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Viscoelastic Effects on Spontaneous Imbibition in Unsaturated

Porous Membranes of Complex Shapes
Ali Gharagozlou, Mohammad Pourjafar-Chelikdani, Azadeh Jafari, and Kayvan Sadeghy*
Cite This: https://doi.org/10.1021/acs.langmuir.3c02947 Read Online

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ABSTRACT: Richards equation is a robust mathematical model

for predicting spontaneous imbibition in unsaturated porous
materials, whether granular or fibrous. The main restriction of
this imbibition model is that it is valid only for Newtonian fluids. In
Downloaded via Keyvan Sadeghy on January 3, 2024 at 06:14:09 (UTC).

the present work, we extend the classic Richards equation to

viscoelastic fluids using a modified version of the single-phase
Darcy’s law reported in the literature for several polymer solutions.
In two-dimensional flows, the viscoelastic Richards model obtained
this way turns out to be in the form of a system of three highly
nonlinear coupled partial differential equations for the moisture
content and the velocity field. The model is numerically validated
against published experimental data for a shear-thinning polymer
solution imbibed in a tight sandstone core sample extracted from a typical oil reservoir. The viscoelastic Richards model is then used
to investigate the effect of a fluid’s elasticity on the quasi-stationary regime in a two-dimensional porous membrane of complex shape
typically used in diagnostic kits. The obtained numerical results suggest that elasticity has a retarding effect on spontaneous
imbibition in capillary-driven, paper-based kits. Based on this new imbibition model, it is predicted that viscoelasticity of the
displacing liquid can extend the duration of the quasi-stationary regime on the test line of diagnostic kits. The conclusion is that, for
extending the quasi-steady regime in capillary-driven kits, it might prove useful to enhance the degree of elasticity of the test fluids
using appropriate rheology modifiers.

■ INTRODUCTION
It is a well-established fact that a wetting fluid such as water
can displace a nonwetting fluid such as air from the pores of
sandstones or filter papers by the action of the capillary forces.1
The phenomenon is called spontaneous imbibition (SI) and
plays a key role in the design of paper-based, capillary-driven
devices such as diagnostic kits, lateral-flow assays, and flow
batteries, among others.2−5 Owing to its significant techno-
logical importance, spontaneous imbibition has been the
subject of extensive studies in the past. For Newtonian fluids,
these studies have already revealed the importance of the
material’s microstructure and the liquid’s thermodynamic
properties on the rate at which the wetting phase is imbibed
or the nonwetting phase is displaced.1 But, industrial and
physiological fluids are often realized to exhibit non-New-
tonian behavior, and for such complex fluids, only recently, we
are witnessing the development of theoretical imbibition
models. One can particularly mention the recent works by
Asadi et al.6,7 for inelastic shear-dependent fluids obeying the
power-law model.8 But, as stands, the effect of viscoelasticity
on spontaneous imbibition still remains unexplored.
In a recent work, Zhu et al.9 experimentally and theoretically
investigated one-dimensional imbibition of certain polymer
solutions (typically used in oil recovery operations as pusher
fluids) in a tight sandstone. They observed a significant
discrepancy between their experimental data and theoretical
predictions for the shear-thinning fluid. Specifically, their
theory (which was developed based on the power-law model)
overpredicts the mass uptake by the sandstone sample. They
speculated that perhaps the weight of the imbibed liquid was to
blame, their theoretical model lacked the gravitational term.
Asadi et al.6 included the gravitational term in their generalized
Richards equation (developed for predicting imbibition of
power-law fluids) and reached to the conclusion that gravity
played no significant role simply because the height of the
sandstone core sample used in the tests was just 5 cm. So, as
stands, the main cause of the discrepancy in the work of Zhu et
al.9 remains unexplored. Interestingly, recent experimental data
reported by Gorthi et al.10 for capillary rise of CMC polymer
solutions (modeled as power-law fluid) in a glass capillary tube
exhibits a similar discrepancy between their theoretical model
and the experimental results. In the present work, we show that
Received: October 1, 2023
Revised: December 15, 2023
Accepted: December 15, 2023

