surface structure. From the observed results, it was concluded that the valleys of the
‘bee’ micro-structure and the interfaces between the periphase and the perpetua phase were the
weakest points on the bitumen surface micro-structure and, therefore, were the first to crack.

4.4. The effect of ageing on micro-structural morphology

There are many factors that can affect the viscoelastic properties of asphalt binders with time,
among which age hardening may be considered as the most important factor. Age hardening
is an irreversible process, which finally contributes to a reduction of the durability. AFM was
utilised to characterise the effect of short-term, long-term ageing and ultraviolet (UV) radiation
on the morphology of asphalt binders (Allen et al., 2013; Das, Kringos, & Birgisson, 2014;
Rebelo et al., 2014b; Zhang et al., 2011). In the laboratory, short-term and long-term ageing is
generally simulated by rolling thin-film oven (RTFO) and pressure ageing vessel (PAV) testing,
respectively. The results from the study by Zhang, Yu, Feng, Xue, and Wu (2012a) showed that
lab-simulated ageing affects the bitumen morphology significantly. Ageing increased the overall
surface stiffness and roughness of the bitumen, and made the asphalt binder surface more solid-
like. As a result of UV ageing, the contrast between the matrix phase and dispersed phase was
increased due to the difference in sensitivity to UV radiation of the bitumen molecules, which
caused or further promoted the phase separation in the binders. It was concluded that regardless
of the ageing procedure carried out, a strong correlation was observed between the changes in
morphology and physical properties as well as chemical compositions of the binders before and
after ageing.
The effects of oxidative ageing on micro-mechanical properties of asphalt binder were
investigated by Allen et al. (2012, 2013). Comparisons and observations of micro-mechanical
properties’ changes in different phases induced by ageing are presented in Figure 11. It was
observed that long-term ageing not only induces changes in phase structure and distribution, but
also in the distinct properties of each phase. In other words, age-induced stiffness increase was
not exclusively attributable to the presence of greater percentages of higher stiffness components
after ageing, but also a general increase can be observed in the stiffness of the dispersed and
continuous phases. For the same binder, ageing increased the stiffness of the dispersed and con-
tinuous phases by approximately 14–56% and 27–63%, respectively. In addition, for all aged
binders, the stiffness of the dispersed phase was approximately 22–67% greater than that of the
continuous phase. Moreover, sometimes an additional phase was observed within the dispersed
phase after ageing, which exhibited a stiffness that was between the values observed for the con-
tinuous and dispersed phases. In another study by the same research group, it was reported that
the relaxation modulus values extracted from age-altered phases of the same asphalts provided
 Road Materials and Pavement Design 709

Figure 11. Creep measurement comparison of aged and non-aged asphalts binders (Allen et al., 2012).

important relationships between micro-structural changes depicted in AFM images and changes
in composite viscoelastic properties obtained from the measurements (Allen et al., 2013).
To investigate the surface ageing, three different types of asphalt binders with different natu-
ral wax contents were conditioned in four different modes: both UV and air, only UV, only air
and without any exposure, for 15 and 30 days (Das et al., 2014). Using the AFM–QNM force
mapping data, the evolution of adhesive force or tackiness due to different types of exposure or
ageing history is shown in Figure 12. It can be seen that with the ageing, the adhesion of the
asphalt binder specimens was negatively impacted. This finding supports the traditional ageing
concept that the binder tackiness decreases with ageing, which may cause an adhesive bond fail-
ure between binder and aggregates. Though it is important to mention that the tackiness is a
property of the bulk. However, ageing would increase polar fractions, which would be reflected

(a)

(b) (c)

Figure 12. Adhesive force measured by AFM–QNM at different levels of exposure of three different types
of asphalt binder (Das et al., 2014).
710 P.K. Das et al.

