Fuel 307 (2022) 121852

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Fuel
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Full Length Article

Behavior comparison of films of Mexican bitumen and its asphaltene and

maltenes fractions at interfaces
M.A. Zúñiga-Hinojosa a, 1, A. Cosultchi b, M.T. Martinez-Martinez c, R.D. Cadena-Nava c, *,
J. Ruiz-Garcia a, *
a
Instituto de Física, Laboratorio de Coloides e Interfases, Universidad Autónoma de San Luis Potosí, Álvaro Obregón 64, 78000 San Luis Potosí, San Luis Potosí, Mexico
b
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, 07730 Ciudad de México, Mexico
c
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Carretera Tijuana-Ensenada Km. 107, 22860 Ensenada, Baja California,
México

A R T I C L E I N F O A B S T R A C T

Keywords: The oil industry has been focused on bitumens and heavy oils due to the depletion of petroleum reservoirs. For
Bitumen this reason, we studied the interfacial behavior comparison of films of bitumen and their asphaltene and maltene
Asphaltenes fractions by means of the Langmuir balance and Brewster angle microscopy at the air–water interface. The films
Maltenes
were transferred by Langmuir-Blodgett technique onto mica and grids to be further analyzed by AFM and SEM at
Langmuir monolayers
Brewster angle microscopy (BAM)
different surface pressures. We found that the isotherm behavior of the bitumen depends on the amount of its
Atomic force microscopy (AFM) asphaltene and maltene fractions, although the isotherm behavior of asphaltene and maltene fractions are quite
different. BAM images of the bitumen and asphaltene samples show the formation of two- and three-dimensional
domains, being the asphaltene domains the most rigid and compact structures. Maltenes seems to form large
areas of mono- or bi-molecular films, and their structures are like those reported for lipid monolayers. The AFM
images for the bitumen morphology exhibited polydisperse mesostructures with spherical and disk-like shapes,
while asphaltene images revealed disk-like microstructures and some of these microstructures coalesce, resulting
in the formation of worm-like and other small structures. AFM images of the maltene film revealed that they form
a fine plaster that might agglutinates the asphaltenes. SEM images of bitumen film show a smooth and slightly
porous surface with some layer detachments, holes and bright spots embedded, while asphaltene images pre­
sented porous surfaces with spherical- or drumstick-like structures. Maltene SEM images showed a surface with
irregular pores. The results support a better understanding of the bitumen, asphaltene, and maltene fractions and
suggest that the interfacial behavior of bitumen presents a synergy between its asphaltene and maltene fractions.

1. Introduction
Bitumens have attracted attention within the oil research and in­
dustry community due to the depletion of petroleum reservoirs. Ac­
cording to SARA analysis, bitumen is divided to saturates, aromatics,
resins (maltenes), and asphaltenes fractions. It is commonly accepted
that the interfacially active components of crude oil prevail in the
highest molecular weight and polar fractions, such as asphaltenes. Thus,
asphaltenes are the most important component for stabilizing emulsions
at the crude/water interface [1]. Although, recent modeling studies and
experiments also suggest that low molecular weight multifunctional
compounds, such as deasphalted crude oil, i.e. maltenes, can also modify
the rock surface properties [2–5]. Petroleum contains numerous surface-
active or polar compounds which, additional to carbon and hydrogen,
contain nitrogen, sulfur, oxygen, and traces of nickel, vanadium, and
other metals [1,6,7]. These are identified as heteroatoms and are known
to display a strong affinity for solid phases, i.e., minerals, organic mat­
ter. Consequently, such species can alter the wetting properties of the
surfaces. Most of these surface-active compounds are concentrated in
the crude oil fraction defined as asphaltenes. Adsorption of polar com­
pounds on surfaces depends on different factors that include the type of
oil and its quality to solvate the polar phase [8–9], brine composition
[10–11], and interfacial [12] and surface properties [13–17]. In this
work, we present a study of Mexican bitumen and its asphaltene and

* Corresponding authors.
E-mail addresses: rcadena74@gmail.com (R.D. Cadena-Nava), jaime@mail.ifisica.uaslp.mx (J. Ruiz-Garcia).
1
Present address. Depto. de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana–Iztapalapa, Ciudad de México, Mexico.

