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© 2013 American Chemical Society 4750 dx.doi.org/10.1021/la304873n | Langmuir 2013, 29, 4750−4759
Langmuir Article
amounts of asphaltene remain in the bulk solution. The frequency dependence of the dilatational modulus of asphaltene
pendant drop is therefore closer to depicting real systems. covered interfaces26−28 that the complex modulus follows a
Further, Langmuir trough experiments for an oil−water power law dependency over frequency:
interface are difficult to interpret, and asphaltene nano-
|E| ∝ ωn (4)
aggregates can fall onto the interface due to gravity settling
and/or solvophobic interactions between asphaltene molecules The exponent, n, appears to be proportional to the phase shift:
on the interface and nanoaggregates.20 ⎛ E″ ⎞ π
Shear rheology experiments also show significant elastic φ = A tan⎜ ⎟ ≈ n
response after long aging times,6,16,21,22 which is a sign of ⎝ E′ ⎠ 2 (5)
typical solidlike behavior. This behavior influenced previous These observations are in line with the predictions of a
analyses of the dilatational rheology data obtained for rheological model for a 2D gel that is close to the gel point.
asphaltenes.23−31 For example, observation of predominantly On the other hand, a somewhat different argument was made
elastic behavior (the elastic modulus E′ being much larger in by analyzing asphaltenes dilatational rheology data by
most instances to the “dissipative” modulus E″) was generally Szurukowski and Yarranton.29,30 They observed behavior
ascribed to the formation of a membrane with solidlike indicative of the LVDT model. At low asphaltenes concen-
behavior. tration (<50 ppm), the total modulus increased with time and
This interpretation of the results of dilatational rheology concentration and is rather insensitive to frequency. The elastic
experiments is not necessarily the only possible explanation. modulus was high, and the dissipative modulus was low. At
Other adsorbents can generate significant elastic moduli higher asphaltenes concentration (>50 ppm), the total modulus
without cross-linking. By analogy with the Gibbs modulus of increased with frequency and decreased with concentration.
a thin liquid film, Lucassen and Van den Tempel (LVDT) The ratio of the elastic modulus to dissipative modulus tended
established a theory for dilatational modulus based upon to decrease. They interpreted their experimental data with the
diffusional exchange between the interface and bulk solution.32 LVDT model. However, this approach only worked for short
Upon instantaneous expansion/contraction of a droplet, surface aging times (up to about 10 min). At longer times the results
coverage changes, as it is inversely proportional to the area of deviated and was ascribed to gelling. Freer and Radke31 took a
the droplet. This causes an instantaneous change in interfacial similar approach and reached a similar conclusion.
tension following the equation of state, which can be translated In addition to the difficulty in obtaining the parameters in the
into an instantaneous elastic modulus: LVDT model (acknowledged by Szurukowski and Yarranton),
−∂Π it should be recalled that the validity of LVDT model relies on
E0 = Γ the exchange between the adsorbed layer at the interface and
∂Γ (1)
the bulk solution being fully controlled by diffusion. In our
where Π is the surface pressure and Γ is surface coverage. recent study,1 we concluded that the adsorption of asphaltenes
For very slow oscillations, surfactants desorb/adsorb to at the water/oil interface is initially controlled by diffusion, so
maintain equilibrium between the adsorbed layer and bulk the LVDT theory should apply at this early stage. However, we
solution. In this case, the interfacial tension is constant and also found that the adsorption process slowed down as the
dilatational modulus vanishes. For finite frequencies, a dynamic surface coverage increased. Here the dilatational rheology
equilibrium establishes between variations of surface coverage results might deviate from the LVDT theory as concluded by
due to area changes and surfactant exchange. This generates a Szurukowski and Yarranton. We also concluded from the
dissipative (imaginary component) modulus E″ and elastic expansion experiments that interfacial tension was a unique
(real) modulus E′. By integrating the diffusion equations, one function of surface coverage irrespective of adsorption
obtains the LVDT model: conditions (time, viscosity of solvent, and concentration
below and above critical nanoaggregation concentration,
(ωτdiff ) + (ωτdiff /2)1/2
E′ = E 0 CNAC). This conclusion led to the hypothesis that there
1 + (ωτdiff ) + (2ωτdiff )1/2 (2) could be a unique equation of state for asphaltene adsorption in
terms of which the dilatational rheology results could perhaps
(ωτdiff /2)1/2 be explained.