by increasing adhesion at the surface. It is the local polar interactions that may reduce the tack-
iness in the bulk. From the AFM investigation after 15 and 30 days of conditioning period, it
was found that regardless of the bitumen type, the percentage of micro-structure on the surface
diminished with the degree of exposure and time. Comparing all the four different exposures, it
was observed that UV radiation caused more surface ageing than oxidation. It was also found
that the combined effect was not simply a summation or multiplication of the individual effects.
Recently, Rebelo et al. (2014b) investigated the short- and long-term ageing of asphalt binder
with different AFM techniques (topography, phase and friction imaging and nano-indentation
experiments). It was observed that the ageing process induces a growth and nucleation of the
asphaltene micelles with a concomitant reduction of the maltene phase, whereas short-term
ageing induces the formation of fractal-like micellar structures. In the same study, the friction
investigation showed that the ageing processes reduce the binder friction coefficient by 50%, and
this reduction occurred predominantly during short-term ageing, while the growth of the micelles
happened predominantly during long-term ageing. Moreover, the micro-indentation experiments
indicated that the ageing processes caused a stiffening of the binder film, which was half-order
of magnitude for short-term ageing and one order of magnitude for long-term ageing. Conse-
quently, the ageing process also increased the apparent viscosity of the binder films by half-order
of magnitude.
The effect of rubber particles on the fundamental internal micro-structure of asphalt binders
with respect to their long-term ageing performance was investigated by utilising AFM (Huang
& Pauli, 2008). Surface structuring became irregular for the PAV-aged rubber-modified binder
and new small spherical particles were also observed due to the rubber modification. It was
concluded that some fractions of the rubber particles may be dissolved in the asphalt due to the
de-vulcanisation of the rubber, and hence could explain the appearance of new phases in the
AFM image of the recovered asphalt samples.
AFM had also been used to investigate the effect of ageing on modified asphalt binders com-
pared with the control binders. Wu, Pang, Mo, Chen, and Zhu (2009), Zhang et al. (2011, 2012a),
Zhang, Yu, and Wu (2012b), Zhang, Xu, Wang, and Yu (2013) and Feng, Yu, Zhang, Kuang,
and Xue (2013) investigated the effect of thermal and UV ageing on organo-montmorillonite,
SBS polymer, expanded vermiculite and UV absorber-modified asphalt binders. The study of
short- and long-term ageing on micro-structural properties of recycled asphalt binder indicated
an apparent change in the surface micro-structure specifically the absence of the bee-shaped
micro-structure in the extracted recycled and aged binders in comparison to the virgin binders
(Poulikakos et al. 2014). The effect of short- and long-term ageing on micro-structures’ evolution
of Advera- and Sasobit-modified binders was investigated thoroughly by Menapace et al. (2015).
It was reported that the ageing effect on the micro-structure morphology of WMA binders was
negligible. All of the studies done on ageing by these research groups clearly indicated that the
AFM can be successfully utilised as a tool to develop better understanding of how the surface
morphology and its physicochemical properties are interlinked.

4.5. Other applications of AFM

• The degree of blending between reclaimed asphalt pavement (RAP) binder and added vir-
gin bitumen, on which the performance of recycled asphalt mixtures depends to a great
extent, is still quite unknown. AFM was utilised to evaluate the interaction and extent
of blending between RAP and virgin binder (Nahar et al., 2013b; Zhao et al., 2015).
The interface between the two binders was identified by following the gradual change
of the micro-structure along the scan line, as can be seen in Figure 13. The morphology
of the blending zone (spatial extent of about 50 μm) exhibited domains of a wide range of
 Road Materials and Pavement Design 711

(a) (b) (c) (d)

Figure 13. A schematic representation of AFM probe trajectory from RAP bitumen toward virgin bitu-
men. A, B, C and D are AFM scans (30 μm × 30 μm) of (a) RAP binder, (b) blended zone, (c) transition
zone and (d) virgin binder, respectively (Nahar et al., 2013b).

micro-structure sizes (160 nm to 2.07 μm) and were considered to be a completely blended
new material. The fully blended binder properties were found to be between those of the
two individual binders, as it was inferred from the averaged micro-structural properties
derived from AFM images of the blending zone. This finding was reported to be consistent
with the results of mechanical tests by dynamic shear rheometer on the same materials.
• The fundamental understanding of self-healing mechanism of asphalt has always been
another challenging issue. AFM technology has been used to understand what causes some
binders to be better ‘healers’ than others (Das, Jelagin, Birgisson, & Kringos, 2012; Hou,
Wang, Pauli, & Sun, 2015; Nazzal, Kaya, & Abu-Qtaish, 2012; Scarpas, Robertson, Krin-
gos, & Pauli, 2009). Nazzal et al. (2012) developed an AFM-based approach to evaluate
the effect of two types of WMA additives (Sasobit and Advera) on the healing character-
istics of asphalt binders. The results indicated that the use of WMA additives enhances
the adhesive intrinsic healing characteristics of the selected asphalt binder. However, the
two WMA additives showed adverse effects on the cohesive intrinsic healing behaviour of
that binder. The self-healing mechanism was investigated by using the phase-field method,
where AFM was utilised to obtain the model parameters (Hou et al., 2015; Scarpas et al.,
2009). Also, it was validated by AFM results that micro-cracks form and disappear in the
stress concentration zones near the phase interfaces because of phase separation. The rate
at which these phase changes occur is of great importance for the practical implications,
since this phenomenon relates to rest periods in the laboratory to assess the healing rates
and the actual healing ability of the asphalt binder.
• In an effort to understand the effect of low temperature fatigue cracking at the micro-
scale, AFM was used to characterise the morphology of asphalt binder (Das et al., 2012).
712 P.K. Das et al.