https://doi.org/10.1016/j.fuel.2021.121852
Received 25 March 2021; Received in revised form 23 August 2021; Accepted 26 August 2021
Available online 13 September 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
M.A. Zúñiga-Hinojosa et al.
maltene fractions on water and mica surfaces using the following tech­
niques: Langmuir trough, BAM, AFM, and SEM. Also, we calculate the
bitumen surface pressure applying mixtures rules.
The Langmuir trough has been used to analyze the thermodynamic
behavior of different monolayer systems related with crude oil, e. g., the
coexistence of phases for bitumen, crude oil, asphaltene, and maltene
films, as well as their compressibility and aggregation at different con­
centrations of spreading solvents [18–30]. It has been proposed that the
asphaltene films form stable monolayers because of their correct balance
between the hydrophilic headgroup and hydrophobic tail, whereas
maltene films presented multilayer films [28]. According to Zhang et al.
[23,27], asphaltenes from Athabasca bitumen showed monolayers even
at low surface pressures (Π), whereas Diaz et al. [20], also indicated that
Puertollano bitumen, asphaltene, and maltene films were organized as
monolayers. Whereas, Hua and Angle [29], and Lobato et al. [31]
pointed out the formation of bitumen, asphaltene, maltene monolayers
by using the Langmuir trough in conjunction with BAM independently of
their concentration. However, Cadena-Nava et al. [24] showed that
asphaltene films form a mixture of two- and three-dimensional domains,
also using the Langmuir trough coupled with BAM; while Alvarez et al.
[18–19] using the abovementioned techniques, suggested that the
asphaltene aggregates begin to form in the spreading solutions. Besides,
Vieira et al. [31] reported that oil films do not form a non-homogeneous
Langmuir film. Hence the monolayer formation for bitumen, crude oil,
asphaltene, and maltene remain a topic of debate. Indeed, some research
groups have a special interest in asphaltene monolayers in order to
elucidate their water surface behavior and the aggregation mechanism
[18–19,31].
It is well known that asphaltenes have a natural tendency to self-
associate in solution forming colloid-like particles [32–39], as well as
shape and size of these colloids [32,40–44]. A colloid is defined only
from a linear dimension between 10− 9 and 10− 6 m, rather than based on
the particle weight or the number of atoms in the particle [45]; whereas
the aggregation is a process by which many particles clump together,
retaining their identity although their kinetic independence is lost. In
the asphaltene aggregation context, the Yen-Mullins model [46,47]
describes the asphaltenes nanoaggregates according to their oil density.
As well as the aggregation depends on the organic solvent-to-asphaltene
ratio. Mullins et al. [7] proposed the critical nanoaggregate concentra­
tion (CNAC) [47], to the minimum concentration for the asphaltene
aggregate formation, which is roughly 10-4 mass fraction, regardless of
the origin of asphaltenes. Accordingly, the aggregation increases as the
asphaltene mass fraction also increases. The asphaltene aggregation has
been studied by small-angle X-ray scattering (SAXS), and small-angle
neutron scattering (SANS) [48–52]; these techniques can unravel the
size and structure of the nanoaggregates, e.g., disk-like [49,53], spheres
[54], ellipsoids and spheres [55], spherical and oblate cylinders
[56–57]. Nevertheless, the obtained asphaltenes from hydroprocessed
crude oils present an aggregation of the micelle cores in conjunction
with metal atoms such as Vanadium or Nickel because high tempera­
tures remove the alkyl chains. As a consequence, asphaltenes present
changes in their morphology [58–65].
Different groups have studied the surface morphology of crude oil
and asphaltenes films by means of AFM; such studies have shown
spherical [66–67], disk-like [66,68], amorphous particles [66–67,69],
oligomer-like structures [70], and different shapes such as mushroom-
like [71], drumstick-like, ribbon-like structures [24]. Moreover, AFM
has been used to understand the mechanism of asphaltene adsorption on
minerals (silica [27,72–73], calcite [67,74], calcium fluoride [75], sili­
con dioxide) [67–68], clay minerals (mica) [24,67,70–71,76–78], and
metals, such as gold [66] and stainless steel [69]. Also, SEM is another
applied microscopic technique widely used to analyze the surface
morphology of asphaltenes. Luo et al. [79] used the three classical light
alkane precipitants, i.e., n-propane, n-pentane, n-heptane, to obtain the
asphaltenes. It is worth mentioning that the precipitated asphaltenes
with n-propane were obtained at high pressures: The precipitated
2
Fuel 307 (2022) 121852
asphaltenes with n-propane showed a smooth and amorphous semi-solid
surfaces, and the surface was much smoother for the obtained asphal­
tenes with n-heptane than with n-pentane. Therefore, such a difference
was attributed to the solvent precipitant, since the asphaltene precipi­
tation with n-heptane was much slower than with n-pentane or n-pro­
pane. Consequently, the obtained asphaltene aggregates with n-heptane
had more time to form tighter surfaces. Hosseini-Dastgerdi et al. [80]
obtained the asphaltenes from live synthetic oil, and they studied the
change in the asphaltene morphology as the pressure decreases. These
asphaltenes presented a spherical and elliptical shape independently of
the pressure at which they were obtained. Although the asphaltene ag­
gregates were more agglomerated, sticky, and irregular as the pressure
decreased. This research group suggested that solubility of the asphal­
tenes decreased; as a result, the asphaltene aggregates coalesced. Also,
the SEM technique has been used to study the asphaltenes from hydro­
processed oils, i.e., such asphaltenes were obtained at high tempera­
tures. Several research groups have observed porous and smooth
surfaces on the spherical aggregates of asphaltenes. According to these
researchers, the pore size increases as the temperature also increases
[58,60,62].
The aim of this work is to apply the mechanical and microscopic
techniques: Langmuir trough, BAM, AFM, and SEM to understand the
interfacial behavior of Mexican bitumen and its asphaltene and maltene
fractions on water and mica surfaces. It is worth noting that such sur­
faces were chosen to mimic the case of hydrophilic surfaces commonly
found in oil wells, which are made of silicates and usually are cover by a
thin layer of water. Surprisingly, the isotherm results show that the
surface pressure of the bitumen follows the thermodynamics rule of an
ideal mixture behavior; this is, since the surface pressure of the bitumen
is the sum of the surface pressure of the asphaltenes plus the maltenes,
even though each fraction is a mixture of a great number of molecular
components. In addition, we show the different structures that bitumen,
asphaltenes and maltenes form. While bitumen and asphaltenes show
similar structures, maltenes at relatively low surface pressure tend to
form more one- and two-layer films that resemble those formed by long-
chain lipids [81].
2. Experimental section
The asphaltene and maltene samples were obtained from a Mexican
bitumen, i.e., as a solid phase. Asphaltenes were precipitated from
bitumen by adding n-pentane (>99%, Sigma-Aldrich, USA) in the ratio
of 1.5 ml to each 0.15 g of sample. The sample was sonicated for 10 min
and applied centrifugation to 12000 rpm for 5 min at 278.15 K. The
liquid (maltene fraction) was decanted through a 0.45 μm membrane.
After 15 solubilization-sonication-centrifugation-decantation cycles
with n-pentane; the samples of asphaltenes and maltenes fractions were
obtained. We analyzed the obtained fractions, and we determined that
the bitumen contained 80 and 20 wt% of asphaltenes and maltenes,
respectively. All bitumen and asphaltene samples were dissolved and
stored in toluene (>99.8 %, Sigma-Aldrich, USA); whereas maltenes
sample was dissolved and stored in n-pentane.
The surface pressure-area (Π-A) isotherms were determined using a
Langmuir balance (Model 601BAM, Nima Technology LTD, Coventry,
England) using a Wilhelmy plate, to measure the lateral surface pres­
sure, Π = γo − γ, i.e., the surface tension difference of the clean subphase
and that of the subphase covered with bitumen, asphaltene or maltene.
Before doing each experiment, the Langmuir trough was thoroughly
cleaned with chloroform (>99.9%, Sigma-Aldrich, USA), absolute ethyl
alcohol (anhydrous, 99.9%, J. T. Baker, USA) and bioresearch grade
water (18.3 MΩ-cm of resistivity, Barnstead/Thermolyne, Dubuque,
Iowa, USA). The Langmuir trough was cleaned until the surface pressure
reading of pure water was zero after full compression and no contami­
nants were observed on the surface of the water by means of the BAM.
Prior to each experiment, the water surface was further cleaned by
aspirating the surface with a Pasteur pipette connected to a vacuum
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

