Front. Struct. Civ. Eng.

2017, 11(4): 380–387

DOI 10.1007/s11709-017-0437-3

RESEARCH ARTICLE

The investigation of fly ash based asphalt binders using

atomic force microscope
Rajan SAHA* , Kyle MALLOY, Emil BAUTISTA, Konstantin SOBOLEV
Department of Civil and Environmental Engineering, University of Wisconsin at Milwaukee, WI 53705, USA
*
Corresponding author. E-mail: [email protected]

© Higher Education Press and Springer-Verlag Berlin Heidelberg 2017

ABSTRACT Atomic Force Microscope (AFM) is a relatively new technique for investigation of construction
materials. In this study AFM was used to investigate the interaction of asphalt binder with fly ash. Fly ash is a coal
combustion byproduct of electric power utilities having pozzolanic properties and commonly used in Portland cement
concrete. In this study, an investigation was made by using different types of fly ash with two types of asphalt binders such
as PG 58-28 and PG 64-28. Asphalt microstructure is divided into four subgroups such as Saturates, Aromatics, Resins
and Asphaltenes (SARA). These four phases can be distinguished by the atomic force microscope. The interaction of
these phases affected by introducing fly-ash was investigated and correlation with rheological properties was observed.

KEYWORDS AFM, fly ash, bee, rheology, asphalt

1 Introduction lines. Each “strip” was around 100–200 nm thick. These

structures have been identified as asphaltenes [1]. This
The use of asphalt dates back thousands of years, when it observation has been also supported by Pauli et al. [7].
was used as a waterproofing material and sealer for cracks A study performed at the University of Wyoming [7]
and joints. While it is known that asphalt is composed involved scans of asphalt samples with varying amounts
mostly of hydrocarbons, the knowledge of its microstruc- and types of paraffin waxes. The samples were also varied
ture is still incomplete [1]. Optical microscopes have been in thickness. It was found that most of the structuring that
used for centuries to study materials [2], but have not been is observed in the sample, including the “bee” structures, is
effective with asphalts due to the opaque and adhesive due to the interaction between the paraffin waxes and the
properties of the substance. In addition to this, the non-wax components of the asphalt. The observed
resolution of an optical microscope is about 200 nm [3] structuring occurs in non-polar asphalt fractions (oil
which is inadequate to reveal the details of structural phase), which would be expected to hold the majority of
buildup of the binder. A relatively new technology that the wax-type materials. The appearance of structure
could provide better insight into the microstructure of patterns was correlated to wax type, wax concentration
asphalt is Atomic Force Microscopy (AFM) enabling the and crystallising conditions, as well as asphalt and asphalt
molecular and atomic resolution [4,5]. fraction crude source.
The AFM was first used to study asphalt by Loeber [6], The effect of temperature and thermal histories on
which resulted in the detection of different phases within asphalt bee structures was further studied by Lu et al. [8]
the asphalt. Asphalt specimens were examined under AFM and Nahar et al. [9]. The research by Nahar et al. involved
and compared to the results from Scanning Electron taking AFM scans of asphalt samples at various stages
Microscopy, and Fluorescence Microscopy. Alternating during a heating and cooling cycle. It was found that the
ridges and valleys, which appear as alternating white and bee structures and surrounding phases melted away at
black bands on an AFM scan, were observed and termed temperatures above 55 °C, and reformed around 45 °C.
by Loeber et al. as “bee” structures. The “bee” structures The asphalt also exhibited a structural memory, with the
were symmetrically aligned with alternating dark and light bee structures forming in similar patterns after they had
been melted. The maximum temperature a sample is
Article history: Received Apr 19, 2015; Accepted Jan 22, 2016 exposed to will also change the surface structure of a
 Rajan SAHA et al. The investigation of fly ash based asphalt binders using atomic force microscope 381

