Professional Documents
Culture Documents
www.elsevier.com/locate/jcis
Abstract
A theoretical model was developed to describe the dynamics of spontaneous penetration of viscoelastic fluids into capillaries. The model
agrees quantitatively with recent experiments on absorption of droplets of polymer solutions by glass capillaries [A.V. Bazilevsky, K.G. Ko-
rnev, A.N. Rozhkov, A.V. Neimark, J. Colloid Interface Sci. (2003)]. The rate of penetration progressively reduces with the increase in fluid
elasticity. Analysis revealed two main contributions to the viscoelastic drag of the liquid column: (i) viscous resistance, which is indepen-
dent of fluid elasticity, and (ii) viscoelastic resistance, known as the Weissenberg effect. We analytically derived an augmented Bosanquet
equation for the maximal velocity of penetration by balancing capillary, inertia, and viscoelastic forces. For slow creep of a liquid column,
the Lucas–Washburn equation was modified by accounting for the Weissenberg effect. A series of numerical calculations were performed to
demonstrate characteristic features of absorption of fluids at different conditions. This article also discusses some problems specific to absorp-
tion of biofluids. We show that deformations of cell membranes in the external converging flow may cause their rupture at the pore entrance.
2003 Elsevier Science (USA). All rights reserved.
1. Introduction
(b)
2. The model and analysis of limiting cases
Fig. 2. Mechanisms of elastic reaction of polymer coils/cells responsible for
meniscus deceleration. Elastic inclusions are pictured as flexible dumbbells.
In a velocity gradient, the dumbbell is transferred with an average velocity
A schematic picture of the absorption experiment is
and is stretched along with the fluid elements. (a) Weissenberg effect: in presented in Fig. 1. An empty capillary is submerged into a
the Poiseuillean flow the dumbbell is stretched, giving rise to an extra liquid and, as soon as the capillary touches the liquid surface,
stress acting normally to the capillary cross section. (b) Spring effect: the the liquid begins to penetrate inside the capillary.
meniscus is pulled back due to the dumbbell extension in the sink-like In capillaries whose radius is greater than the characteris-
external velocity field. Both effects act simultaneously.
tic coil/cell size, the fluid flow may be considered within the
framework of continuum hydrodynamics. The driving force
Poiseuillean flow. Extension flow deformations in the con- of the process is not the pressure gradient, but the wetting
verging stream at the pore entrance cause another effect, re- force acting at the contact line. Therewith, the contact line
ferred to as the spring effect. drags the meniscus, and the flow pattern at the vicinity of
the meniscus is a plug-like flow with an almost constant ve-
1.1. Weissenberg effect in shear flow locity profile. The development of a boundary layer and the
transition from the plug-like flow to the Poiseuillean flow are
In a Poiseuillean flow with a parabolic velocity profile, beyond the scope of this article. A non-Newtonian consti-
elastic inclusions of the fluid are stretched due to the velocity tutive equation accounts for the fluid structural complexity.
gradients. Their stretching causes a force directed counter to We use the upper convected Maxwell model for description
the flow (Fig. 2a). Essentially, the stretching of a viscoelastic of viscoelastic fluids [24,28]. The Maxwell model is suit-
fluid gives rise to an extra stress additional to the pressure. able for fluids displaying an elastic response within short
This effect, known as the Weissenberg effect [25], causes a time intervals and behaving as viscous fluids at longer times
reduction of the capillary pressure at the meniscus, leading [13,28–33]. The elastic response is characterized by the re-
to a weakening of the driving force. laxation time λ = η/G, which is the ratio of fluid viscosity η
to the elastic modulus G of the fluid.
1.2. Spring effect in extension flow
2.1. Basic equation
In a sink-like flow at the capillary inlet, the velocity gra-
dients cause stretching of elastic inclusions also. However, Accounting for the Maxwellian rheology, the equation of
the mechanism explaining the friction drag is different from meniscus motion through capillary of radius R is written as
the Weissenberg effect. Imagine a spring (Fig. 2b), of which
one end is attached to the meniscus, and the other is kept ρR 2 d (x + cR)dx/dt dt + 8ηx dx/dt
outside the capillary. As the meniscus propagates inside the + (16λη)(dx/dt)2 + R 2 F (dx/dt, λ, η)
capillary, the spring is strained and pulls the meniscus back-
− 2σ R cos θ + ρgxR 2 = 0. (1)
ward. The effect may be significant at the initial instants of
penetration, within the time intervals comparable to the char- The details of derivation of the model for viscous fluids can
acteristic time of relaxation of elastic inclusions. be found in [34]; the terms specific for viscoelastic fluids
In this article, we focus on the physical mechanisms of are derived in Appendix A. In Eq. (1), x is the meniscus co-
absorption of viscoelastic fluids by capillaries. We restrict ordinate, t is the time, and ρ is the density. The first term
ourselves to sufficiently wide pores, for which a continual in Eq. (1) is the inertial force. Parameter c accounts for the
hydrodynamic theory can be applied. In Section 2 we derive apparent mass contribution due to the external flow and is
the basic governing equation taking into account the Weis- of the order of one [34–36]. The second term is the friction
senberg and spring effects (Appendix A contains the mathe- force due to the fluid viscosity. The third term expresses the
matical details). An asymptotic analysis of the model illus- Weissenberg effect. The fourth term accounts for the spring
K.G. Kornev, A.V. Neimark / Journal of Colloid and Interface Science 262 (2003) 253–262 255
Fig. 4. UVE given by Eq. (8) as a function of capillary radius for aqueous
solutions of polyacrylamide (PAM). η = 4 mPa s, λ = 0.027 s for 100 ppm
and λ = 0.05 for 200 ppm solutions of PAM. σ = 71 mN/m, θ = 0 for both Fig. 5. Noninertial motion of meniscus of viscoelastic and viscous fluids.
