Dynamics of Confined Polymer Chains

Dynamics of confined polymer chains
F. Brochard
Laboratoire de Physique des solides, Universite Paris-Sud, 91405 Orsay, France
P. G. de Gennes
College de France, Place Marcelin Berthelot-75231 Paris Cedex 05, France
(Received 2 February 1977)
We study the motions of a single polymer chain trapped inside a very thin capillary (or slit). We
incorporate all excluded volume effects and hydrodynamic interactions through a scaling analysis. We find
that the Debye-Bueche approximation, which was qualitatively correct for three-dimensional dilute
solutions, becomes completely incorrect for confined chains: the local fluctuations of the monomer
concentration which are ignored in the Debye-Bueche picture allow for channels of easy flow of the
solvent inside the chain. We obtain scaling formulas (with unknown numerical coefficients) for the
diffusion constant and we also analyze the internal mode structure: inside a tube, for wavelengths larger
than the diameter, we recover an unexpectedly simple structure of Rouse modes. Finally, we analyze the
possibility of "sucking in" one chain inside a slightly tapered pore, by imposing a certain flow of the
solvent. We find that the threshold pressure difference Ilpc for aspiration of the chain depends only on the
smallest diameter of the pore and is independent of the molecular mass. The magnitude of IIp, is not too
large, and the experiment may be feasible.
I. INTRODUCTION
The properties of flexible polymer molecules inside
finely porous media have important applications in many
fields such as membranes, gel chromatography, oil re-
cuperation, heterogeneous catalysis, etc. There are
numerous measurements on (a) partitioning and (b) dif-
fusion of macromolecules within porous structures
(listed in Ref. 1). Problem (a) has been discussed very
recently2 in terms of a scaling method which goes beyond
the mean field (Flory-Huggins-Edwards) theory.
Here we investigate Problem (b) (statistical motions of
confined chains) using the dynamical scaling method,
which is known to give reasonably good results for bulk
polymer solutions. 3
We consider flexible polymer chains moving in pores
of cylindrical shape. Such pores can be realized in var-
ious ways, for instance in porous glass by leaching, 1
or between compactly pressed fibers, or in an inverse
hexagonal structure of lipid + water. We assume no ad-
sorption (this can be achieved by chemically treating the
pore wall
l
). Our entire discussion is restricted to
chains dissolved in good solvents where monomers re-
pel each other. (We do not dicuss the case of 0 solvents
for the following reason: in good solvents we can show
that a single chain makes very few knots on itself; but
in a poor solvent there are many self-knots and the
dynamics is more complex: it will be discussed in a
separate publication. )
A. Summary of static behavior
The configuration of the chains under the same condi-
tions has been described by Daoud and de Gennes.
2
For
a single chain in a capillary of diameter D, we have two
behaviors depending on the ratio RF/D, where RF is the
Flory radius in a bulk dilute solution,
3
11=='5. (1.1)
a is the monomer Size, and N is the polymerization in-
dex.
52 The Journal of Chemical Physics, Vol. 67, No.1, 1 July 1977
If RF<D, we have a conventional bulk solution. If RF
> D, the chains are deformed into long "cigars" of di-
ameter D and length R". As shown in Ref. 2, the length
of the Cigar is
R" r
/3

(1.2)
The chain can be seen as a succession of "blobs" of
radius D (Fig. 2). The number g of monomers in a blob
is defined by D == art as in Eq, (I. 1), and the chain length
corresponds to N / g blobs:
R" == (N/g)D , (1.3)
in agreement with Eq. (1. 2). In a blob, i. e., at dis-
tance r less than D, excluded volume effects are main-
tained and the average distance between a given pair of
monomers is 1 rn - rm 1 1 n - rn I" a. [It must be em-
phasized that we discuss only the limit D/a 1. Then
the number g of monomers in one (D/a)5/3 is
large and excluded volume effects are dominant. Typi-
cal values would be D ==200 A, a == 5 A, giving g- 500.
Of course, a large D imposes a very large polymeriza-
tion index N. Our picture assumes N g; Thus, we
would want to have N or molecular weights of order
10
6
.J For distances exceeding D the chain is axially
stretched and 1 rn - rml (I n - rn 1 fa) D. The monomer
concentration goes to zero near the pore wall.
B. Analogy with stretched polymers
The configuration of the isolated chain trapped in a
capillary is very similar to the configuration of a chain
strongly stretched by applying a force f to the ends of
the chain (Fig. 1). The scaling laws for a stretched
chain in a good solvent have been discussed by Pincus. 4,5
He showed that the stretched chain behaves like a se-
quence of blobs of radius == k BT If. Inside each blob
excluded volume effects prevail, but between separate
blobs they become negligible. The average end-to-end
length Z (in the limit Z/R
F
1) is Z == There
is a strong analogy between the stretched chain and the
Copyright 1977 American Institute of Physics
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F. Brochard and P. G. deGennes: Dynamics of confined polymer chains
53
/ "g monomers
/BLOB (size D) ,
FIG. 1. Chain configurations and water channel for a confined
chain: the statistical fluctuations of the local concentration
allow for a relative easy flow of the solvent through the chain
(or vice versa). We have represented below the configuration
of a stretched chain for comparison.
confined chain. The analog of D is ~ t and the analog of
Z is R
II
[There is one minor difference: in the con-
fined chain the blobs are completely aligned in the axial
direction. But in the stretched chain lateral fluctuations
are allowed and the projection of the chain on a plane
normal to f extends over distanceSR.L='; N/g ~ t (Fig. 4).