© XXXX American Chemical Society https://doi.org/10.1021/acs.langmuir.3c02947

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such discrepancies can be explained in terms of the elasticity of
the test fluids.
The fact is that polymer-extended pusher fluids used in oil
recovery operations are viscoelastic, in addition to being shear-
dependent. Although Zhu et al.9 did not disclose the name of
their polymer solutions (apparently, for proprietary issues), it
can be argued that the polymer solutions used by them were
certainly viscoelastic. This is mainly because the same
mechanism which is responsible for shear-thinning behavior
of polymer solutions is also responsible for their elastic
behavior.8 In addition to relaxation and normal-stress differ-
ence effects, elasticity of polymer solutions exhibits itself by
their huge resistance to elongational deformations, as reflected
in their large extensional viscosity.8 Since flow through porous
materials such as sandstone involves elongational deformations
(due to the converging/diverging nature of the pores), the
resistance to elongational deformations exhibits itself as an
extra pressure drop in pressure-driven, single-phase Darcy
flow.11−17 It is speculated that qualitatively a similar effect
might be witnessed in imbibition flows of polymer solutions in
porous materials, but there is currently no imbibition model
for viscoelastic fluids to corroborate this speculation.
It is one of the main objectives of the present work to show
that by including an elastic term in the two-phase Darcy’s law,
the experimental imbibition data reported by Zhu et al.9 can be
closely recovered although it should be conceded that, in real
world, other mechanisms might be concurrently responsible
for the discrepancy mentioned above. For example, polymer
macromolecules adsorbed at the surface of the grains of a
porous material or stuck in the smaller-sized pores can easily
affect the wetting dynamics of the displacing fluid and/or the
permeability of the medium in a negative sense. For
investigating the effect of elasticity on imbibition flow, one
would normally need the constitutive equation of the
viscoelastic fluid involved in the problem. Since such
information is not available for the polymer solutions used
by Zhu et al.,9 the best we can do is to resort to the modified
Darcy’s law reported in the literature for certain well-known
polymer solutions similar to the ones used by Zhu et al.9 One
can particularly mention the recent experimental work by
Ibezim et al.17 who measured the pressure drop of PAA and
PEO polymer solutions in their flow through a fully saturated
porous glass foam. They proposed a modified single-phase
empirical Darcy’s law for these polymer solutions, which can
be effectively used as the starting point for extending the classic
Richards equation to viscoelastic fluids. It will be shown that,
in two-dimensional flows, the viscoelastic Richards model
obtained this way is in the form of three coupled partial
differential equations (with two of them being highly
nonlinear), which must be solved numerically. The perform-
ance of the viscoelastic Richards equations (VRE) developed
in this work will be tested against limited imbibition data
reported by Zhu et al.9 for a typical shear-thinning polymer
solution.
The outline of the work is as follows. In the next section, we
extend the classic Richards equation to viscoelastic fluids. We
then proceeded with describing the numerical method. The
one-dimensional version of the VRE model is validated against
experimental imbibition data for a shear-thinning polymer
solution typically used as pusher fluid in the oil industry. The
two-dimensional version of the model is used to investigate the
effect of a fluid’s elasticity on the quasi-stationary regime in
porous membranes of complex shape typically used in
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diagnostic kits. The work concludes by discussing the
technological significance of the numerical results and their
impact on the field of paper-based microfluidics.
■ THEORETICAL METHOD
Physiological fluids such as blood, mucus, synovia, and the like
are known to be elastic.8 Imbibition of these liquids in rapid
diagnostic kits can be influenced by the fluid’s elasticity. In fact,
it can be argued that because these kits work only for a couple
of minutes and the substrate used to transfer the fluid in these
kits is usually of high porosity, the elastic effects might indeed
be significant (particularly, at early stages of imbibition where
the rate of deformation is large). The question then arises as to
what extent the velocity at the test line is influenced by a fluid’s
elasticity. This is an important questions because, as discussed
by Mendez et al.,18 current theoretical models concerned with
the kinetics of chemical reactions on the test line of such kits
(for detecting an analyte) all assume that the average velocity is
constant on the test line; see ref 19.19 As such, it is desirable to
establish a constant velocity regime at the test line for as long
as possible. To answer the above question, we need an
appropriate two-phase mathematical model for predicting
imbibition of viscoelastic fluids by porous materials. Although
robust imbibition models are available for Newtonian fluids in
different types of porous materials,20,21 to the best of our
knowledge, no such models are available in the open literature
for any viscoelastic fluid in any type of porous material. In the
present work, we intend to develop a theoretical imbibition
model for viscoelastic fluids for the first time. To that end, we
extend the classic Richards equation20 to viscoelastic fluids
using a modified version of the single-phase Darcy’s law
reported in the literature for several polymer solutions.
Single-Phase Modified Darcy’s Law for Viscoelastic
Liquids. Richards equation is a classic partial differential
equation (PDE) developed originally for predicting water
infiltration into dry soils and sands.20 In later developments, it
was found out that this robust mathematical model is valid also
for fibrous materials.21 The equation was derived by modifying
the classic Darcy’s law (which is valid for fully saturated
materials) to unsaturated or partially saturated materials by
replacing the driving pressure in the Darcy’s law with the
capillary pressure and assuming that it is saturation dependent.
The permeability of the porous material was also assumed to
be saturation dependent in deriving the classic Richards
equation. By combining the two-phase Darcy’s law obtained
this way with the continuity equation for the moisture content
(i.e., the volume of the liquid imbibed), the classic Richards
equation was obtained, in mixed form, as20
ij k(S) yz
pc (S)zzzz
S
·jjjj
=
t z
k eff { (1)
where S is the saturation field, k(S) is the permeability field,
pc(S) is the capillary pressure field, and ε is the porosity of the
material. In general, these two functions depend on the
constitutive behavior of the porous material and the