sample. The amount and size of the bee structures was

observed to be contingent on the wax content of the
sample, but the areas containing the bees seemed to
fluctuate relative to presence of asphaltenes.
The AFM methods have been used to study the effects of
aging on the micro-morphology and micro-rheology of
bitumen. Rebolo [10] used AFM to conduct topography,
phase and friction imaging and nano-indentation experi-
ments on aged and unaged asphalt. It was found that the
asphalt films consisted of asphaltene micelles suspended
throughout a hydrocarbon matrix. The micelle structure
could not be detected topographically in the unaged
Fig. 1 The effect of aging on the structure of bitumen binders
sample, but was detected on the aged sample. The aging with nano-clay, from Sobolev et al. [13].
process seemed to increase the size of the micelles.
Eventually, the micelles formed a connected network with micelle structures and the stiffness of the asphalt sample.
the hydrocarbon matrix filling in the void. There was a This reported research evaluates the effects of different
50% reduction in the friction coefficient due to short term types of fly ash on nano-structure of asphalt binders.
aging, but no further reduction occurred after the long-term
aging. Nano-indentation confined showed that aging
increased the stiffness of the sample. 2 Materials and sample preparation
The mechanical properties of asphalt were also analyzed
by Dourado et al. [11]. This test involved using the AFM to Two different types of asphalt binders, PG 58-28 and PG
make indentations on different areas of an asphalt sample 64-28, were used in this study for each type of asphalt.
in order to determine the elastic modulus. The hydrocarbon Different samples were produced with three different types
matrix, the bee structures, and the areas containing bee of fly ash at three different concentrations. The specimens
structures were analyzed. It was found that the areas were designed with fly ash at content of 5%, 15% and 25%
containing bee structures had a lower elastic modulus than by volume. The PG 64-28 binder has higher stiffness than
the surrounding matrix, with the bee structure itself having PG 58-28. Fly ash was mixed with asphalt using a low
a lower elastic modulus compared to the overall area. It shear mixer at 1300 rpm. Asphalt microstructure is divided
was concluded that the areas containing bee structures are a into four subgroups: saturates, aromatics, resins and
mixture of asphaltenes and resins, with the resins forming asphaltenes (SARA). These four subgroups can be
the bright bands of the bee structure. effectively distinguished by atomic force microscope as
The interaction of asphalt with substances representing different phases. Table 1 shows the description and the
various fillers in asphalt cement was studied using AFM by chemical compositions of SARA.
Fischer [12]. The AFM was used to measure the contact Asphaltenes impart high viscosity to crude oils resulting
angle of asphalt on various mineral samples. In each case in increased stiffness of the asphalt binder, which
the peri/catana phase had a smaller contact angle than the negatively impacts production and causes a number of
perpetua phase indicating that the affinity of the peri/catana problems in production. This model demonstrates how
phase for the filler is larger than for the perpetua phase. It asphaltene molecules are dispersed in resins. Both
was also observed that the bees in the peri/catana phase asphaltene and resins are dispersed throughout the oil
were smaller in size and number (density) near the and aromatic portions of the asphalt. The asphalt binders
bitumen-filler interface. PG 58-28 and PG 64-28 were collected from local vendors.
The scans of aged bitumen samples were also reported Fly ash is divided into two classes: C and F. When the
by Sobolev et al. [13]. Among others results, the study sum of SiO2, Al2O3, and Fe2O3 make up more than 50% of
reported on the effect of a nano-clay (Acti-gel) additive and a fly ash specimen, it is considered as class C (Table 2).
simulated aging process in a pressure vessel. The scans When the same components make up 70% of the fly ash, it
reported by Fig. 1 revealed an increase in the area of the is considered class F. Fly ash WE05 class C, WE07 class F,
micelle structures, which can be correlated to increased and WE08 class C were supplied by WE Energies (WI,
stiffness of the samples. This provides evidence that there USA) [13–15].
is a relationship between the area associated with the The most important factor in microscopic observations

Table 1 Chemical composition of asphalt [1]

saturates aromatics resins asphaltenes
n- and iso- alkanes (simple and a type of hydro-carbon which has alternating viscous liquid carbon, hydrogen, nitrogen, oxygen, and
least reactive hydrocarbon) double and single bonds between carbon sulfur as well as trace amounts of vana-
atoms forming rings dium and nickel
382 Front. Struct. Civ. Eng. 2017, 11(4): 380–387

Table 2 Chemical composition of fly ash [13]

chemical composition, %
materials ID class
Al2O3 CaO Fe2O3 SiO2 MgO Na2O K2O TiO2 P2O3 SO3
WE05 C 22.3 24.6 5.4 32.9 6.3 2.8 0.5 1.3 1.6 1.8
WE08 C 23.9 23.1 4.5 34.4 5.3 2.2 0.6 1.3 1.5 2.1
WE07 F 27.2 5.0 14.0 45.6 1.0 0.7 1.8 1.1 0.5 2.7