solutions [1]. η = 4 mPa s, σ = 71 mN/m, θ = 0.
a significant role. The characteristic velocity is given by where t0 is an integration constant. Equation (10) plays the
2σ R cos θ same role as the Lucas–Washburn equation of front prop-
UVE = UB / 1 + 16ηλ/ρR 2 = . (8) agation in the case of viscous fluids [44,45]. The differ-
ρR 2 + 16ηλ
ence between Eq. (10) and the Lucas–Washburn equation,
In the preceding paper [1], we demonstrated experimen- (t − t0 )σ cos θ/ηR = 2x 2 /R 2 , is shown in Fig. 5. There is
tally that the modified Bosanquet velocity, Eq. (8), quantita- no doubt that the Weissenberg effect is significant and dis-
tively describes the rate of penetration of droplets of poly- tinguishable from the effect of Poiseuillean friction. Thus,
mer solutions into capillaries (see Table 1 in Ref. [1]). Equa- the method of dynamic absorption suggested in the preced-
tion (8) gives a nonmonotonous dependence of the velocity ing article [1] is quite promising not only as a mean for char-
UVE on the capillary radius. Remarkably, √ the velocity UVE acterization of fluid/wall interactions, but also as a tool for
attains a maximum at the radius RVE = 4 λη/ρ, which is studying the fluid rheology. The elastic modulus G = η/λ
independent of the wetting properties of liquids. If the pore can be found from an analysis of the meniscus propaga-
radius is smaller than RVE , the velocity decreases due to the tion, provided that other parameters are determined indepen-
Weissenberg effect. If the radius is greater than RVE , the ve- dently. Below, we numerically investigate the problem of the
locity decreases because of a reduction of the driving capil- meniscus motion to find the distance range where Eq. (10) is
lary pressure. As shown in Fig. 4, the difference between ab- applicable.
sorption rates of simple and viscoelastic fluids is significant.
As a typical example, we have presented the data for aqueous
solutions of polyacrylamide (PAM). This well-documented 3. Numerical analysis of the model
system was used to model the blood rheology [21,22,43].
3.1. On applicability of the approximation of
2.3. Noninertial flow, or the Lucas–Washburn limit
noninertial flow: no gravity
At the intermediate time scale when the entrance effects
can be neglected and the inertial forces are dominated by the From the asymptotic analysis of the model, we concluded
friction forces, Eq. (1) can be rewritten as that the spring effect plays a minor role for most cases under
consideration. Hence, the fourth term in Eq. (1) may be ne-
8ηxdx/dt + (16λη)(dx/dt)2 glected and the equation takes on the form
− 2σ R cos θ + ρgxR 2 = 0. (9)
ρR 2 d (x + cR)dx/dt dt + 8ηxdx/dt
Equation (9) admits the exact integration, yet the form of the
integral is complex. Ignoring gravity, the solution reduces to + (16λη)(dx/dt)2 − 2σ R cos θ = 0. (11)
ρR 3 /2σ cos θ and taking the radius of capillary as a char-
acteristic length scale. Within this normalization, Eq. (11)
takes on the form
d (H + c)dH /dT dT
+ ΩdH /dT (H + De dH /dT ) = 1, (12)
where
8τ η
H = x/R, T = t/τ, Ω= , De = 2λ/τ.