rheological model of the fluid. And, in principle, they must
be determined experimentally.22,23 For granular materials,
based on extensive experimental tests, Brooks and Corey24
proposed certain empirical relationships for k(S) and pc(S).
The classic Richards equation combined with the Brooks−
Corey (BR) correlations has been successfully used in the past
in soil mechanics for accurately predicting infiltration of
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rainwater in dry soils. Using the BR correlations, a numerical
solution of the Richards equation is then becomes possible. A
solution of this equation then provides us with the saturation
field from which we can calculate the volume of the liquid
imbibed in the porous material as a function of time. We can
also compute the time evolution of the velocity at any location
by solving the two-phase Darcy’s law. In recent works, the
classic Richards equation together with the BR correlations
have been found to work well even for fibrous materials.25,26
It is important to note that although two phases are involved
in the Richards equation (e.g., water and air), the viscous drag
caused by the nonwetting phase (air) is ignored due to its low
viscosity. In fact, in this model, the effect of air is introduced
only through the surface tension and the contact angle. The
equation can then accurately predict spontaneous imbibition of
viscous liquids in dry or partially saturated porous materials,
whether granular or fibrous, provided that the pressure of the
nonwetting phase remains uniform (e.g., atmospheric) during
the imbibition. In addition to this important restriction, the
classic Richards equation suffers from the main drawback that
it is valid for Newtonian fluids only. In this work, we intend to
extend the classic Richards equation to viscoelastic liquids such
as polymer solutions. The idea is to rely on the modified
Darcy’s law proposed by Gogarty et al.11 and Ibezim et al.17 for
fully saturated flow of certain polymer solutions through
porous materials. Gogarty et al.11 proposed the following
correlation between the driving pressure (p) and the flux (q)
for one-dimensional, pressure-driven flow of CMC polymer
solutions through a tube packed with sands or glass beads:
p i y A comparison between Ibezim et al.’s equation17 (i.e., eq 6)
= jjj eff qzzz + (C1qC2)
L k k { (2)
where L is the length of the tube, k is the permeability of the
medium, q = Q/A is the average velocity where A is the tube
cross-sectional area and Q is the volumetric flow rate. In this
equation, μeff = f(m,n,ε,dg) is the effective viscosity, where dg is
the grain size and (m,n) are the parameters of the power-law
model, which, in one-dimensional flows, reads as τ = mγ̇n,
where τ is the shear stress and γ̇ is the shear rate. The second
term on the right-hand side of eq 2 is the elastic term, which
incorporates two parameters (C1,C2) obtained from the least-
squares fit to the experimental data, and they are specific to
each polymer additive. Among these two parameters, C1
obviously plays a more crucial role because by simply setting
C1 = 0, the elastic term is completely eliminated from this
equation. Their experimental data showed that C1 is propor-
tional to μeff/k demonstrating that this parameter is a function
of the fluid’s rheology and the material’s microstructure
(porosity, grain size, tortuosity, etc.). On the other hand, C2
was found to be nearly equal to unity or a weak function of the
polymer concentration. Their modified one-dimensional
single-phase Darcy’s law can be recast in the following form
p p=
= eff q(1 + q )
L k (3)
where (α,β) are the parameters related to the elasticity of the
fluid. In subsequent sections, α is referred to as the elasticity
coefficient, whereas β is referred to as the elasticity index. For
CMC solutions, for example, Gogarty et al.11 reported that α =
0.243. But while for the 2% solution β was reported to be equal
to 0.950 for the 4% CMC solution, it was found to be equal to
0.998. In a more recent work, Ibezim et al.17 experimentally
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showed that for pressure-driven flow of PAA and PEO
solutions through a foam of glass beads, the pressure drop data
satisfy the following modified Darcy’s law:
p
= 0 q + Cq2
L k (4)
where η0 is the zero-shear viscosity of the fluid with ρ being its
density. The second term on the right-hand side of this
equation is the Forchheimer term where the coefficient C is the
drag coefficient related to the resistance introduced by the
porous material’s skeleton. But while for Newtonian fluids C
was found to be a function of just the Reynolds number (Re),
for polymer solutions, they realized that it is also a function of
the elasticity number, El, defined as17
El =
d p2/ 0 (5)
where χ is the relaxation time and dp is the pore size. (For the
purposes of the present work, their elasticity number can be
interpreted as the dimensionless relaxation time, which was
reported to be of the order of 10 ms.17) In general, C was
found to be a strong function of the elasticity number, EI. But,
for sufficiently small elasticity numbers (say, less than 0.1),
they reported that C is nearly constant. With these in mind, eq
4 can be rewritten as
ÅÄÅ ÑÉÑ
p 0 Å
Å
Å jij Ck zyz ÑÑÑ
= qÅÅÅ1 + jjj zzzqÑÑÑ
L k ÅÅ k 0 { ÑÑÖÑ
ÅÇ (6)
and the Gogarty et al.’s equation11 (i.e., eq 3) suggests that the
two models are equivalent by simply setting
= ( k / 0 )C ; =1 (7)
The general conclusion is that although Gogarty et al.’s11
modified Darcy’s equation was obtained based on experimental
data for CMC polymer solutions through packed beds, it is
also valid for the flow of PAA and PEO polymer solutions
through glass foams. Due to the fundamental nature of the
present work, we have decided to proceed with the Gogarty et
al.’s11 modified Darcy’s law for developing the viscoelastic
Richards equation simply because it has two adjusting
parameters (α,β) making it more flexible at the time of
validating the VRE model against published experimental data.
But, unlike Gogarty et al.,11 we allow α to be a function of the
elasticity number, whenever needed. Their modified Darcy
model also incorporates the effective viscosity concept for
power-law fluids, making it more suitable for validation with
experimental data for polymer solutions. In vectorial form, the
modified single-phase Darcy’s law, to be used in the present
work, reads as
eff
q( 1 + q )
k (8)
where ∥q∥ refers to the magnitude of the Darcy velocity
vector.
Two-Phase Imbibition Model for Viscoelastic Liquids.
To extend eq 8 from single phase to two phase, the driving
pressure is replaced by the capillary pressure (with a negative
sign) and is assumed to be saturation dependent. Similarly, the
permeability (k) and the effective viscosity (μeff) are both
assumed to be S-dependent. The two-phase form of the
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modified Darcy’s law, valid for imbibition of viscoelastic fluids, experimental data for pc(S) and k(S) for any viscoelastic fluid