aspirator. Bitumen, asphaltene, or maltene samples were spread at the

air/water interface by carefully depositing the samples drop-by-drop on
the surface of deionized water, using 100 μl microsyringe. The volumes
and concentrations of bitumen, asphaltenes, and maltenes solutions
spread in the water surface are shown in Table 1.
Surface pressure versus area per molecule (Π -A) isotherms were
obtained by compressing the asphaltene films slowly at the rate of 20
cm2/min. Such compression was started from an initial (maximum)
trough area of 710 cm2. Before the deposited films were compressed, we
waited at least 30 min., an estimated time to be enough for the different
solvents used to evaporate.
Observations of the bitumen, asphaltene, and maltene textures at the
air/water interface were performed with BAM (Mod. I-Elli2000, Nano­
Film Technology, Göttigen, Germany) placed above the LB trough. BAM
is a very sensitive technique specially designed to look at mono­
molecular films at the air/water interface [82,83]. All the images were
taken with 10x objective and were geometrically corrected for the
deformation introduced by observing at the Brewster angle. The lateral
resolution of the BAM images is approximately 2 μm. The entire
experimental setup was mounted on a vibration-isolated optical table
(MICRO-g, TMC, U.S.A.). The average molecular weight used in the
isotherm determination was 1500 Da [24] for asphaltenes; whereas the
average molecular weight of maltene fraction was determined from a
Mexican heavy crude oil [84], the obtained value is 362 Da. With regard
to average molecular weight for bitumen; we consider the same value
from asphaltenes because bitumen contains 80 wt% of asphaltenes.
After recording the isotherm and selecting a given surface pressure,
the Langmuir films of bitumen, asphaltene and maltene films, were
transferred onto freshly cleaved mica from the air/water interface by the
Langmuir-Blodgett technique, at constant surface pressure, and a slow
transfer rate of 1 mm/min. All experiments were carried out at room
temperature (~298 K).
The surface morphology of transferred films was analyzed by AFM
(Nanoscope IIIa, Digital Instruments, Santa Barbara, C.A.). All AFM
images were obtained using both contact and tapping modes, using
standard silicon nitride tips with a normal spring constant of 0.12 and
40 N/m, respectively, at a scan rate of 2 Hz. The AFM images were taken
at a scan size of 100 μm × 100 μm down to 0.5 μm × 0.5 μm using a J-
scanner. The transferred films were also examined by a SEM (Model
Philips XL30) attached to an energy dispersive X-ray spectrometry (EDS,
Model 350C, Edax Inst.). The SEM micrographs were taken under an
Fig. 1. (a) Langmuir isotherms, surface pressure versus area (Π versus A) for
accelerating voltage of 10, 15 and 20 kV. bitumen, asphaltene, and maltene samples spread at the air/water interface,
and calculated Langmuir isotherm, calculated surface pressure versus area (Π
3. Results and discussion versus A) for bitumen. (b) Asphaltene and bitumen isotherms but rescaled with
respect to isotherm shoulder position (Π/ Πc versus A/ Ac). The inset presents
3.1. Isotherm measurement and BAM characterization how the bitumen shoulder position was calculated in the Langmuir isotherm of
bitumen, surface pressure versus area (Π versus A).
Fig. 1a shows the isotherms for bitumen and their asphaltene and
maltene fractions spread at the air/water interface. As can be seen in that bitumen and asphaltene isotherms are analogous to typical car­
Fig. 1a, the shape of the Langmuir isotherms is similar for the asphaltene boxylic fatty acids [83,85] and that their isotherms show a similar
and bitumen samples, both films present sigmoidal curves, unlike the behavior; this behavior could be due to bitumen contains 80 % of
maltene isotherm. The shape of the asphaltene and maltene isotherms asphaltenes. It is important to note that the three isotherms start at very
are analogous to isotherms reported for other authors [18–24,27,29,31]. low surface pressure, c. a. Π ≪ 1 mN/m. When isotherms of Langmuir
Although, to the best of our knowledge, the shape of the isotherm for films show a very low surface pressure usually is due to the presence of a
bitumen cannot be found in the scientific literature at room tempera­ two-dimensional gaseous phase (G); in this case, a gas phase means a
ture, as we showed it. It can also be observed, as the films are com­ phase with a very low surface density of molecules or regions of almost
pressed, that different phase changes are present. It is interesting to note pure water. Since the surface pressure is practically constant, the
isotherm behavior does not correspond to the presence of a pure gas
phase, but rather it must resemble a coexistence region between the
Table 1 gaseous phase and a condensed phase. BAM images, Fig. 2a, b, Fig. 3a,
Bitumen, asphaltene, and maltene concentrations in toluene used.
and Fig. 4a, b, c for bitumen, asphaltene, and maltene films, respec­
Sample Concentration Spread volume Mass deposited tively, confirmed this. On further compression, the surface pressure in­
μg/μl μL μg creases, and it is observed a steep slope in the range of 31.5 to 18.3 and
Bitumen 0.254 1000 254 37.1 to 22.6 Å2/mol for asphaltene and bitumen films, respectively. It
Asphaltenes 1.120 132 148 means that such part of the isotherms behaves in a similar way as the
Maltenes 1.580 23 37
liquid-condensed (LC) phase; since our systems are not made of pure

3
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

Fig. 2. BAM images of bitumen film formed at the air/water interface, corresponding to a concentration of 0.254 μg/μl: (a) and (b) Π = 0 mN/m and A = 40.3 Å2/
mol., (c) Π = 14 mN/m and A = 26.1 Å2/mol., and (d)) Π = 22 mN/m and A = 21.6 Å2/mol. The images are 504 × 462 μm2.

Fig. 3. BAM images of asphaltene film formed at the air/water interface, corresponding to a concentration of 1.120 μg/μl: (a) Π = 0 mN/m and A = 48.3 Å2/mol.,
and (b) Π = 55 mN/m and A = 4.2 Å2/mol. The images are 504 × 462 μm2.

components, the gas phase does not disappear right after surface pres­ and 21.3 mN/m, respectively. It could indicate that such films are folded
sure take-off, but at a few mN/m after that. In addition, the asphaltene and buckled. Nonetheless, a continuous collapse occurs after the change
and bitumen films show a slope change at surface pressures around 24 of slope and become more notorious as the surface pressure increases,