ρR 2
The parameter Ω characterizes the magnitude of the viscous
forces, and the Deborah number De, the magnitude of the
elastic forces, as compared with the driving force of pene-
tration. Fig. 6. Meniscus velocity normalized by the Bosanquet velocity as a
The term responsible for the viscous drag is proportional function of the traveled distance measured in radii of the capillary. Two
to the distance traveled by the meniscus, ΩH (dH /dT ). asymptotes are calculated by Eq. (10) with λ = 0.03 s and λ = 0.05 s,
This term may be very small at the initial instance of time respectively.
compared with the Weissenberg term which is independent
of the distance, ΩDe(dH /dT )2 . Hence, the elastic forces 3.3. Capillary rise
resist the motion effectively even at the very beginning of
penetration, and the greater the relaxation time, the stronger Considering the problem of capillary rise, we also neglect
the effect. the fourth term in Eq. (1). The natural length scale in this
In calculations, we set c = 1 as a reasonable approxima- problem is the Jurin length, cap = 2σ cos θ/ρgR, i.e., the
tion of experimental situations [36]. The contact angle is height of the liquid
assumed to be zero. All physical parameters correspond to column under equilibrium conditions.
The time τr = cap /g of free fall of liquid column of
those of water: length cap serves as a characteristic time. Taking this
normalization, we rewrite Eq. (1) in dimensionless form as
η = 1 mPa s, σ = 72 mN/m, 2R = 0.65 mm,
ρ = 1000 kg/m . 3 d (H + α)dH /dT dT
We vary only the relaxation time λ to display the effect + Ωr dH /dT (H + Der dH /dT ) = 1 − H, (13)
of fluid elasticity. As a typical example, in Fig. 6, we plot where
the meniscus velocity as a function of the traveled distance.
The velocity takes its maximal value when the meniscus had H = x/cap , T = t/τr , α = cR/cap ,
traveled few capillary diameters. The maximums are smaller
than UB (viscous fluids) and UVE (viscoelastic fluids), but Ωr = 8ηcap /(ρR 2 gτr ), Der = 2λ/τr .
the differences are insignificant. Therefore, the characteristic Due to the difference in the time scales, the Deborah
velocities UB and UVE provide a correct estimate for the number Der is different from that introduced in Eq. (12).
initial velocity. It characterizes a relation between the effects of elasticity
The asymptotic formula (10) works quite well: the greater and inertia. For a quantitative analysis of the elastic effect,
the relaxation time, the better the approximation. For a par- we plot in Fig. 7a the column height measured in the Jurin
ticular case of aqueous solutions of PAM, whenever the length as a function of the dimensionless time, scaled by τr .
meniscus travels about 10 diameters, the approximate for- All physical parameters correspond to water.
mula is applicable for concentrations greater than 100 ppm For viscoelastic fluids, the time needed for the liquid
(λ > 0.03, see Fig. 7 in Ref. [1]). column to achieve a certain vicinity of the limiting Jurin
height increases drastically as the relaxation time increases.
3.2. Penetration of droplets into capillaries The effect is apparent in Fig. 7b where the meniscus veloc-
ity is shown as a function of the traveled distance. While
In the preceding article [1], we applied Eq. (11) to predict gravity is insignificant at the beginning when the meniscus
the rate of absorption of droplets of polymer solutions into accelerates to its maximal velocity, the gravitation-induced
capillaries. Equation (11) was modified to account for the deceleration prevails just after this maximal point (Fig. 7c).
gravity and the varying size of a penetrating droplet. It Figure 7c shows that a significant decrease in the rate of
was shown that the model predicts the rate of absorption absorption due to gravity can be expected only for visco-
fairly well without any adjustable parameters (see Fig. 11 elastic fluids with a small relaxation time: the greater the
in Ref. [1]). relaxation time, the smaller the effect of gravity.
258 K.G. Kornev, A.V. Neimark / Journal of Colloid and Interface Science 262 (2003) 253–262
(a)
Fig. 8. Inside the semisphere of radius Rcr the biocells are stretched, while
outside this region their shape is almost unperturbed.
boundary r = Rcr , we get elastic inclusions in the external convergent flow, and the
l E(l − Rcell ) Weissenberg effect of stretching of elastic inclusions in the
ηΓ |r=Rcr ≈ . (15) internal Poiseuillean flow. Commonly, the restoring force
h Rcell
due to the spring effect is much smaller than that due to the
Here, η is the fluid viscosity. Substituting Eq. (14) in Weissenberg effect.