reads as in any type of porous material due to the pioneering nature of
the present work, we intend to rely on the Brooks−Corey
ij (S) yz
+ pc (S) = jjj eff qzz[1 + q ] correlations in our parameter study. Numerical results
j k(S) zz obtained this way are still useful, as they can serve as the
k { (9)
baseline for future works when such information becomes
Now, what remains to be done is to properly model μeff(S), available for viscoelastic fluids. Knowing ∇⃗pc(S), k(S), and
k(S), and ∇⃗pc(S) in this equation. For μeff(S), we rely on the μeff(S), the two-phase Darcy’s law valid for imbibition of
relationship recently developed by Asadi et al.6 for power-law viscoelastic fluids can be obtained as
fluids
jij k maxpc,min zyz 2 + 1/
ij 3n +
(n 1)/ n
1 yzij 1 yz jj zzS S = V[1 + V ]
j zzjj zz (n 1)/ n jj (S) zz{
eff (S) = mj (| pc (S)|) k eff (11a)
k 4n {k 2m {
(n 1)/ n This equation should be solved coupled with the continuity
ij y
jj 8 (19/18)
ln /ln(8/9)
S 0.4
·k(S) zzz equation for the liquid phase, that is,
jj zz
jj zz
k { ij S yz
jj zz + ·V = 0
(10a) k t{ (11b)
where κ is a parameter related to the tortuosity of the porous where the Darcy velocity (q⃗) has been replaced by the
material. For k(S) and pc(S), as mentioned earlier, we rely on interstitial velocity vector as V⃗ = q⃗/ε. Equations 11a and 11b
the Brooks−Corey (BR) correlations, that is,24 constitute our new imbibition model for viscoelastic fluids
3 (called the VRE model). In Cartesian coordinates, the VRE
k(S) = k maxS 3 + 2/ where k max = dg2 model in two-dimensional flows reads as
16Kck(1 )2
ij k maxpc,min yz
(10b) jj zzS2 + 1/ S = u[1 + (u 2 + v 2) /2
jjj z ]
4 cos( ) k eff
(S) zz{ x (12a)
1/
pc (S) = pc,min S where pc,min =
dmax (10c)
jij k maxpmin zyz 2 + 1/ S
jj zzS = v[ 1 + (u 2 + v 2) /2
]
where λ, σ, θ, dmax, dg, and Kck are, respectively, the pore size j (S) z{ y
distribution index, surface tension, contact angle, maximum k eff (12b)
pore size, the grain size, and the Carman−Kozeny constant. S u v
Finally, based on eq 10c, the ∇⃗pc(S) term can be obtained as + + =0
t x y (12c)
pc,min
pc (S) = S (1 + 1/ ) S where (u,v) are the velocity components in the xy-plane. It is
(10d)
interesting to note that while for Newtonian fluids the classic
At this stage, we would like to stress that the Brooks−Corey Richards equation is in the form of a single PDE (in terms of
correlations used in the VRE model were obtained based on the saturation field, S) for two-dimensional imbibition of
extensive infiltration tests of Newtonian liquids through viscoelastic fluids, the modified Richards model (VRE) is in
unsaturated granular porous systems such as sands and soils. the form of a system of three coupled partial differential
As such, their validity for viscoelastic fluids is questionable. In a equations in terms of the saturation field (S), and the velocity
recent work, Qin et al.28 have demonstrated that, for field (u,v); see eqs 12a−12c. This system of highly nonlinear,
Newtonian fluids, the closed conduits in heterogeneous porous coupled partial differential equations should be solved
materials such as sandstone can affect the wetting dynamics of numerically to investigate the effect of the elastic parameters
the displacing liquid. It can be argued that the situation (α,β) on the imbibition characteristics. To that end, with no
becomes much more complicated for viscoelastic fluids loss of generality, we assume that (α,β) is constant, unless
because, for such fluids, the open conduits are regions of otherwise stated. As mentioned earlier, this assumption is
high elastic stresses, while the closed conduits are regions of tantamount to saying that the displacing fluid is weakly elastic.
low shear stress. The stress gradient generated this way can It is important to note that the three equations governing
force polymer chains to diffuse into these stagnant regions spontaneous imbibition of viscoelastic fluids (i.e., eqs
giving rise to a concentration gradient that can further 12a−12c) reduce to the classic Richards equation for
influence the impeding effect of the closed pores by affecting Newtonian fluids by simply setting α = 0 and replacing μeff
the wetting dynamics of the invading liquid in the open with μ. All we have to do is to insert u and v from eqs 12a and
pores.12 The conclusion is that variation of the capillary 12b into eq 12c to obtain the classic Richards equation, which,
pressure and permeability with moisture content (say, in saturation form, reads as25,26
saturation) may be influenced at the presence of macro- Ä É
S k maxpmin ÅÅÅÅ i 2 + 1/ S y ij 2 + 1/ S yzÑÑÑÑ
molecules to such an extent that correlations such as Brooks−
= ÅÅ jjjS zz +
z
jjS zzÑÑ
Corey become less valid. Fortunately, as will be shown shortly, t ÅÅ x
ÅÅÇ k x{ y jjk y zz{ÑÑÑÑÖ (13)
numerical results obtained using VRE model (which rely on
the BR correlations) could closely recover the experimental Initial and Boundary Conditions in the VRE Model.
data reported by Zhu et al.9 for their polymer solutions. The To numerically solve the system of equations in the VRE
implication is that these correlations are applicable for weakly model (i.e., eqs 12a−12c), we need appropriate initial and
elastic dilute polymer solutions. Since there is no published boundary conditions. As the initial condition, we can assume
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that at t = 0, the two velocity components (u,v) and the
saturation field (S) are equal to zero, which tacitly means that
the porous material is completely dry. In practice, however, to
avoid numerical instability related to the nonlinearity of the
VRE model, we have found it advisible to assign a very small
value to the saturation field at t = 0 (say, S0 = 0.005). As the
boundary condition, the saturation (S) is set equal to unity at
the inlet edge of the porous material, which is tantamount to
saying that the inlet section of the geometry is connected to a
large reservoir of the displacing liquid. On all other edges, we
impose the no-flux condition on the velocity field, i.e., V⃗ ·n̂ = 0,
where n̂ is the unit vector normal to an elemental area on the
edges of the membrane. It is important to note that unlike the
classic Richards equation (eq 13) where no-flux is imposed on
the saturation field on all edges other than the inlet edge
(simply because, for Newtonian fluids, the flux vector is
proportional to the saturation gradient) for viscoelastic fluids,
we have to proceed with imposing the no-flux condition
directly on the velocity field at the side edges mainly because
the momentum equations are nonlinear (see eq 11a).
Having decided on the initial and boundary conditions, eqs
12a−12c can be solved numerically using the finite element
software package COMSOL. As mentioned earlier, our main
objective is to investigate the effect of the elastic parameters
(α,β) on the spontaneous imbibition of viscoelastic fluids
typically encountered in the oil industry or in paper-based