4
M.A. Zúñiga-Hinojosa et al.
Fig. 4. BAM images of maltene film formed at the air/water interface, corresponding to a concentration of 1.580 μg/μl: (a) Π = 0 mN/m and A = 111.9 Å2/mol., (b)
Π = 0 mN/m and A = 107.4 Å2/mol., (c) Π = 0 mN/m and A = 93.6 Å2/mol., and (d) Π = 14 mN/m and A = 25.1 Å2/mol. The images are 504 × 462 μm2.
observed with BAM because the number of brighter structures increases,
similar to a typical isotherm of fatty acid monolayers [83,85–88]. In this
work, the surface pressures keep increasing up to 55.5 and 27.5 mN/m
for asphaltene and bitumen films, respectively, i.e., these films do not
present any abrupt collapse in this surface range; but they do show a
continuous collapse. According to Cadena-Nava et al. [24] and Alvarez
et al. [19] after the folding and buckling point, the asphaltene film
became flexible when the surface pressure is increased. Hua and Angle
[29] suggested that such flexible behavior is due to its elasticity. These
authors [89] confirmed later the elasticity properties of bitumen and
asphaltene films by interfacial rheology. The obtained elasticity results
showed that bitumen films are more elastic than asphaltene films. We
will also present below the elasticity behavior by BAM images for
bitumen and asphaltene films. Regarding the maltene isotherm, we
observed that as the barriers are moved closer, the surface pressure
takes-off at 81.2 Å2/mol, and it increases gradually up to about 25 Å2/
mol, i.e., the maltene isotherm does not exhibit a steep slope. Accord­
ingly, we assumed that there does not exist the liquid-condensed (LC)
phase, only the equivalent to the so-called liquid-expanded (LE) phase in
such isotherm. According to Ese et al. [25], the long hydrocarbon chains
of the resin fraction are able to pack them to form an overfilm before
reaching the liquid-condensed phase. They also stated that the inter­
locking forces among methyl groups of hydrocarbon chains present a
high-energy barrier to be overcome before attaining a condensed state.
Nonetheless, Alvarez et al. [19] mentioned that if an overfilm is formed,
then the maltene aggregates would grow, and the surface pressure
5
Fuel 307 (2022) 121852
would also increase. They concluded that such behavior had not been
found in the scientific literature. In this work, we confirm that the
molecules of the maltene fraction are able of packing and forming a
mixture of two- and three-dimensional layers as shown below by Figs. 4,
7, and 14, which are BAM, AFM, and SEM images, respectively.
As can also be seen in Fig. 1a, the slopes of the bitumen and
asphaltene isotherms at the liquid condensed phase are not very high,
even more, the maltene isotherm shows a much smaller slope. It in­
dicates that the continuous two- and three-dimensional domains of the
three samples are quite compressible, being the maltene film the most
compressible film. An examination of this figure also shows that the
isotherm behavior of bitumen is the result of adding the behavior of
asphaltene and maltene isotherms multiplied by their molar fractions,
respectively, i.e., it is described by the mixing rule. Therefore, the area
(A) and the surface pressure (Π) can be expressed as:
Abit ≅ 0.8Aasph + 0.2Amalt (1)
Πbit ≅ 0.8Πasph + 0.2Πmalt (2)
It can also be seen in Fig. 1a that the bitumen and asphaltene iso­
therms present a shoulder in a range of (20–25) mN/m. SEM images
show the differences of the surface morphology between the bitumen
and asphaltene films before and after the isotherm slope changes, which
are presented below by Fig. 8 for the bitumen film and Figs. 11 and 12
for the asphaltene film. The corresponding surface pressure and area to
each shoulder (i.e., to each slope change) we denominated it as a change
M.A. Zúñiga-Hinojosa et al.
Fig. 5. AFM images for bitumen transferred at Π = 25 mN/m and A = 18 Å2/mol. Fig. 5a shows a 20 × 20 μm2 region and a maximum height of 45 nm, Fig. 5b
presents a 15 × 15 μm2 region and a maximum height of 25 nm, and Fig. 5c shows a 7 × 7 μm2 region and a maximum height of 25 nm.
of slope condition of the film. We use the weighted average procedure
[90] to obtain the change of slope properties from experimental data for
asphaltene and bitumen films; their results are presented in Table 2.
It was surprising that the bitumen isotherm can be obtained as an
addition of the asphaltene and maltene isotherms, since both fractions
are a collection of a very different mixture of molecules, thus we
calculate the bitumen isotherm from the isotherms of its fractions. First,
we determine the change of slope surface pressure for bitumen calcu­
lating the area of maltene film at its hypothetic slope using the equation
( )
Amalt Abit − 0.8Aasph /0.2. Accordingly, the obtained value of the mal­
tene film is 39.8 Å2/mol, and its corresponding surface pressure is 8.8
mN/m. Consequently, we apply the equation Πbit ≅ 0.8Πasph +
0.2Πmalt , to calculate the change of bitumen film’s slope surface pres­
sure; the obtained value is 20.9 mN/m, whereas the experimental value
is 21.3 mN/m. Thus, the average percent deviation (APD%) is 1.87%. On
the other hand, to show that from the addition of the asphaltene and
maltene isotherms, the bitumen isotherm can be obtained, we also
calculate the average area for bitumen and its fractions. The obtained
values are 25, 35.8, and 77.7 Å2/mol for asphaltene, bitumen, and
maltene films, respectively. Such values were also estimated using the
weighted average procedure [90]. Then, we apply Eq. (2), the calculated
6
Fuel 307 (2022) 121852
area for bitumen film is 35.9 Å2/mol, and the APD% is 0.3%. Thus, to
calculate the bitumen isotherm, we determine a straight line from the
values of change of slope surface pressure (Π c) and area (Ac), and the
average area for bitumen, 37.1 Å2/mol, at a surface pressure of ≈0 mN/
m. The APD% is 5.66%, see Fig. 1a. Therefore, the isotherm behavior of
bitumen is the result of applying the mixing rules to the asphaltene and
maltene fractions.
Another interesting result reported here is that when asphaltene and
bitumen isotherms are rescaled with respect to their change of slope
surface pressure (Π c) and area (Ac), a master isotherm curve is formed,
as shown in Fig. 1b. The literature points out that the formation of this
type of shoulder in isotherms of asphaltene samples from other sources is
a general feature [23,29–30]. In the case of the asphaltene and bitumen
films, their shoulders do correspond to a transition-like behavior from a
solid-like to a plastic-like behavior of the film [24]. We suggest that the
isotherms behavior and the process of folding and buckling films could
be controlled by the chemical and/or electrostatic molecular in­
teractions of the dominating fraction of the bitumen composition.
Accordingly, the interfacial behavior of bitumen could also be deter­
mined by the dominating fraction, in our study by the asphaltene frac­
tion, but in other type of bitumen the maltene could be the dominating
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

Fig. 6. AFM images for asphaltenes transferred at Π = 10 mN/m and A = 22.5 Å2/mol. Fig. 6a shows a 30 × 30 μm2 region and a maximum height of 25 nm, Fig. 6b
and 6c present a 20 × 20 μm2 region and a maximum height of 30 nm, Fig. 6d shows a 10 × 10 μm2 region and a maximum height of 50 nm, and Fig. 6e shows a 5 ×
5 μm2 region and a maximum height of 15 nm.

7
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

Fig. 7. AFM images for maltenes transferred at Π = 10 mN/m and A = 35.8 Å2/mol. Fig. 7a and 7b show a 50 × 50 μm2 region and a maximum height of 10 nm.