E″ = E 0 To test this hypothesis, a regime of experiments was
1 + (ωτdiff ) + (2ωτdiff )1/2 (3)
undertaken using the same model systems used in our previous
where τdiff ≈ (1/D)(∂Γ/∂c) is the characteristic time of
2
study. The pulsating drop technique was used to measure the
diffusion and ω is the pulsation. interfacial rheological properties taking care to verify that
For low surface coverage (i.e., low surface pressure), τdiff is viscous and inertial effects do not alter measurements.
always very large, and E′ ∼ E0 for all practical frequencies (and Oscillation amplitude and frequency were varied for a range
E″ ∼ 0). When surface coverage and surface pressure increase, of oil viscosities, bulk asphaltene concentrations, and aging
τdiff decreases, E0 increases, and E′ tends to decrease (while E″ times. The elastic and dissipation moduli were derived from
increases). The LVDT model has been verified for a wide these data as discussed later. Of course, increasing amplitude,
variety of surfactants and proteins.32−35 Also, according to frequency, and viscosity also generates hydrodynamic effects,
LVDT, ω increases, E′ ≈ E0, which is called as instantaneous which render the use of the usual pendant drop equation
elasticity of the interface. invalid for extraction of interfacial tension and modulus data
With the LVDT model in mind, we discuss the interpretation from droplet shape analyses. In all cases we must verify that
of dilatational rheology results for asphaltenes containing oil− such hydrodynamic effects remain negligible compared to
water systems. Proof of cross-linking at the oil−water interface surface forces.
is not necessarily provided by the behavior of the elastic Several studies show that asphaltenes are a mixture of many
moduli. Perhaps a supporting argument can be found from the compounds.18,36−38 However, approaches to capture some
4751 dx.doi.org/10.1021/la304873n | Langmuir 2013, 29, 4750−4759
Langmuir Article
aspects of asphaltene behavior, particularly at the nanoscale, are are not accounted for in the calculations of interfacial tension and
often based on the average structure of asphaltene monomers, elastic modulus.
some of which associate to form nanoaggregates, and these in There are several ways to assess the importance of those forces in
turn can form clusters, the so-called Yen−Mullins model.3,4 As the chosen test conditions (up to 3 Hz and viscosities up to 28 cP)
with respect to the use of the Young−Laplace equation for
the current study focuses on macroscopic measurements of interpretation of the pendant drop results.