Eq. (15), and setting l ≈ (1 + ε)Rcell , ε 1, we get an The Weissenberg effect gives rise to a reduction of the
estimate of the critical distance as driving pressure drop, which, in turn, results in the hin-
ηRcell R 2 U 1/3 drance of absorbency. The effect is pronounced in the case
Rcr = . (16) of negligible gravity, for which an analysis of the limiting
Eεh
cases is analytically performed. At the initial instance of
Substituting Eq. (2) into Eq. (16), we come to the relation-
time when the flow is controlled by inertial, capillary, and
ship
elastic forces, the spring and Weissenberg effects can be
√
ηRcell R 3/2 2σ cos θ 1/3 distinguished. An analysis becomes evident if the apparent
Rcr = √ . (17) mass of the liquid column is neglected. Therewith, the ini-
Eεh ρ
tial velocity of the meniscus propagation is a constant, which
For a crude yet instructive estimate, we take the typical serves as an estimate of the maximum rate of absorption. For
parameters for red cells and blood as [54,56,57]
small Weissenberg numbers defined by Eq. (6), the spring
Rcell ≈ 10 µm, E ≈ 103 Pa, σ ≈ 50 mN/m, effect dominates the Weissenberg one. The maximum veloc-
ity expressed by Eq. (7) differs slightly from the Bosanquet
η ≈ 1 mPa s, ρ ≈ 1000 kg/m , 3
value. As the Weissenberg number increases, thus manifest-
θ ≈ 0, h ≈ 0.01 µm. ing the fluid elasticity, the Weissenberg effect prevails over
√ √
Then Rcr ≈ 0.2 R/ 3 ε cm. For 10-µm capillaries and ε = the spring effect and the maximum velocity is estimated by
0.1, the critical radius is about one order of magnitude Eq. (8). As shown by solving the problem (11), (12) numeri-
greater than the pore radius. As shown above, the Bosanquet- cally, this estimate is quite accurate. The maximal achievable
like regime of spontaneous absorption lasts about ≈ R/U . velocity of the meniscus depends on the radius of capillary
This time interval is small, yet sufficient to produce giant nonmonotonously; there is a capillary, for which the veloc-
√
stresses which, most likely, the cell membrane cannot with- ity is maximal, RVE = 4 λη/ρ. This estimate determines
stand. For example, red blood cells are able to sustain only the size of the most efficient capillary for fluid absorption.
about 140% extension before the rupture [54]. An asymptote for the slow noninertial motion of menis-
Thus, the scaling analysis shows that the small-sized cap- cus, similar to the Lucas–Washburn equation for viscous flu-
illaries are unsuitable for testing cell deformability in the ids, is found for viscoelastic fluids. It is shown numerically
spontaneous mode of absorption. The use of porous per- that the asymptotic formula (10) works well for distances of
meable substrates instead of capillaries is questionable also, penetration greater than about 10 capillary diameters. This
though the flow pattern at the membrane surface is differ- formula operates with the elastic modulus of the fluid. We
ent. It is worth noting that substrates for which the charac- conclude that the elastic modulus of biofluids can be esti-
teristic distance between pores is sufficiently larger than the mated from the absorption experiment, provided that the sur-
pore radius could be appropriate as efficient wound covers. face tension and the contact angle are known, or measured
Indeed, cell membranes, which are ruptured in the suction independently.
flow, would coat the pore walls, promoting the subsequent
We showed that the stretching in the converging flow
platelet adherence [58]. The effect of the cell rupture in the
might lead to the rupture of cell membranes in the process
process of spontaneous absorption is worth further studies.
of biofluid absorption by fine capillaries. This effect is likely
to be more important than the pore clogging by deformed
5. Conclusions cells. A cell can be delivered safely only to a pore whose
size is greater than the cell diameter. The analysis of biofluid
The problem of spontaneous penetration of viscoelastic absorption by capillaries and porous substrates may have
fluids and biofluids into capillaries has been analyzed. practical implications in health care and medicine, ranging
The hydrodynamic theory of absorption of viscoelastic from blood tests to wound treatment.
Maxwellian fluids is applied for the description of meniscus The model developed in this article was used in the
propagation. We show that the absorption kinetics can be preceding article [1] for the interpretation of experimental
quantitatively described by Eq. (1), a generalized Lucas– data on spontaneous penetration of droplets of polymer
Washburn equation. This equation accounts for acceleration solutions into capillaries. It was shown that the model
of the flow caused by the Laplace pressure, inertia of the describes the experiments without any adjustable parameters
fluid column, gravity, viscous friction due to the Poiseuillean involved and gives correct relations between the rate of
flow inside the capillary, the spring effect of stretching of penetration and rheological parameters.
260 K.G. Kornev, A.V. Neimark / Journal of Colloid and Interface Science 262 (2003) 253–262
[58] H.L. Goldsmith, in: D.A. Siginer, D. DeKee, R.P. Chhabra (Eds.), [60] T. Hasegawa, T. Iwaida, J. Non-Newtonian Fluid Mech. 15 (1984)
Advances in the Flow and Rheology of Non-Newtonian Fluids, Vol. A, 279.
Elsevier, New York, 1999, p. 1. [61] J.Y. Yoo, M. Ahrens, D.D. Joseph, J. Fluid Mech. 153 (1985) 203.
[59] T. Hasegawa, T. Iwaida, J. Non-Newtonian Fluid Mech. 15 (1984) 257. [62] M.A. Brutyan, P.L. Krapivsky, Adv. Sci. Technol. VINITY 4 (1991) 3.