Fig. 8. SEM images for bitumen transferred at (a) Π = 10 mN/m and A = 28 Å2/mol, and magnified 820×, (b) Π = 15 mN/m and A = 25.6 Å2/mol, and magnified
2654×, (c) and (d) Π = 22 mN/m and A = 25.6 Å2/mol, and they were magnified 800× and 1490×, respectively.

fraction.
Fig. 2 shows BAM images for the bitumen film that correspond to its
Langmuir isotherm of Fig. 1a at different surface pressures. As can be
seen in Fig. 2a, the bitumen film almost covers the water surface, but
continuous domains with different thickness can be observed after the
sample is freshly spread on the water surface, i.e., at a surface pressure of
≈0 mN/m and an area of 37.1 Å2/mol. Such film contains two- and
three-dimensional domains, which are represented by bright spots and
dark or gray areas domains. That is, the bitumen film exhibits different
molecular thickness since thicker regions reflect more light, therefore
they look brighter. Whereas, the black regions might correspond to
uncovered water surface or are regions with a low density of molecules
(gas phase), as shown in Fig. 2b. We can also observe that the few black
regions, gas phase, represent the low compressibility of the bitumen
film. Hua and Angle [29] also showed a low reflectivity with few bright
spots at a surface pressure of 18 mN/m in a concentration of 10 mg/ml,
with a spreading volume of 250 μl, this is a deposited mass of 2500 μg;
while in our case we observe such behavior at a surface pressure of ~ 0
mN/m using a concentration of 0.25 μg/μl, with a spreading volume of
1000 μl, thus the deposited mass is 250 μg. We consider that this

8
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

Fig. 9. SEM images for asphaltenes transferred at Π = 0 mN/m and A = 48.3 Å2/mol. Fig. 9a, 9b and 9c were magnified 1242×, 9934×, and 20000×, respectively.

Fig. 10. SEM images for asphaltenes transferred at Π = 10 mN/m and A = 22.5 Å2/mol. Fig. 10a and 10b were magnified 42× and 173×, respectively.

difference could be attributed to the asphaltene content of the bitumen:
Hua and Angle [29] reported a molar fraction of asphaltenes of less than
0.20 in their studied bitumen, whereas our bitumen contains a molar
fraction of asphaltenes of 0.80. As was mentioned above, the isotherms
of Langmuir films at low surface pressures show two-dimensional re­
gions of the gaseous phase, i.e., dark regions of almost pure water.
Nevertheless, Fig. 2a and b show that three-dimensional domains also
are formed. Therefore, the bitumen film presents a coexistence region
between the gaseous phase and a “liquid-condensed” multilayer phase at
~0 mN/m. Then, the domains correspond to aggregated bitumen do­
mains. As the barriers move closer, the bitumen film shows a more
compact and continuous film, as can be seen in Fig. 2c. As the surface
pressure keeps increasing, the bitumen film becomes more compact, and
the black regions disappear. Accordingly, the reflectivity increases
slightly from black to gray, shows domains with different heights (See
Fig. 2d).
Fig. 3 shows BAM images of the asphaltene film; in Fig. 3a the
asphaltene sample presents two- and three-dimensional domains after it
is deposited on the water surface at a very low surface pressure, 31.5
mN/m. Note the resemblance of the asphaltene domains with those of
the bitumen, but the asphaltene domains are somewhat bigger. There
exist very few asphaltene-free areas since they tend to form an almost
continuous multilayer, i.e., the asphaltene film does present very few
black regions or gas phase and the asphaltene aggregates appear as
bright domains surrounded by mostly different gray regions indicating
that asphaltenes consist mainly of three-dimensional structures with
different thicknesses [24]. It has been reported that asphaltenes can
form island- or archipelago-like structures independently of asphaltene

9
M.A. Zúñiga-Hinojosa et al. Fuel 307 (2022) 121852

Fig. 11. SEM images for asphaltenes transferred at Π = 20 mN/m and A = 19.5 Å2/mol. Fig. 11a, 11b, and 11c were magnified at 83×, 645×, and 1288×,
respectively.

Fig. 12. SEM images for asphaltenes transferred at Π = 30 mN/m and A = 14.8 Å2/mol. Fig. 12a and 12b were magnified at 84× and 343×, respectively.

Table 2
Change of isotherm slope conditions of bitumen and asphaltene films.
Sample Change of slope surface pressure, Π c Change of slope area, Ac
mN/m Å2/molecule
Table 3
Bitumen 21.3 22.6 Elemental composition of asphaltene sample compared to Mexican asphaltene of
Asphaltenes 24 18.3
a crude oil collected from an offshore well, wt %.
Elements This work Reported asphaltene [66]
concentration, according to Chacón-Patiño et al. [91], who studied two Carbon 85.5 81.5
types of bitumen with FT-ICR MS, the Yen-Mullins molecular structure Hydrogen 6.5 7.6
cannot be used to describe all asphaltene samples because of island-like Nitrogen 0.9 1.9
and archipelago-like models coexist. Nevertheless, they showed using Oxygen 0.2 1.8
Sulfur 6.9 7.2
the extrography fractionation that a structural continuum is formed, H/C atomic ratio 1.0 1.1