diagnostic kits. As the first step, in the next section, we provide
some details about our numerical scheme.
■ NUMERICAL METHOD
In this section, we describe the numerical scheme used to solve
the VRE model. Due to the severe nonlinearity of the VRE
model, an analytical solution of the equations in this model
(i.e., eqs 12a−12c) is deemed out of sight, and so we look for a
numerical solution. In our recent works,6,7 we have shown that
the PDE solver of the finite element software package
COMSOL can be used with great success for simulating
imbibition flows of non-Newtonian fluids obeying the power-
law model. For this reason, in the present work, we have
decided to rely on the same solver for simulating the
imbibition flow of viscoelastic fluids. The PDE solver of this
software has been optimized for certain well-known partial
differential equations (PDE) such as the Laplace equation,
Poisson equation, wave equation, and advection−diffusion
equation. For other types of PDEs, this module is equipped
with a subbranch called “General Form PDE” which enables
the users to define their own equations using mathematical
operators such as the “unsteady” operator, “convective”
operator, “diffusion” operator, and also the “source term”
operator. In the present study, we have relied on this module
to construct all equations pertinent to the VRE model except
the filter function (to be defined shortly) for which we have
relied on the Poisson equation predefined in this solver.
Although, due to proprietary issues, not all details are available
in the open literature for this solver and how it works, there are
certain things we know about the scheme used in the present
work. For example, as the convergence criterion, the relative
tolerance is set at 0.005. For time discretization, the backward
difference formulation (BDF) was utilized in this solver. Based
on this scheme, all governing equations are discretized in an
implicit manner based on the current time step in such a way
that a solution can be obtained for the saturation and velocity
field at that step. In practice, a system of linear equations is
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obtained this way at each time step (after linearization of the
originally nonlinear governing equations) where the maximum
size of the time step has been set as “automatic” in the solver.
This scheme enables the solver to automatically set the
optimized time step in the course of the computations by
constantly monitoring the degree of the nonlinearity of the
equations to be solved.
For solving the linearized system of equations (obtained
after discretization), Parallel Direct Solver (PARDISO) has
been used with an initial damping factor of 1, minimum
damping factor of 0.0001, and recovery damping factor of 0.75.
We also vary the order of the BDF from 1 (known as the
backward Euler method) to 5 for higher-order methods.
Higher-order schemes are preferable because they offer good
damping features, but to achieve numerical stability (partic-
ularly, in situations where stiff gradients are encountered, say,
at the boundaries or near the advancing front) a lower-order
scheme is automatically employed by the solver, whenever
necessary. Due to the severe nonlinearity of the VRE model, to
obtain accurate results, we have activated the “geometry shape
order” in the PDE solver and set it to the “automatic” mode.
This scheme enables the solver to invoke different classes of
predefined shape orders such as “linear shape order”,
“quadratic shape order”, “cubic shape order”, and higher-
order shapes in the course of the computation to ensure
accurate results, depending on the nonlinearity of the
equations. We have tried both quad and triangular elements
to discretize the computational domain and reached to the
conclusion that they virtually render the same results, although
for the complex 2D shapes, we intend to use triangular
elements with higher resolutions near the stiff edges. Mesh
independency has also been checked, as will be discussed
shortly.
In the course of the computations, we have observed that it
is possible for S to take on nonphysical values (say, larger than
unity or even negative values). The reason for the rise of such
nonphysical values for S is the nonlinear nature of the VRE
model (see eqs 12a−12c). The issue with nonphysical S values
becomes more severe in locations where there exists a sharp
change in the saturation field (e.g., adjacent to the advancing
front) simply because computing the spatial gradient of S
becomes less accurate. To screen out such nonphysical results
for the saturation field, we employ an appropriate filtering
function, which is in the form of an artificial diffusion term;27
see the Supporting Information for the details.
VRE Model Validation. The VRE model reduces to the
classic Richards equation for Newtonian fluids by simply
setting α = 0 and n = 1, and in a recent work by our research
group,6 we have already validated the reduced Newtonian
model against experimental imbibition results reported by
Mendez et al.18 in a 270°, fan-shaped membrane made of
nitrocellulose. On the other hand, by simply setting α = 0 and
n ≠ 1, the VRE model reduces to the GRE model for power-
law fluids, and in another recent work by our research group,7
it has been validated against experimental imbibition data
obtained by Zhu et al.9 in a tight sandstone. So, all we have to
do in the present work is to validate the VRE model for
viscoelastic fluids (i.e., for α ≠ 0). Unfortunately, a literature
survey revealed that work on the imbibition of viscoelastic
fluids is quite rare. In fact, to the best of our knowledge, Zhu et
al.9 are the only researchers who have addressed this
challenging fluid mechanics problem. In a recent work, they
reported limited experimental data for one-dimensional
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Figure 1. Performance of the VRE model in predicting the imbibition behavior of viscoelastic fluids. The dotted curve is an approximate curve
fitted by us to the experimental data reported by Zhu et al.9 for an unnamed shear-thinning polymer solution (n = 0.8) imbibed in sandstone.
imbibition of two polymer solutions in tight sandstone, with
one of them being shear-thinning and the other one shear-
thickening. Based on the viscosity data, the two polymer
solutions used in their study were modeled as power-law fluids.
Their shear-thinning fluid had (m,n) = (0.05,0.8), whereas for
their shear-thickening fluid, these parameters were (0.05,1.2).
They also reported experimental data for a Newtonain fluid (n
= 1) with dynamic viscosity equal to μ = m = 0.05 Pa·s. The
specific gravity of all three fluids was equal to SG = 1.005.
More importantly, the surface tension of all three test fluids in
contact with air was reported to be equal to 0.07 N/m. Their
data for the shear-thinning fluid interest us more because, for
this particular solution, the difference between their experi-
ment and theory was more significant suggesting that the