interfacial behavior, the results obtained primarily elucidate the First, in all test conditions, the profile analysis algorithm was able to
average state and composition of asphaltenes at the interface. fit the droplet shape well. (Droplet images and the Young−Laplace fit
As discussed later, theories for surfactant mixtures39−41 are to them are presented in the Supporting Information.) Second,
difficult to evaluate using these data. experiments have been carried out on the behavior of interfaces
between water and pure fluids (i.e., without asphaltenes) varying both
2. MATERIALS AND METHODS frequency and viscosity. These results are summarized in Table 2. It is
2.1. Chemicals. Chemicals used in this study are the same as
reported in our previous study. The water was deionized Milli-Q Table 2. Interfacial Moduli for Clean Water−Oil Interfaces
grade, with a conductivity of ∼0.05 μS/cm. It was premixed with 43 g/ over the Frequency Range Used in the Study
L of NaCl and 7 g/L of CaCl2, and the final pH was adjusted to 7 with
0.1 M NaOH. The asphaltenes were extracted by precipitation with 20 Nexbase 2002 (6 cP) Nexbase 2008 (28 cP)
vol of n-heptane to 1 vol of crude oil from the Norwegian continental freq (Hz) E′ (mN/m) E″ (mN/m) E′ (mN/m) E″ (mN/m)
shelf, stirring overnight at room temperature, followed by filtration and
0.02 0.68 0.02 0.252 0.102
rinsing with n-heptane. A stock solution of 1000 ppm asphaltenes in
toluene was prepared by sonication for 5 min (Sonics Vibra-Cell, 0.05 0.76 0.11 0.31 0.02
Newtown, CT) and then stored in a sealed glass vial wrapped in 0.1 1.22 0.67 0.529 0.221
aluminum foil to prevent exposure to light. Before use, the stock 0.25 0.45 0.233 0.854 0.233
solution is sonicated again for 5 min. Then the appropriate volume of 0.5 0.74 0.112 0.535 0.306
stock solution is withdrawn and further diluted with toluene before 1.25 1.05 0.532 0.786 0.3
mixing with an aliphatic synthetic oil of the Nexbase oil 2000 series 2.5 1.11 0.23 1.56 −1.34
(Neste Oil, Finland). The obtained asphaltene solution is then 3 0.98 0.002 1.453 −2.22
sonicated for a further 1 min. Asphaltene solutions are discarded after
24 h in order to avoid the effect of long-term phase segregation on
measurements. evident from the table that the moduli for oil−water interfaces without
The choice of the Nexbase 2000 series oil relies on the availability of asphaltenes are very small and when compared to data, presented later,
grades with varying viscosity without varying the chemical nature of on the moduli for asphaltene-bearing interfaces are essentially
the base oil (all are poly-α-olefins but with different chain lengths). negligible. The same range of frequencies was used for the asphaltene
The composition and viscosity of the different mixtures studied here bearing systems so that the pure fluid system could be considered as a
are reported in Table 1. Viscosity was measured using a 2° cone and reference.
In general, the method loses accuracy at high frequencies and
Table 1. Viscosities of Different Nexbase 2000 Series Oils highest viscosity tested. This is likely to be due to hydrodynamic
with 15% Toluene effects associated with the oscillation; i.e., the flow does not remain
purely radial. Such effects can be detected as they lead to negative loss
oil viscosity (Pa·s) moduli values (down to −2 mN/m). Data taken under these high-
85% Nexbase 2002 +15% toluene 0.0065
frequency and high-viscosity conditions are not considered further in
the current study. Only conditions at which we get positive values of
85% Nexbase 2008 +15% toluene 0.0280
moduli of clean interfaces are used. As a note, the elastic modulus
values do not, however, seem to be much impacted by hydrodynamic
plate configuration on a TA Instruments AR 2000 ex rotational effects. At low surface pressure (π = γ0 − γ) it is expected that E′ ∼ E0
rheometer at room temperature (298 K). Asphaltene concentration ∼ π, where E0 is Gibb’s elasticity and Π is the surface pressure. This is
ranged from 10 to 500 ppm, i.e., way below and way above CNAC (80 indeed the case: γ0 ∼ 41 mN/m, γ ∼ 40 mN/m, E′ ∼ 1 mN/m. It is
ppm1). also expected that the effect of hydrodynamic forces will be low on the
2.2. Pulsating Drop Module. Interfacial rheology experiments larger values of moduli measured for asphaltenes containing systems
were performed using pulsating drop module (PD200) in a KSV (both E′ and E″).