10
M.A. Zúñiga-Hinojosa et al.
where archipelago-like structure is more likely to form as the molecular
weight and polarity of asphaltenes increase. Table 3 presents the
elemental analyses of the asphaltene sample of the studied bitumen in
this work and a reported crude oil from a Mexican offshore well. Note
that such crude oil shows a series of islands of different thickness [24].
As can be seen in Table 3, our asphaltene contains a higher amount of
carbon than the asphaltene from crude oil; while, the amount of
hydrogen in our asphaltene is less than the reported asphaltene of crude
oil from the offshore well. It suggests that the studied asphaltene sample
consists of a higher amount of aromatics rings and less amount of hy­
drocarbon chains. For this reason, the BAM images of asphaltene film
show an almost continuous film, with very few low-density zones, as can
be appreciated in Fig. 3a at a surface pressure of ~0 mN/m. According to
Headen et al. [92], who studied the asphaltene aggregation using mo­
lecular dynamics simulations, the island-like asphaltene structures have
a large aromatic core, as is our case (See Table 3) and a strong steric
tendency for π-π stacking, leading to the formation of the oblate struc­
tures. Thus, we suggest that such oblate structures mimic two- and three-
dimensional domains and they could cause the bright aggregates; then,
the formation of stacked structures could form more rigid films of
asphaltene. However, Lobato et al. [30] stated that the self-aggregation
of asphaltenes does not occur for their more soluble asphaltene fraction
(18:1). Accordingly, the bright aggregates do not exist. We present
bright asphaltene aggregates in Fig. 3. As the barriers are moved closer,
the very few thinner regions tend to disappear, whereas the three-
dimensional domains begin to approach each other in order to attach
themselves and form bigger aggregated of asphaltenes; accordingly,
such aggregates are brighter due to they become thicker, independently
of the asphaltene film phase. These observations are consistent with the
results reported by other groups [18–19,29]. The presence of very few
black zones in the asphaltene films indicates very low compressibility, as
it was demonstrated through its Langmuir isotherm in Fig. 1a. When
barriers keep compressing the asphaltene film, we do not observe a
significant change in its BAM images, even at higher surface pressures
than the slope surface pressure change, as shown in Fig. 3b; this figure
shows the asphaltene film at a surface pressure of 55 mN/m, which is the
maximum surface pressure reached. As it can be observed, the white,
three-dimensional domains are somewhat greater than the domains in
Fig. 3a, as well as the dark asphaltene-free zones almost disappear from
the compressed film. Note that the phase transitions or points of change
of slope surface pressure and area do not show significant changes
through the BAM images as the Langmuir isotherm of asphaltenes does.
Fig. 4 shows BAM images of the maltene film at ~0 to 14 mN/m.
Fig. 4a presents a mixture of two- and three-dimensional domains when
the maltene sample has been deposited on water surface. It is interesting
to note that the thicker, brighter domains are inside the darker domains.
Even more, the film exhibits rounded domains of different reflectivity
surrounded by gray zones similar to cholesterol films [93]. The forma­
tion of dark circular domains indicates a low-density of maltene film and
they are identified as a gas phase. Whereas the gray zones contain less
bright circles, which could represent the liquid expanded-like phase. It is
important to note that the thickness of the gray regions is very ho­
mogenous, and it shows large extensions of gray hues that resembles a
foam-like structure, as shown in Fig. 4b; this type of structures resembles
those formed by Langmuir monolayers of fatty lipids. According to
Alvarez et al. [18] a gray color represents the formation of extremely
thin films in the gas phase, as maltene film shows it. It can also observe
in Fig. 4b the presence of three-dimensional elongated domains. A
peculiar characteristic of maltene film is its mobility not observed in
bitumen and asphaltene films. As the boundaries of the domains
approach each other, the two-dimensional domains coalesce and form
larger domains, as shown in Fig. 4c. An examination of this figure also
shows different gray hues in rounded areas; such hues could be caused
by the less mobile domains formed by hydrocarbon chains of maltene
fraction, which could rearrange as the borders move closer. Note also
that these domains are not completely circular, thus the line tension is
11
Fuel 307 (2022) 121852
not capable to form a smooth boundary as the surface pressure increases,
as has been observed in mixtures of DMPC-dihydrocholesterol [94].
Fig. 4d presents the maltene film at 14 mN/m, where it can be observed
the film is already collapsing, since there are a good number of small
bright domains, i.e., the maltene film shows an almost homogenous film
with out-of-plane three-dimensional domains. Nevertheless, the maltene
isotherm does not present any change of slope, indicating that the for­
mation of the bright three-dimensional domains is due to a continuous
collapse process. Alvarez et al. [19] stated that an overfilm is formed
when the aggregates grow as the surface pressure increases, which
agrees with our observations.
3.2. AFM characterization
Figs. 5–7 present the AFM images of bitumen, asphaltene, and mal­
tene films, respectively, on mica to point out their differences on surface
morphologies at a microscopic scale. Fig. 5 shows the AFM images of
bitumen film at Π = 25 mN/m and A = 18 Å2/mol. Fig. 5a shows a 20 ×
20 μm2 region of such a film surface with a maximum height of 45 nm,
and it contains disk-like structures of different sizes. Note the presence of
three large particles, which are surrounded by a series of small spherical
and elongated structures. Regarding the thickness of the film, it is worth
mentioning that at the nanometer scale some of such small structures are
taller than the big particles. Fig. 5b shows a region (15 × 15 μm2 and a
maximum height of 25 nm) rich in small disk-like and elongated struc­
tures. A similar disk-like morphology at the film surface have been
shown by Batina et al. [66] for Mexican oils. Nonetheless, they prepared
their samples by depositing an oil drop over a gold substrate. To confirm
the formation of disk-like and elongated particles, Fig. 5c shows a closer
look at a 7 × 7 μm2 region and a maximum height of 25 nm. It can be
observed the existence of drumstick, Argentine bola, and crochet hook
mesostructures as they have been previously reported for asphaltenes
[24]. Since the bitumen sample has a high fraction of asphaltenes, it is
not surprising that some of the structures observed in the bitumen
sample are similar to the asphaltene samples.
Fig. 6 shows AFM images of the topography of the asphaltene film at
Π = 10 mN/m and A = 22 Å2/mol. Fig. 6a presents a 30 × 30 μm2 and a
maximum height of 25 nm region. As can be observed, the asphaltene
particles are clumped together, and their morphology looks like large
grains with clearly defined edges. However, the larger grains are made
from the coalescence of smaller grains, because they still show defect-
like lines on their surface as a result of the coalescence process. A re­
gion of 20 × 20 μm2 and a maximum height of 30 nm observed in Fig. 6b
shows several structures with different sizes and shapes. On the left side,
it can be seen rounded structures of similar size but towards the center of
their surface it can be observed small granules that indicate that these
rounded domains could be the result of the coalescence of smaller
granules. In fact, at the bottom of the image, asphaltene particles of very
small size but with different shapes. It is important to highlight that in
the upper right of this image, it can be observed an elongated and even a
wormlike mesostructures, which has also been reported before [24].
Fig. 6c shows a closer look at the wormlike structure, which is the largest
structure of this image. According to Cadena-Nava et al. [24], the small
disks, either drumstick, Argentine bola, or crochet hook mesostructures,
may elongate to form thin ribbons. Moreover, these ribbons can coalesce
to form irregular wormlike structures when they are under high surface
pressure or in contact with a hydrophilic surface. An exemplification of
the process mentioned above, can be observed in Fig. 6c. In this figure,