The binder film over the silicon bar was subjected to thermal fatigue with heating and
cooling cycles. A freezer was used to regulate the low temperature at − 20°C and a room
with controlled temperature at 25°C was used for thawing. The micro-cracks were found
at the interface of the different phases due to stress concentration. Jahangir, Little, and
Bhasin (2015) performed finite element (FE) simulations to study the effect of bitumen
micro-structure on internal stress distribution. Furthermore, a custom-made loading frame
in conjunction with an AFM device was used to examine the effects of tensile strain on
bitumen micro-structure. Both the FE simulation and experimental results indicated that
applying strain resulted in damage/phase separation concentrated in the interstitial zone
between neighbouring bee-structures, defined as load-induced phase separation. Similar
findings were also reported in another study by Hou et al. (2015), in which the authors
investigated the same phenomenon through FE analyses and arrived at conclusions similar
to Jahangir et al. (2015). Thus, AFM helped to visualise the hypothesis that asphalt binder
itself may also crack due to its inherent heterogeneities under environmental and traffic
loading.

5. Concluding summary
AFM is an extremely valuable analytical resource and technique, which is proven to be useful
for the qualitative and quantitative surface analysis with sub-nanometer resolution. The advan-
tages of AFM are that the sample preparation is rather simple, time efficient and does not induce
any artefacts, and can operate both under ambient conditions and at any specific temperatures.
Importantly, the observed micro-structures under AFM has been proven to be a unique and repro-
ducible property of any specific asphalt binder (Nahar et al., 2013a; Soenen et al., 2014), which
makes AFM a versatile research tool for a complex material like asphalt. Although all the stud-
ied literature indicated promising results, AFM as a technique itself has some limitations. The
main disadvantage of AFM is that it needs a smooth surface and can only detect what occurs
on the surface of the sample. One should, therefore, be aware that the sample preparation could
influence what is measured at the surface. Also, AFM results only reflect the surface properties,
which may not always be reflective of bulk properties.
Sample extraction and preparation for conducting AFM are very important factors. Special
attention is needed to obtain homogenous samples with sufficient thickness and no surface
contamination. During sample extraction, using the material from the surface of a can is not
recommended as age hardening and dust collection mainly occurs at the surface. It was found
in the literature that spin casting and heat casting are the two most commonly practiced sample
preparation techniques. Using solvent during sample preparation, inconsistency in the observed
micro-structure due to film thickness and complex sample preparation technique are the main
drawbacks of the spin casting technique. However, the heat casting technique does not have
these drawbacks and it is a rather simple and easy process. Based on the literature review, it
can be concluded that the preparation should include a high temperature treatment to provide a
smooth homogenous surface and the annealing/resting period of the sample has to be sufficiently
long, at least 24 h under ambient temperatures.
Identifying the phenomenon behind the appearance of bee-shaped micro-structures has always
been a concern. The summary of all the investigations and their findings related to this issue
are listed in the appendix. It can be seen that at the starting, the hypothesis was that these
micro-structures are mainly attributed to asphaltenes. With time and help of technological devel-
opment, most of the recent research projects have concluded that bee-shaped micro-structures
are mainly wax-induced. Only a few researches have been conducted to identify whether these
 Road Materials and Pavement Design 713