shear-thinning solution was more elastic than the shear-
thickening solution.
Figure 1 shows the predictions of the VRE model for Zhu et
al.’s9 shear-thinning fluid, modeled once as an inelastic fluid (α
= 0) and then as an elastic fluid (α ≠ 0). For the former case,
our numerical results for the mass uptake by the sandstone
sample are realized to be virtually the same as those obtained
by Zhu et al.’s9 fractal theory for power-law fluids; see, also,
Asadi et al.6 For the latter case, however, Figure 1 shows that
for α = 0.25, and β = 0, the VRE model can closely predict the
experimental results reported by Zhu et al.9 for this particular
polymer solution. In fact, according to Figure 1, by including
the elastic term in the Richards equation, the discrepancy
observed by Zhu et al.9 for this polymer solution is completely
resolved. It is worth-mentioning that we have also tested the
VRE model against Zhu et al.’s9 experimental data for the
shear-thickening polymer solution (n = 1.2) and found out that
by setting α = 0.05 and β = 0, the VRE model closely recovers
their published data (not shown here) demonstrating that the
shear-thickening solution was indeed less elastic than the
shear-thinning solution. The numerical results presented in
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Figure 1 support the notion that elasticity has a retarding effect
on imbibition flows, and this effect can be captured by the VRE
model.
This result reported in Figure 1 demonstartes that elasticity
by itself can explain the discrepancy observed by Zhu et al.9
between their theory and experiment. Having said this, it
should be conceded that in the real world, other parameters
may have concurrently contributed to the discrepancy. For
example, it can be argued that the air trapped in the dead-end
pores of the consolidated sandstone used in their study may
have affected the permeability dynamics of the wetting liquid;
see Qin et al.28 To this should be added the fact that, although
the names of the polymer solutions used in the tests by Zhu et
al.9 have not been disclosed, they mentioned that their polymer
solutions were typical of those used as pusher fluids, which
means that perhaps they used PEO, PAA, CMC, or XC
additives for preparing their polymer solutions. When
dissolved in water, at equilibrium, the radius-of-gyration of
these polymer chains is less than one micron. But, when fully
stretched, their size becomes around 150 μm,17 or larger,
which is comparable to the size of the pores of the sandstone
used in the tests. Although it is very unlikely that the polymer
chains become fully stretched during the tests in a Lagrangian
sense (simply because pores comprise both converging and
diverging sections) the amount of stretching experienced by
the polymer chains might have been large enough to block
smaller-sized pores in Zhu et al.’s9 experiments. And this can
further affect the wetting dynamics of the displacing liquid and
the permeability of the medium in a negative sense.
■ RESULTS AND DISCUSSION
The VRE model developed in the present work can be used for
design purposes in several applications such as (i) oil/gas
recovery operations to investigate the effect of a pusher fluid’s
elasticity on sweep efficiency and (ii) diagnostic kits to
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investigate the effect of a wetting fluid’s elasticity on the quasi-
steady regime. Although we are primarily interested in the
application of the VRE model in designing paper-based,
capillary-driven diagnostic kits, we start with extending Zhu et
al.’s9 work to viscoelastic fluids through a proper parameter
study, as a supplementary to their work. The new results can
also prove useful in oil industry where spontaneous imbibition
is widely used for oil and gas recovery.29−31 We then focus on
the effect of elasticity on the performance of the diagnostic kits.
In both applications, the objective is to investigate the effect of
(α,β) on the imbibition characteristics.
Imbibition in Sandstone: Oil Industry. Table 1 presents
the key parameters related to the microstructure of the
Table 1. Properties of the Sandstone9
property value
porosity (ε) 10%
pore diameter (dmax) 92 μm
grain diameter (dg) 500 μm
pore size distribution index (λ) 0.5
Carman−Kozeny constant (kck) 1100
tortuosity parameter (κ) 27
contact angle (θ) 70°
sandstone used in Zhu et al.’s9 tests. Their core sample was
circular in shape, having a height of 5 cm and a diameter of 2.5
cm. With imbibition being one-dimensional, we can use a
planar geometry of the same height and the same cross-
sectional area for the simulations. Figure 2a shows the
geometry adopted for the simulation in the present work;
see Asadi et al.7 In Figure 2a, the computation domain has
been discretized using quad elements. As mentioned earlier,
unlike the classic Richards equation (where the boundary
conditions can be imposed on just the saturation, S, on all
edges) for viscoelastic fluids, the VRE model requires that on
some edges the boundary conditions should be imposed on the
velocity components (u,v) instead of the saturation (S); see
Figure 2a.
As the starting point, we studied the grid independency. We
have tried three different mesh resolutions offered by the PDE
solver of the software labeled: Coarse, Normal, and Fine ware.
These three mesh resolutions correspond to 450, 1035, and
1682 elements, respectively (selected by the solver itself to
achieve maximum efficiency). According to Figure 2b, all three
mesh resolutions render virtually the same result, even for the
worst-case scenario, that is, α = 4. To be on the safe side, we
will use the finest mesh (N = 1682) for the rest of the work.
Figure 2b also shows a typical saturation profile at t = 10,000 s;
see the inset in Figure 2b.
Figure 3a,b shows the effects of α and β in the VRE model
on the mass uptake in the sandstone core sample. Figure 3a
suggests that by an increase in α (starting from zero), the mass
uptake is monotonically decreased. On the other hand, by
increasing β (starting from zero) the mass uptake is increased.
The effect of β, however, appears to be saturated around β =
0.5. To explain this unexpected behavior of β, it should be
noted that this parameter appears as the exponent of the flux
vector in the VRE model, whereas α appears as a coefficient
(see eq 11a). And because the velocities involved in imbibition
are very small, the effect of β becomes less important when it is
progressively increased, as is seen in Figure 3b.
Figure 4a shows the effect of the elasticity coefficient (α) on
the variation of the velocity profile in the vertical direction after
t = 10 h. The retarding effect of α is evident in Figure 4a. This
figure clearly demonstrates that the velocity involved is very
small (say, of the order of 10−6 cm/s). This notion can better
be seen in Figure 4b, which presents the velocity of the
advancing front. In this figure, h(t) is the instantaneous height
of the front defined as
S(x , y , t )xdA
h(t ) =
S(x , y , t )dA (14)