of asphalt and asphalt binders is sample preparation. which was developed specifically for AFM scans. The
Asphalt has a high viscosity at ambient temperatures and program allows for viewing scans as a 2D or 3D image.
high temperature sensitivity. Glass slides were used for Fig. 2 provides examples of scans of both asphalt types
sample preparation. Initially, the asphalt binder was placed with 5% of fly ash.
in the oven at 130 °C for 60 minutes to lower the viscosity These scans demonstrate how the “bee” structures form
to a point where it can be sampled. A small drop of asphalt the spikes in the vertical direction. It also appears that spikes
was then placed on the slide. The glass slide with the can form multiple ridges which look like the classical “bee”
asphalt drop was placed in the oven for 1 minute. During structure, as seen in the PG64-28 asphalt, or these can exist
this step, the asphalt drop spreads out equally and forms a as solitary spikes, as shown for the PG58-28 asphalt. The
very thin layer. Heat cast samples were used due to the fact type of crystal structure seems to be related to the type of
that solvent cast (by using solvent with asphalt) samples asphalt, and is not affected by the presence of fly ash.
did not show any bee structures. The Gwyddion software was used to measure two
An atomic force microscope 5420 AFM from Agilent specific aspects of the crystal formation (Fig. 3). The first
Technologies was used in this study. The AFM used a very was the height of the crystals, which in this case meant
small silicon cantilever (type PPP-NCH) with frequency measuring the peak crystal height in the scan which
300 kHz to scan the surface of the sample. The change in consisted of strictly the catana phase. The second method
height of the sample is captured by a photo-diode which would involve measuring the overall area occupied by the
measures the position of a laser beam reflected off the back crystals, which defines the catana phase and the peri phase.
of the cantilever arm during the scan. Usually the These areas were selected using a tool in Gwyddion that
cantilevers consisted of a macro scale rectangular base, a allows the user to select areas based on height threshold.
long, thin arm, and a fine tip. The images were of 20 µm  The height threshold was adjusted to select the cells. This
20 µm size recorded in non-contact mode. was possible due to the cells being slightly lower than the
rest of the area on the scan. After the areas were selected,
the height and area calculations were executed by a
3 Results and discussion statistical analysis tool in Gwiddion, which provides the
data on the area selected. All analyzed scans are reported
All of the images were analyzed using Gwyddion software, by Figs. 4 and 5.

Fig. 2 The 2D and 3D images of PG58-28 and PG64-28 binders and effect of adding of 5% fly ash
Rajan SAHA et al. The investigation of fly ash based asphalt binders using atomic force microscope 383

Fig. 3 The ashphalt phases detected by AFM and small area analyzed by Gwyddion

Fig. 4 The AFM scans of PG58-28 based mastics

384 Front. Struct. Civ. Eng. 2017, 11(4): 380–387

Fig. 5 The AFM scans of PG64-28 based mastics

The test results and the height of crystals proved no lization to occur. This would result in the increased area of
correlation between the volume of fly ash added (Fig. 6). the micelle structures.
The most of the peaks were in the 10-15 nm range with The effects of cooling rate were also investigated and
higher peaks observed on the PG64-28 samples. This was reported by Fig. 8. Samples of PG58-28 mixed with 5%,
most likely due to the variation in source of the asphalt. 15%, and 25% fly ash were produced. Two duplicate
According to Pauli et al. [16], “bee” structure crystal height samples were produced at each concentration of fly ash.
correlates with the wax content. From these, one sample was allowed to cool at a room
The surface area calculations demonstrated a slight temperature, while the other was quenched at –10°F in a
increase in the catana and peri phase area for specimens freezer.
with higher content of fly ash (Fig. 7). Masson et al. [1] It appears that the quenched samples formed micelle
found a strong correlation between the size of the cell structures that are smaller in size, but greater in numbers.
structures and the presence of nickel and vanadium and so The surface area occupied by the micelle structures
the presence of these elements in fly ash might contribute increased with fly ash content in both the room-cooled
to the increased area of the peri phase. Fly ash may have and the quenched samples. In the quenched samples, the
also provided more points within the asphalt for crystal- components of the micelle structure were not able to
Rajan SAHA et al. The investigation of fly ash based asphalt binders using atomic force microscope 385

Fig. 6 The effect of fly ash on crystal height as recorded by AFM

Fig. 7 The effect of fly ash on resin and asphltene area as measured by AFM
386 Front. Struct. Civ. Eng. 2017, 11(4): 380–387

Gwyddion software. The peak height and the surface area

of the micelle structures were measured. No correlation
was found between the fly ash content and the height of the
peaks. It was found that the addition of fly ash can increase
the area of the micelle structures. However, it was found
that the complex modulus increased with the addition of fly
ash and the area of the micelle structures. This can be
interpreted that the micelle structures contribute to the
stiffness of an asphalt sample.
Further research can focus on the investigation of the
effect of fly ash particles on the formation of large bumps
on the surface. Fly ash particles are relatively large and so
must be easily detectable on the slides. A thinner sample
may be required in order to investigate the effect of fly ash
distributed within the sample.

Acknowledgements The authors acknowledge the financial support of the

Energy and Power Research Institute. The support from WE Energies and
Advanced Analytical Facility at University of Wisconsin-Milwaukee is
appreciated.

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