However, this difference is weak and essentially irrel-
evant for our later discussion.] We shall show in the
present paper that the dynamics of confined chains also
reflect this similarity.
C. An incorrect model: the sponge
It is tempting to picture the chain as a sponge, or
porous object, in the spirit of the Debye-Bueche ap-
proximation. 6 In the present section, we shall recon-
struct the essential features of this description, and
show that it leads to a very low chain mobility. In the
next section, we analyze the effects of local fluctuations
in the monomer concentration and show that these fluc-
tuations are essential: they allow for a relative flow of
solvent/polymer which is much easier than expected in
the Debye-Bueche picture.
Let us now write down the equations for the sponge
model, assuming for the moment that the monomer con-
centration c is uniform in the region occupied by the
chain,
_ N
c= RIID2
(I. 4)
We call v the solvent flow velocity, and r the velocity of
the sponge. The sponge is treated for the moment as
rigid: r is the same at all points.
Then a fluid element is subjected to three forces: vis-
cous force, pressure gradients, and friction against the
sponge. In steady state the three forces add up to zero:
(1.5)
where 11s is the solvent viscosity, t is the friction co-
efficient for one monomer, and p is the pressure. Tak-
ing the curl of Eq. (1.5) we find
(1.6)
where {1 is the vorticity, and Ki} is the "Debye screen-
ing length" defined by
(1.7)
Dimensionally we may write t - 61T 11s a H, where a H is the
hydrodynamic radius of one monomer and is of order a.
Thus K ~ - ca. Inserting the value (1.4) for c and Eq.
(I. 2) for RII we obtain
(1.8)
Thus the screening length is very small when compared
to D. Consider now a problem where the chain moves
with uniform velocity r inside the tube. Two regimes
are possible:
(a) If the mechanical pressure p is the same at both
ends of the tube, the sponge drags some solvent with
itself. The flow pattern at one cross section inside the
sponge is a "plug flow." The velocity v is equal to r in
most of the section and drops to zero in one screening
length near the wall:
b) If the ends of the tube are closed (no solvent flow),
the only solution to Eq. (1.5) is v'" 0 everywhere and
vp =ctr. This case is the one which is relevant for a
discussion of mobilities and diffusion constants for one
chain in a long tube. The friction coefficient for the
whole chain is then easily seen from (1.5) to be very
large,
tnebye-Buechc =N to
(1.9)
All these results remain qualitatively the same when the
average concentration c is allowed to vary radially (in
actual cases with nonadsorbing walls, c vanishes at the
wall).
It took us a long time to realize that Eq. (I. 9) is in
fact completely incorrect, because it ignores the local
fluctuations of the concentration c. This shall be ex-
plained in the next section.
II. KIRKWOOD CALCULATION OF THE CHAIN
MOBILITY
We shall now estimate the friction coefficient of a
chain confined in a slit or a tube of diameter D, using
the method of Kirkwood, 7 and we shall show that the fric-
tion is much smaller than estimated through the Debye-
Bueche approach. We rewrite a simplified version of
the argument in Ref. 7 as follows: the velocity rn of the
nth monomer is of the form
(II. 1)
where Pm is the force acting on the mth monomer, and
Tnm is the backflow tensor. [It is convenient to write
Tnn = t
o
1
and to lump the first term of (II. 1) into the sec-
ond.]
(a) In an infinite sea of solvent, T nm decreases like
the inverse distance r = I rn - r m I,
J. Chern. Phys., Vol. 67, No.1, 1 July 1977
54
<----
('<<If'l' <t< < //tel ({(/t//(tt
)'>'>'>'"">;;;>;;;;>;';>

E- ---
FIG. 2. The method of images to treat boundary conditions at
the walls of the pore: the flow induced in a slit by the point
force is identical to the flow produced by and its images
(represented as dotted sources) in an infinite fluid. This meth-
od of images is simple for scalar fields; for the vector velocity
field it is more complex,9 but the principles remain similar:
the flow becomes very small at distances larger than the slit-
width D.
1 ( r r)
T(r):: -8 - 1 + -2-
1f1/.r r
(11.2)
(b) It is important to realize that in a pore or in a slit,
T(r) decays exponentially at large distances (r > D). For
instance, in a slit, when r is much larger than D, the
dominant factor in T(r) is exp(- 1fr/D). This rapid de-
crease is due to the boundary conditions at the walls: a
qualitative understanding may be reached by treating the
wall effect through a method of images, as shown in
Fig. 2. For quantitative discussions the reader may
refer to the literature on the motion of a small sphere
in a pipe filled with a viscous fluid.