Figure 2. (a) The sandstone core sample discretized using quad elements showing the boundary conditions on S, u, and v. The fluid is imbibed
from the bottom edge where S = 1. (b) Effect of the number of elements (N) on the mass uptake by the sandstone obtained using the VRE model.
The inset shows a typical simulation result at t = 10,000 s (α = 4, β = 0, n = 0.8).

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Figure 3. Effect of the elastic parameters (α, β) in the VRE model on predicting the mass uptake of the shear-thinning fluid (n = 0.8) used by Zhu
et al.9 in imbibition tests: (a) effect of α for β = 0; (b) effect of β for α = 0.25.

Figure 4. (a) Effect of the elasticity coefficient: (a) on the velocity profile in the x-direction obtained at t = 10 h; (b) on the velocity of the
advancing front (dh/dt) as a function of time, where h(t) is the height of the front (n = 1, β = 0).

Figure 5. (a) An approximate curve fitted to the drag coefficient data (C) and its variation by the elasticity number drawn based on the results
reported by Ibezim et al.17 for the glass foam. (b) Effect of the elasticity number on the mass uptake by the Zhu et al.’s9 geometry if made of glass
foam.

where the coefficient ξ is set equal to unity if S lies in the range front is reduced the larger the elasticity coefficient, α. The
of [0.005,0.01] and to zero, otherwise. This definition effect appears to be more pronounced at short times, evidently
accurately identifies a thin layer near the advancing front at because the rate of elongational deformation is high in the
each time step (where saturation is anywhere between 0.005 early stages of imbibition (i.e., when the viscous drag is not so
and 0.01). Based on Figure 4, the velocity of the advancing significant). At prolonged time, however, the effect of the
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Figure 6. Effect of the number of elements (N) on the average velocity at the test line (x = 2 cm) of the fan-shaped geometry (made of NC
membrane) used by Mendez et al.18 (α = 0, β = 0, n = 1).
elasticity coefficient on the velocity of the advancing front is
predicted to diminish. This is not surprising, realizing the fact
that, owing to a significant rise in the viscous drag at later
stages of imbibition, the rate of extension is reduced, and so
the polymer chains become less stretched. As a result, the role
played by the elasticity becomes less important when the
system approaches equilibrium.
In the simulations described above, we have assumed that
the elasticity coefficient (α) is constant. This is in accordance
with the Gogarty et al.’s classic work.11 The recent work by
Ibezim et al.,17 however, has demonstrated that this is true only
for sufficiently small elasticity numbers. In fact, their
experimental data suggest that, for the Darcy flow of PEO/
PAA solutions, the drag coefficient (C) rises sharply after a
critical elasticity number of roughly 0.1. Figure 5a shows a
master curve fitted to their experimental results for the drag
coefficient, C. Since C is related to the elasticity coefficient α
through the relationship α = (ρk/μ)C, one can conclude that α
becomes a strong function of the elasticity number as soon as
El becomes larger than a threshold (say, 0.1). Knowing α as a
function of the elasticity number, the VRE model can be used
to investigate its effect on the imbibition of viscoelastic fluids.
For these simulation, we rely on the same geometry depicted
in Figure 2a, but because the experimental data for C
correspond to the porous foam used by Ibezim et al.,17 we
assume that the porosity and permeability of porous material
are equal to ε = 71% and k = 8.4 × 10−10 m2, respectively. With
the same argument, the zero-shear viscosity of the viscoelastic
fluid is set at η0 = 1.75 mPa·s. Figure 5b shows the effect of the
elasticity number (say, the dimensionless relaxation time) on
the imbibition of this particular polymer solution. The
retarding effect of the elasticity number is evident in Figure 5b.
In the next section, we use the VRE model to investigate the
effect of a fluid’s elasticity on imbibition flow in diagnostic kits
made of nitrocellulose membrane. Although, the VRE model
(combined with the Brooks−Corey correlations) is based on
extensive experimental data for granular materials, with no
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such data available for fibrous materials, we have decided to
proceed with using the VRE model for fibrous materials, too.
Justification for extending the VRE model (verified with
sandstone data) to fibrous materials such as nitrocellulose (for
which no verification is possible, as stands) arise from the fact
that recent works by Cruz et al.,25 and Suo et al.26 have
demonstrated that the classic Richards equation combined
with the Brooks−Corey correlations (which are based on
extensive data for granular systems) are also valid for fibrous
materials. The numerical results to be reported shortly can
serve as the baseline for ensuing works when more accurate
correlations become available for imbibition of viscoelastic
fluids in fibrous materials. Due to the comparative nature of
the present work, with no loss of generality, in the next section,
we assume that (α,β) are constants.
Imbibition in Nitrocellulose Membrane: Diagnostic
Kits. As mentioned earlier, physiological fluids are often
realized to be viscoelastic, and so the effect of elasticity should
be investigated in the operation of diagnostic kits. To that end,
we adopt the geometry used by Mendez et al.18 which is in the
form of a 270° fan-shaped porous membrane; see Figure 6. We
are primarily interested in investigating the sole effect of a
fluid’s elasticity on the velocity at the test line (x = 2 cm). As
such, with no loss of generality, we ignore the shear-thinning
behavior of the test fluids and set n = 1 in the simulations. (In a
recent work, Asadi et al.6 have already investigated the sole
effect of shear-thinning on the imbibition of inelastic liquids in
this particular geometry.) We also use the fluid’s zero-shear
viscosity, arbitrarily set at 0.89 mPa·s in the simulations. Figure
6 shows the geometry of the membrane used by Mendez et
al.,18 which is made of the HF-135 nitrocellulose paper
(Millipore Corp.). The membrane comprises a rectangular part
(width = 1 cm, height = 3.1 cm), which is connected to the
circular sector segment (radius = 4 cm) so that the total length
of the membrane in the x-direction is equal to 8 cm. The “test
line” is located at 2 cm x = 2 cm on the rectangular part. The
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microstructural parameters of this membrane are listed in
Table 2.
Table 2. Properties of the HF-135 Membrane18
property value
porosity (ε) 80%
pore diameter (dmax) 12 μm
fiber diameter (df) 1.4 μm
pore distribution index (λ) 0.65
Carman−Kozeny constant (kck) 0.5
contact angle (θ) 70°
tortuosity parameter (κ) 1 nearly 25%. The conclusion is that, if constant velocity is
As the first step, we proceeded with conducting a mesh
study for the Newtonian results (α = 0, β = 0), which will serve
as the baseline with which we can comment on the effect of
elasticity on the flow characteristics. To that end, the domain is
discretized with triangular mesh (see Figure 6). The test fluid
is water, and we have tried three different mesh resolutions for
checking mesh independency. As seen in Figure 6, they all
render virtually the same result. To be on the safe side, we will
rely on the finest mesh (N = 2646 elements) for the rest of the
work. It is worth-mentioning that simulations have been
carried out starting from t = 0, but we have purposely plotted
results from t = 50 to 750 s to better show the quasi-steady
regime.
It should also be noted that the displacing liquid requires a
certain time to reach the test line of the kit. In fact, as shown in
Figure 7, the fluid needs roughly 10 s to reach the test line,
which is located at x = 2 cm. The average velocity then rises
sharply at this location, while the pores are being progressively
filled. But because the fluid is diffusing in the x-direction
beyond the test line, a progressive rise in the viscous drag
means that the velocity should eventually reach a maximum. As
seen in Figure 7, the peak in velocity corresponds to t = 17.5 s.
The drop in velocity continues until the fluid reaches the
circular sector (around t = 40 s), at which point in time, it
Figure 7. Variation of the average velocity with time at the test line (x = 2 cm) during the transient phase of the device for Newtonian fluids (α = 0,
n = 1).
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becomes nearly flat because the retarding effect of viscous drag
is nearly counterbalanced by the accelerative effect of the
capillary force, which has dramatically increased due to the
new pores offered to the fluid as soon as it enters the circular
section.
The numerical results shown in Figure 6 suggest that, for
Newtonian fluids, in the range of t = 250−500 s, the average
velocity at the test line remains nearly constant. This notion
can better be seen in Figure 8 which shows the variation of the
average velocity in the x-direction. As shown in Figure 8, from
t = 250 to 500 s, the drop in the average velocity at the test line
is less than 3%, but by proceeding to t = 1000 s, it becomes
desired, this kit should not be used for times larger than 500 s.
We now investigate the effect of a fluid’s viscoelasticity on
the imbibition characteristics in the NC membrane. Figure 9a
shows the effect of the elasticity coefficient (α) on the time
evolution of the velocity at the test line (x = 2 cm). As
mentioned earlier, α is a measure of the fluid’s resistance to
elongational deformations while it flows through the
converging/diverging pores of the medium. As is seen in
Figure 9a, at short times, the average velocity is reduced at the
test line the larger is the elasticity coefficient. More
importantly, the time span over which the velocity is nearly
constant is significantly increased by increasing the elasticity
coefficient, α. For example, for α = 2 the average velocity is
predicted to be nearly constant at the test line for nearly 2000
s, whereas for its Newtonian counterpart (α = 0), the constant
velocity prevails up to t = 500 s.
An important design coefficient to decide upon is the
location of the test line on the rectangular section. As
mentioned earlier, the test line should be placed at a location
where the velocity remains nearly constant with time. The test
line cannot be placed too close to the inlet section because the
rate of flow may become too large so that the assumption of
creeping flow (and therefore the use of Darcy’s law) may no
longer be valid. It should also be sufficiently far from the
circular sector segment, where the streamlines are quite curved
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Figure 8. (a) Variation of the average velocity with time along the centerline of the rectangular segment with the test line drawn at x = 2 cm. (b)
Variation of the average velocity along the centerline of the whole membrane obtained at t = 250 s (α = 0, n = 1).