we can see the presence of several drumstick and crochet hook structures
around the wormlike structure. Therefore, the wormlike structure could
be formed from the drumstick and crochet hook structures. Fig. 6d
shows a region of 10 × 10 μm2 and a maximum height of 50 nm. The
presence of many drumsticks structures indicates the possibility of
wormlike structures formation at a higher surface pressure. Headen
et al. [92] studied the effect of asphaltene aggregation of five different
asphaltene structures, i.e., island or archipelago type models, in toluene
M.A. Zúñiga-Hinojosa et al.
or heptane solutions using molecular dynamics simulations, as was
mentioned above. They found that the degree of asphaltene aggregation
is higher in heptane than in toluene, independently of the asphaltene
structure. Whereas the asphaltene formation of monomers, dimers, and
trimers was more significant when using toluene as a solvent. They also
observed that the aggregation is stronger when small aggregates are
present and, the only way for clusters to grow is that these small clusters
coalesce themselves. Therefore, these results agree with our AFM ob­
servations. Moreover, these researchers observed clear differences be­
tween the asphaltene aggregates formed from island- and archipelago-
like structures. The archipelago-like asphaltene structure favored the
formation of long prolate structures, whereas island-like asphaltene
structure favored the formation of oblate shapes. They also proposed
that the island-like asphaltene structures have a large aromatic core and
a strong steric tendency for π-π stacking, leading to the formation of the
oblate structures. However, Pacheco-Sánchez et al. [95] showed that
many asphaltene aggregates are not only in stacking form at the end of
every molecular dynamics simulation. They also remained in irregular
forms such as T-shaped (π-σ interaction) and offset-stacked (σ- σ inter­
action) aggregates. On the other hand, Javanbakht et al. [96] studied the
interaction type between nanoaggregates in clusters using atomistic
molecular dynamics simulations. They considered two interaction types:
van der Waals and electrostatic interactions. Nonetheless, these re­
searchers considered that the H-bonding and the polar functional groups
are absent in the van der Waals interaction. Their results show that the
van der Waals interaction is stronger than electrostatic interaction. Be­
sides, this research group suggested that the asphaltene aggregate con­
figurations are the T-shaped, edge-edge stacking, and angular stacking,
being the latter configuration dominant. Accordingly, these orientations
and interactions could lead to the formation of different shapes of
asphaltene aggregates such as drumstick, Argentine bola, or crochet
hook mesostructures, which we observed in AFM images. Fig. 6e pre­
sents a region of 5 × 5 μm2, with a maximum height of 15 nm. Such a
region contains many tiny globular particles at micron-scale, which
confirms that the asphaltenes behave as “colloidal” particles [24]. Raj
et al. [67] studied the morphology of asphaltene solutions by using
different substrates such as cleaved mica, calcite, silicon dioxide, and
graphite. They show that the shape and height of asphaltenes are
different depending on the substrate polarity. According to these re­
searchers, the asphaltenes form globular structures, and they can adhere
to a hydrophilic surface (like mica) through their heteroatoms.
Regarding the hydrocarbon chains, they also stated that these chains are
out of the surface, or they are buried within the aggregates due to their
hydrophobicity. Moreover, because of the low polarity, the hydrocarbon
chains can adhere easier to calcite and silicon dioxide surfaces and the
asphaltenes present irregular aggregates on these surfaces.
On the other hand, to the best of our knowledge, the maltenes have
not been studied using AFM. One of the purposes of the present work is
thus to show the behavior of maltene films with AFM. Fig. 7 presents the
AFM images of a maltene film at Π = 10 mN/m and A = 35 Å2/mol. It
shows a 50 × 50 μm2 region whose maximum height is 10 nm, see
Fig. 7a. It can be observed that the film contains regions with different
high, many rounded domains with disk-like shape, whereas their height
is at the nanometer scale; the difference in height between the different
structures is of the order of 2.4 nm, see Fig. 7b. This is typical a height of
lipid monolayers [88,92,97–98]. Therefore, maltenes play a significant
role in bitumen film since they behave like a fine plaster that aggluti­
nates the asphaltenes.
3.3. SEM characterization
Fig. 8 shows the SEM images of the bitumen film at different mag­
nifications. Fig. 8a presents a bitumen film at 820x magnification, Π =
10 mN/m and A = 28 Å2/mol. As can be seen, the bitumen film presents
a smooth and slightly porous surface with some additional bright spots
embedded in such surface. Pérez-Hernández et al. [99], who studied the
12
Fuel 307 (2022) 121852
asphaltenes from hydroprocessed oils, stated that the bright spots are
inorganic particles. As well as, Young-Jun [62] considered that the alkyl
chains linked to aromatic cores are removed during hydrotreating,
causing that asphaltene polarity increases and the aromatic cores get
stacked. Thus, the inorganic compounds stand out of the surface. It can
also be seen in Fig. 8a the detachment of the film; we consider that the
dewetting of maltenes could cause such layer detachment because they
are more labile than the asphaltenes, since the maltenes contain less
aromatic cores and smaller and hydrocarbon chain molecules than the
asphaltenes, which can cause the surface dewetting forming thick do­
mains due to cracking as the one observed at the top of Fig. 8a. Fig. 8b
shows a bitumen film transferred at Π = 15 mN/m and A = 26 Å2/mol,
which shows mostly a smooth surface with some tiny globular domains
and some holes. The smooth surface could be attributed to the bitumen
content of 80 % of asphaltenes and its large amount of aromatic cores.
On the other hand, maltenes could contribute to the surface porosity
because they contain less amount of aromatic cores. Therefore, as the
surface pressure increases, the maltene compounds could have more
tendency to form small three-dimensional rounded domains and cause
layer detachments, forming holes in the bitumen film. Fig. 8c and
d present a bitumen film transferred at Π = 22 mN/m and A = 21.6 Å2/
mol at 800× and 1490× magnification, respectively. Both images reveal
the behavior of bitumen film after the change in the slope of the Lang­
muir isotherm. It refers to the transition-like behavior from solid-like to
the plastic-like behavior of the bitumen film. We can observe in Fig. 8c
and d a fragile film with holes, i.e., the film is not continuum and
smooth, as shown in Fig. 8a, and b. Also, we can appreciate some de­
tachments inside of such holes. It could be attributed that hydrocarbon
chains are cracking, and some aromatic cores, as mentioned above.
Fig. 9 presents asphaltene images obtained when the sample was
freshly spread on the water surface, i.e., at a surface pressure of ~ 0 mN/
m. The image in Fig. 9a at 1242× magnification, reveals a discontinuous
film; dark and white zones correspond to the asphaltene film with
different thickness, whereas the white regions represent the uncovered
grid surface. It can also be observed that the asphaltene form big and
small domains; the bigger domains have a more defined shape than the
smaller ones. Fig. 9b shows an asphaltene film at 9934× magnification
with a closer look of the aggregates. The particles present several shapes,
e.g., disks, drumsticks and crochet hooks. Fig. 9c at 20000× magnifi­
cation shows a very thread-like structures that could aggregate to form
the particles mentioned above; these images are similar to the ones
observed by AFM in Fig. 6.
Figs. 10–13 exhibit the morphologies and textures of asphaltene
Fig. 13. SEM images for asphaltenes transferred at Π = 35 mN/m and A = 11.8
Å2/mol., and it was magnified at 84×.
M.A. Zúñiga-Hinojosa et al.
Fig. 14. SEM images for maltenes transferred at Π = 10 mN/m and A = 35.8 Å2/mol. Fig. 14a, 14b, and 14c were magnified at 160×, 1282×, and 2564×,
respectively.
films at different surface pressures. Fig. 10 shows different magnifica­
tions of an asphaltene film at Π = 10 mN/m and A = 22 Å2/mol. Fig. 10a
at 42× magnification shows the asphaltene film with a discontinuous