micro-structures are a bulk or surface phenomenon. Based on the findings from these research
projects, so far it seems promising that these micro-structures are not only present in the surface
but also exist in bulk.
Besides the characterisation of the observed micro-structures, their effects due to binder mod-
ification, which evolves due to ageing and influences the long-term performances, were also
assessed in different studies. It was observed that simultaneously with the topology at the micro-
scale, AFM was successfully utilised to acquire micro-mechanical information such as: relative
stiffness/Young’s modulus, stickiness/adhesion, hardness, energy loss and sample deformation
quantitatively. The phase and micro-mechanical forces change due to asphalt modification such
as rubber-modified asphalt, oil-in-water emulsions, low-molecular-weight reactive isocyanate-
terminated polymer, PPA, cashew nut oil, isocyanate-functionalised castor oil and warm mix
additives were investigated using AFM as a tool. Furthermore, the micro-scale changes were
correlated to the physical, chemical and rheological performance of the modified binder.
AFM is one of the few methods that are capable of measuring adhesion of asphalt binders
at the micro-scale. The flexibility of using different functionalised tips opens a new window to
investigate the moisture sensitivity of asphalt binder and the effect of different additive agents on
it. This technique has also been used to characterise the effect of short-term, long-term ageing and
UV radiation on the surface morphology and micro-mechanical properties of asphalt binder. It is
important to mention that several research projects investigated PAV-aged residue to understand
the evolution due to long-term ageing. However, the PAV residue undergoes heating and cooling
several times during sample collection and preparation. Due to this thermal history, the aged
surface layer melts down in the asphalt and results in a homogeneous matrix. Thus, the surface
changes entirely and AFM scanning may show completely different surface information, which
could be far from the real field ageing. Hence, the surface information from the disturbed PAV
residue bitumen may not even represent the bitumen surface right after the PAV ageing, which
remains still a large drawback and needs to be investigated further.
AFM has also been successfully used as a tool in other applications in the asphalt domain, such
as blending between RAP and virgin binder, de-vulcanisation of the rubber in asphalt binder,
healing characteristics, stress concentration due to phase separation and low temperature fatigue
cracking of asphalt binder. All of the studies that led to the investigation of asphalt binder clearly
indicated that AFM can be successfully utilised as a tool to develop better understanding on
how the surface morphology and its physicochemical properties are interlinked and related to the
binder performances.

Disclosure statement
No potential conflict of interest was reported by the authors.

ORCID
Prabir Kumar Das http://orcid.org/0000-0002-4041-3657

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Appendix
Summary of all the investigations on bee-shaped micro-structure and the key findings.

Sample
Binder preparation Conclusion/key
Reference information methods AFM mode Temperature findings

Loeber et al. (1998) Asphalt binder with Heat casting Contact mode, tapping Ambient Oscillation of the oil
unspecified type and mode phase
source
Pauli et al. (2001) Eight SHRP binders Spin casting Tapping mode Ambient Associated with
asphaltene fraction
Jäger et al. (2004) Five different binders with Heat casting Non-contact mode, Ambient Related to the presence
different penetration pulsed-force mode of asphaltene
grades
Masson et al. (2006) Twelve SHRP binders Heat casting Tapping mode Ambient Correlate to the
from different crude vanadium and nickel

Road Materials and Pavement Design

sources and a 85/100 metals
penetration grade
binder
De Moraes et al. 30/45 penetration grade Spin casting Tapping mode Between 25°C and 75°C Paraffin wax
(2010) binder crystallisation
Schmets et al. (2010) Eight SHRP binders, same Heat casting Tapping mode Ambient Wax-induced micro-
as Pauli et al. (2001) structure
Zhang et al. (2011) SK-70 binder Heat casting Tapping mode Ambient Wax crystallisation
Pauli et al. 2011) Eight SHRP core asphalts Heat casting, spin casting Intermittent-contact mode Ambient Wax-induced phase
(WaveMode) separation
Das et al. (2013) Four different types of Heat casting PeakForce QNM mode Heating and cooling Wax-induced micro-
70/100 penetration cycle 30–60°C structure
grade binder

(Continued).

717
 718
Sample
Binder preparation Conclusion/key
Reference information methods AFM mode Temperature findings

P.K. Das et al.

Nahar et al. (2013b) Three binders from Heat casting Tapping mode Thermal cycle 25–75°C Asphaltene contents
different crude sources steer the size of the
micro-structures;
metal content affects
the area fraction of
the bee-phase; wax is
related to a hysteresis
effect during the
heating–cooling cycle
Lyne et al. (2013a) Seven different types of Heat casting PeakForce QNM mode Ambient Physically caused by
70/100 penetration surface wrinkling and
grade binder chemically wax phase
is responsible
Soenen et al. (2014) Four different types of Heat casting Tapping mode Ambient Wax-induced phase
70/100 penetration separation
grade binder
Pauli et al. (2014) Eight SHRP binders Spin casting Intermittent-contact mode Heated or cooled in 3°C The interactions between
(WaveMode) increments starting at crystallising n-paraffin
ambient temperature waxes and the
remaining non-wax
asphalt molecules are
responsible for much
of the structuring
Allen et al. (2014) Ten modified binders Spin casting Contact mode with Ambient Saturates content of
obtained from two functionalised tips, asphalt seems to be the
parent binders from tapping mode primary contributing
separate crude sources factor causing
(ARC-BI0001 and ‘bee’ structuring of
ARC-BI0002) non-aged asphalts
Hofko et al. (2015) An unmodified, straight- Heat casting Dynamic mode At + 25°C Concentration appears
run 70/100 penetration to be correlated to
grade binder (B287A) the occurrence and
shape of the bee-like
inclusions