Figure 9. Effect of the elasticity coefficient, α: (a) on the average velocity at the test line (x = 2 cm); (b) on the velocity along the rectangular
segment at t = 250 s (n = 1, β = 0).

and the uniformity of the velocity is no longer valid. A plot of

the velocity with distance can prove useful for deciding on the
best location for the test line and whether it is affected by a
fluid’s viscoelasticity. As can be seen in Figure 9b, elasticity
allows the test line to be drawn slightly closer to the transition
between the two segments, but x = 2 cm appears to be a
conservative value for all cases studied in this figure.
Finally, in Figure 10, we have investigated the effect of the
elasticity index β. Figure 10 demonstrates the strong effect of
the elasticity exponent β in the VRE model on the quasi-
stationary regime. That is, while for β = 1, the duration of
quasi-steady regime is rather short, it becomes quite large for β
= 0. Again, we are witnessing that the effect of this parameter
saturates when it approaches unity. To be more specific, the
results for β = 0.5 is nearly the same as the results for β = 1.
The general conclusion is that to extend the duration of the
constant velocity regime at the test line of diagnostic kits,
polymer additives should preferably be used, which have a
large α and a small β.
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■ CONCLUSIONS
Physiological fluids, such as blood, are known to be elastic.
Elasticity of such fluids is speculated to affect their imbibition
in fibrous materials, such as nitrocellulose membranes, which
are widely used as the substrate in diagnostic kits. A
viscoelastic version of the Richards equation has been
developed in the present work (called the VRE) to investigate
the effect of elasticity on imbibition flows in paper-based,
capillary-driven kits. To that end, we have relied on the
modified Darcy’s law reported recently in the literature for
pressure-driven flow of certain polymer solutions (PAA/PEO/
CMC) through fully saturated porous materials. By extending
the single-phase Darcy’s law to its two-phase version using
Brooks−Corey correlations, a system of three coupled
nonlinear PDEs has been obtained in two-dimensional
imbibition of viscoelastic fluids for the saturation and velocity
fields. Having solved these equations numerically, the VRE
model is found to be well capable of predicting published
experimental imbibition results (Zhu et al.9) for two unnamed
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Figure 10. Effect of the elasticity exponent (β) on the average velocity at the test line, x = 2 cm (n = 1, α = 2).
polymer solutions imbibed in a tight sandstone. We then used
the VRE model to investigate the effect of elasticity on the
quasi-stationary regime at the test line of a typical diagnostic
kit of complex geometry. The following conclusions can be
made based on the numerical results obtained in the present
work:
• Elasticity of physiological fluids should be included in
any theoretical model aimed at accurately investigating
the quasi-stationary regime in diagnostic kits.
• In diagnostic kits, elasticity reduces the fluid velocity at
the test line but increases the time span over which the
quasi-stationary regime is sustained.
• Polymer additives (preferably, those having a high α and
a low β) can be used as a passive means for extending
the quasi-stationary regime at the test line of diagnostic
kits.
The VRE model developed in this work can also be used for
designing gas recovery operations in the oil industry. It can
also be used in studies concerned with harnessing the
contamination of underground water (using polymer addi-
tives) during oil spill. The main shortcoming of the VRE
model is that it relies on the Brooks−Corey correlations for the
variation of the capillary pressure and permeability with the
moisture content. These correlations are strictly speaking valid
for Newtonian fluids flowing through granular systems. With
no such correlations available in the literature for any
viscoelastic fluid in any fibrous system, they have been used
in our pioneering work for predicting the imbibition flow of
viscoelastic fluids in diagnostic kits. Evidently, in future works,
this gap in knowledge should be filled for imbibition flow of
viscoelastic fluids for having more accurate results. A good
feature of the VRE model developed in this work is that it does
not require any knowledge of the constitutive equation of the
viscoelastic fluid in question. All we need to do is to determine
the elasticity parameters (α,β) of the viscoelastic fluid of
interest in pressure-driven Darcy flow and insert these
parameters in the VRE model to predict its imbibition
behavior in diagnostic kits or oil recovery operations. In
cases where the constitutive equation of the fluid is known, it is
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possible to embark on a more rigorous imbibition analysis
provided that the single-phase Darcy’s law is available for that
specific fluid. Fortunately, for viscoelastic fluids obeying the
Maxwell or Oldroyd-B model,8 the single-phase Darcy’s law is
available.31,32 Thus, in principle, one should be able to extend
the classic Richards equation to these viscoelastic fluid models.
These models represent constant viscosity viscoelastic fluids
and enable one to focus on the sole effect of elasticity in any
given flow. Such an analysis is worthwhile because it would
enable one to investigate the effect of the relaxation time,
elastic stresses, and extensional viscosity on spontaneous
imbibition in any given application, such as diagnostic kits and
paper-based flow batteries. Work is currently ongoing in our
research group to extend the Richards equation to the Maxwell
viscoelastic fluid model.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.3c02947.
Explaining the need for a filter function as to the
saturation field; introducing an appropriate filter
function in the form of an artificial diffusion; discussing
the importance of the diffusion coefficient in the filter
function on the numerical results (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Kayvan Sadeghy − School of Mechanical Engineering, College
of Engineering, University of Tehran, P.O. Box 11155-4563
Tehran, Iran; orcid.org/0000-0001-8823-2479;
Phone: +98 9121718828; Email: sadeghy@ut.ac.ir
Authors
Ali Gharagozlou − School of Mechanical Engineering, College
of Engineering, University of Tehran, P.O. Box 11155-4563
Tehran, Iran
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Mohammad Pourjafar-Chelikdani − Caspian Faculty of
Engineering, College of Engineering, University of Tehran,
43841-119 Rezvanshahr, Iran
Azadeh Jafari − School of Mechanical Engineering, College of
Engineering, University of Tehran, P.O. Box 11155-4563
Tehran, Iran; orcid.org/0000-0002-1331-6640
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.3c02947
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
K.S. would like to thank Iran National Science Foundation
(INSF) for supporting this work under Contract No. 4006154.
Special thanks are also due to the respectful reviewers for their
constructive comments.
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