tensiometer. Pulsation of the droplet is carried out using a piezo crystal The amplitude dependence of the elastic modulus in systems
system, which is connected to the end of the needle. Amplitude and containing asphaltenes was also checked. For both membranes and
frequency of the sinusoidal oscillation can be monitored using the surfactants (with LVDT type elasticity), the complex dilatational
Attention Theta software by KSV. Droplet shape is analyzed by means modulus, E, should not depend on amplitude at least within the limit
of the usual pendant drop method which is based on the Young− of the linear elastic domain, which is the case with asphaltenes in the
Laplace equation42 to extract interfacial tension. Area and interfacial low-viscosity solvent.45,46 On the other hand, hydrodynamic forces do
tension variations are converted into a complex dilatational modulus depend upon the amplitude of oscillations (i.e., the flow rate of liquid
defined as in and out of the droplet). Figure 1 shows that even up to 3 Hz, elastic
dγ dγ moduli remain unchanged for strains between 2.0 and 4.5%, suggesting
E= =A that hydrodynamic effects are negligible if we stay in this frequency
d ln A dA (6)
range. Further, this also suggests that the stress−strain relationship is
From the phase shift between area and interfacial tension oscillations linear in this range of percent strain. (The amplitude range throughout
Φ, one can calculate the real (elastic) and imaginary (viscous) moduli: this study is kept at 2−3%.)
E′ = |E| cos ϕ , E″ = |E| sin ϕ (7) 2.3. Pendant Droplet as a Langmuir Trough (Expansion
Experiments). To investigate the relationship between interfacial
The use of high frequencies and viscosities could minimize exchange tension and surface coverage in various adsorption conditions, the
between the interface and bulk fluid (so that E′ ∼ E0, i.e., the pendant droplet apparatus is used as a Langmuir trough following a
instantaneous elasticity arising from the equation of state). However method developed for surfactants47,48 and applied to asphaltenes.1
this could lead to a bias in the measurement of interfacial tension due After a certain adsorption time, the droplet is rapidly expanded to the
to increasing hydrodynamic forces (both viscous and inertial43,44) that point of droplet detachment. Interfacial tension is measured as a
Figure 4. Instantaneous elasticity (f = 1.25 Hz) vs adsorption time for Figure 7. Instantaneous elastic modulus against square root of time/
different concentrations in Nexbase 2002. viscosity for 100 ppm in Nexbase 2002 and Nexbase 2008.
■
which we do not have for our systems.
oil−water interfaces was studied using the oscillating pendant Droplet images and the Young−Laplace fit to them. Graphs
drop technique, care being taken to ensure that the range of which show repeatability of moduli. This material is available
free of charge via the Internet at http://pubs.acs.org.
■
conditions was such that the technique was applicable. The
elastic modulus is found to be a function of frequency and
AUTHOR INFORMATION
adsorption conditions (concentration and aging time). For each
test condition, the elastic modulus was found to reach a plateau Corresponding Author
with increasing frequency (the instantaneous elasticity). The *E-mail banerjee@che.ccny.cuny.edu.
plateau value was found to be a unique function of interfacial Notes
The authors declare no competing financial interest.
■
tension, which in turn is a unique function of surface coverage.
These findings agree with aspects of the LVDT model at short
adsorption times and also reveal a unique equation of state ACKNOWLEDGMENTS
irrespective of adsorption conditions. The fit of the relationship This work is performed at the City College of New York under
between interfacial tension and surface coverage by a Langmuir the auspices of the FACE centrea research cooperation
equation of state allowed prediction of the relationship between between IFE, NTNU, and SINTEF. The centre is funded by
instantaneous elasticity and interfacial tension. This suggests The Research Council of Norway and by the following
that cross-linking is absent. The corresponding parameter (Γ∞) industrial partners: Statoil ASA, GE Oil & Gas, Scandpower
corresponds well to the expected size and interfacial Petroleum Technology AS, FMC, CD-adapco, and Shell
conformation of asphaltenes molecules adsorbed with their Technology Norway AS.
polyaromatic cores lying flat on the interface and the aliphatic The authors thank Professor Charles Malderelli for useful
chains perpendicular. This interpretation of the results is discussions and PhD student Sharli Zarkar for help with the
consistent with the picture proposed in the Yen−Mullins model experiments.
for asphaltene aggregation in the bulk fluid. The EOS fits
suggest that asphaltene monomers adsorb at the oil−water
interface but the nanoaggregates do not. Perhaps this is because
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