smooth surface. Fig. 10b presents the image of asphaltene film, at higher
resolution. It can be observed that the surface has different heights due
to the formation of porous or holes. This film structure could be
attributed to a continuous collapse as the barriers of the Langmuir
trough move closer, increasing the surface pressure, this causes stacking
of the aromatic cores and the bending of the alkyl chain. Then, as
Langmuir trough barriers get closer, the compression breaks the film
that begins to stack to form a non-uniform three-dimensional film. It can
also be observed some bright regions on the smooth surface of the
asphaltene film.
Fig. 11 shows the asphaltene film at Π = 20 mN/m and A = 19 Å2/
mol. Fig. 11a shows some regions of the smooth surface mix with a
porous layer, which is above the smooth surfaces. Then, as the barriers
of Langmuir trough begins to move closer at this surface pressure, the
asphaltene film break continuously, causing the formation of multi­
layers that do not form homogeneously, forming large pores. Fig. 11b
shows the image of asphaltene film at a higher magnification that de­
picts the inhomogeneities of the surface. It can be observed the forma­
tion of deep holes as well as the formation of small flake-like domains at
the bottom right side of the image. However, what it is interesting is that
it seems that the material that was expelled from the elongated hole
moved towards the bottom of the image creating a wave-like structure,
while at the top of the hole it seems to have created an elongated and
taller edge. This is also observed in the hole formed at the top of the
image, where the material formed thin edges where the material formed
thin and flexible edges between the holes. Even more, Fig. 11c shows a
closer look of the asphaltene film breakage, which might have occur at a
defect line, where the asphaltene material that is expelled out of the hole
13
Fuel 307 (2022) 121852
begins to form a fractal-like structure with the material that is being
expelled. As there are no other holes nearby, the material is ejected
evenly on both sides along the hole forming the fractal-like structure.
Fig. 12 presents the images of an asphaltene film at Π = 30 mN/m
and A = 14 Å2/mol, which are conditions above the surface pressure
where the isotherm has a change of slope; where this slope is lower that
the slope that the isotherm present before this slope change, which in­
dicates that the asphaltene film is more compressible than at lower
surface pressure. Fig. 12a shows very few smooth surfaces, since a very
disorganized white area with different thickness predominates, and
appears to be on a darker, more homogeneous and smooth surface. It can
be confirmed in Fig. 12b, which was taken from the central part of
Fig. 12a, it can be observed that the surface is porous, of different
thickness and quite disorganized. Fig. 13 shows an image of asphaltenes
transferred at Π = 35 mN/m and A = 11 Å2/mol, which clearly shows
the formation of different thicknesses in the film, as well as a rather
disorganized surface. Therefore, Figs. 12 and 13 confirm that under
these conditions of surface pressure, the asphaltene film is in continuous
collapse, as was mentioned above.
To the best of our knowledge, as in the case of AFM studies, the
behavior of maltene films have also not been reported using SEM. Thus,
images of maltenes transferred at Π = 10 mN/m and A = 35 Å2/mol and
obtained by SEM at different magnifications, are presented in Fig. 14.
Fig. 14a corresponds to the maltene film and its texture is extremely
porous and, therefore, fragile. A closer look at the film pores is observed
in Fig. 14b and c, which these images show that there are pores of
different sizes but their shapes are mostly round, and that there is a
thicker film on top of another film, in good agreement with the BAM and
AFM images, see Figs. 4 and 7, respectively. As mentioned above, those
holes are not completely rounded with a disk-like shape, as shown also
by BAM and AFM techniques.
M.A. Zúñiga-Hinojosa et al.
4. Conclusions
Bitumens have been gained a lot of interest in the past few years due
to the depletion of oil reservoirs. Therefore, a deeper understanding of
the behavior of the interfacial properties of bitumen and their asphal­
tene and maltene fractions will be helpful. In this work, we perform the
study of the interfacial behavior not only of bitumen but also of
asphaltene and maltene films by using the Langmuir through, BAM,
AFM, and SEM experimental techniques. Accordingly, significant dif­
ferences in interfacial properties between bitumen and its fractions have
been revealed. Additionally, the description of the isotherm behavior of
bitumen, asphaltenes, and maltenes requires mixing rules since the re­
sults obtained indicate that the mixing rules can satisfactorily represent
both the surface pressure and area. We also show that the Langmuir
isotherm of bitumen presents a strong correlation between the amount
of asphaltene and maltene fractions contained in bitumen. The results
indicate that the interfacial behavior of bitumen depends on the mo­
lecular interactions of the dominating fraction and not only on the
molecular weight of its components.
Regarding BAM images, the bitumen, asphaltene, and maltene films
contain two- and three- dimensional domains when the sample are
freshly spread on water surface. However, the asphaltene domains look
more rigid and more compact than those of bitumen, whereas the
thickness of the maltene film is extremely thin. Therefore, a peculiar
characteristic of the maltene film is its mobility not observed in bitumen
and asphaltene films. As well as we observed that the thicker, brighter
domains are inside the darker domains, and as domain boundaries get
closer to each other, the two-dimensional domains coalesce and form
larger domains.
On the other hand, the AFM images showed that the bitumen film is
the result of the agglomeration or stacking of the asphaltene “colloidal”
particles in the maltene overfilm. Note that to the best of our knowledge,
this work is a pioneer in studying the maltene film with AFM and the
films of bitumen and maltene using SEM. Therefore, no comparison with
other studies can be made. The SEM images confirmed the results ob­
tained with AFM, since they showed that the morphology of the
observed asphaltene structures is similar by both techniques, when the
samples are spread on the water surface. Additionally, the asphaltene
film presented single layer detachments as the surface pressure in­
creases, which resulted in the formation of an asphaltene porous layer.
We attribute the transition-like behavior from solid-like to a plastic-like
behavior of the bitumen and asphaltene films, i.e., the change in their
slopes, to the formation of a porous layer as these films are being
compressed. On the other hand, the texture of the maltene film is
exceptionally porous, and the pores have different sizes. Therefore, the
SEM and AFM images support the colloidal behavior of asphaltenes,
whereas the images for maltenes give a better understanding of their
overfilm formation and interfacial behavior. It is remarkably that the
maltene sample form a film that show BAM images similar to those
observed in Langmuir monolayers of long chain lipids at the air/water
interface, and that the thickness of the layers is similar to those of long
chain lipids. In addition, we can conclude that the maltenes play a sig­
nificant role in the bitumen, since they embed the asphaltenes. In
summary, the interfacial behavior of bitumen depends on the amount of
asphaltene and maltene fractions, i.e., such behavior is a function of the
dominating interactions regardless of the molecular weight of asphal­
tene and maltene fractions.
Author contributions
M. A. Zúñiga-Hinojosa did experimental work, data analysis and
contributed to writing the manuscript. A. Cosultchi did the design the
scientific work, M. T. Martínez-Martínez did experimental work, data
analysis and contributed to writing the manuscript, R. D. Cadena-Nava
did experimental work, data analysis, designed the scientific work and
contributed to writing the manuscript, J. Ruiz-Garcia designed the
14
Fuel 307 (2022) 121852
scientific work, contributed with the founding and to writing the
manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
We gratefully acknowledge the National Council for Science and
Technology of Mexico (CONACyT) for providing financial support for
this work, Grants CB-254981 and CB-237439.
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