9
Returning now to the equation of motion (11.1), let us
separate the forces <Pn into an internal contribution
and an external contribution The forces <pInt in-
clude both the local spring contributions of the Rouse
theorylO and the more subtle forces due to excluded vol-
ume interactions between segments m and n which are
widely separated on the chain backbone (I n - m I large).
Fortunately, in the Kirkwood approximation, it will not
be necessary to write down the structure of I>lnt in de-
tail.
We consider the case where the external force n :: N I>tot ,
and write the average chain velOCity as
1 ",. 1 '" (Int 1 )
r:: N LJ rn:: N LJ Tnm I>m + N I>tot
n nm
(11.3)
In Eq. (11.3) we average Tnm over all chain configura-
tions (Tnm - Tnm). This approximation leads to a coef-
ficient of which is then independent of m (except
for inSignificant end effects in the terminal blobs at both
ends of the chain). Since 2:m I>!:t:= 0 by the action/reac-
tion prinCiple, we are led to the Kirkwood formula for
the mobility:
'/ 1 '" -
r I>tot = N2 LJ Tnm
nm
(II. 4)
Let us now estimate the sum by a scaling argument. As
explained before, the range of the kernel Tnm is of or-
der D (apart from the wall effect, seli....consistent
screening also limits the range of the kernel to the blob
size D: see Ref. 3). Thus we have
"T ",,_1_
LJ nm - 61f1/ D g
m
(II. 5)
when g (the number of terms in the sum) is the number
of monomers in one blob, and is defined below Eq.
(1. 2): g- (D/a)5/3
The friction coefficient for the chain in a tube is thus
bchain = I>totH (ND/g) 61f1/.
61f1/sR" (tube).
(II. 6)
(11.7)
We shall now compare this to the Debye-Bueche esti-
mate [Eq. (1.9)J
D61f1/. an
bDB gbO D a
(II. 8)
We see that the Debye-Bueche estimate is qualitatively
wrong for a chain in a tube. A similar result has been
found for bulk solutions of entangled chains, where the
friction coefficient is much smaller than expected from
a simple Debye-Bueche picture.
3
We end up this section by a remark concerning chains
trapped in a slit: for this case too the tensor Tnm is
screened out at distances D and thus Eq. (II. 6) remains
valid (apart from unknown numerical coefficients).
III. INTERNAL STRUCTURE AND MODES
. The results of Sec. II on the mobility of one chain can
also be related to the blob concept of Sec. I. Each blob
(of size D) is hydrodynamically independent of its neigh-
bors and has a friction coefficient of order 61f1/.D. The
reason why the friction for one blob is not larger than
this (no plug flow effect) is that the blob does not uni-
formly fill the tube section: the concentration, mea-
sured on spatial scales D, has fluctuations of relative
order unity.
These remarks allow us to derive simply the struc-
ture of internal modes of the chain for wavelengths oX
::2rr/q such that D oXR". The deformation associated
with one of these modes is shown in Fig. 3. If the local
displacement of the blob (parallel to the tube axis) is u,
the elastic energy between blobs (p) and (p + l) has the
scaling form
F /blob :: Tf (UP+1
D
- Up)
(III.l)
J. Chem. Phys., Vol. 67, No.1, 1 July 1977
55
FIG. 3. Schematic representation of internal modes of a con-
fined chain: the blobs are periodically compressed and dilated.
u defines the local displacement of the blob.
where D is the blob Size, and can be expanded as
,I (UP+l - u
p
)2
Ftblob=Fo+T 2D2 +
(III. 2)
[Note the difference between the scaling form (III. 2) and
the corresponding form for ideal chains, where D 2
would be replaced by ga
2
, where g is the number of
monomers per blob. ]
We may now write the balance force for blob(p) in the
form
(III. 3)
Since the average distance between blobs is D, we may
write, for slow space variations,
and we arrive at an equation of a diffusive type,
au a
2
u
6 TfTls D at = T ax 2 (I1I.4)
The modes have a plane wave structure
(III. 5)
with a dispersion law of the form
(
J:... < q < J..)
RII D
(III. 6)
Again the numerical coefficient in (III. 6) is unknown,
but the structure of the result is interesting. Already
in Eq. (III. 3) the analogy with Rouse modes is striking.
The following features should be noted:
(a) The basic units in (III. 3) are the blobs, not the
monomers;
(b) For this one-dimensional set of blobs, there is a
linear correspondence between the positions along the
chemical sequence (index p for the blobs or index n =pg
for the monomers) and the poSitions along the tube axis
(x =pD). This is very different from usual three-di-
mensional chains, and explains why 11r. q2 while in
three dimensions the characteristic width of a Rouse
chain Aw. behaves like q4, as shown long ago by one of
us. 11
(c) Finally, Eq. (III. 6) holds only for wavelengths
much larger than D. For wavelengths smaller than D
confinement is not important, and we expect to return
to the three-dimensional scaling lawS;
T
Aw -- q3 (qD>l).
6TfTls
(III. 7)
Note that (III. 6) and (III. 7) join smoothly at qD = 1.
(d) The slowest collective mode of the chain corre-
sponds to qRII = 1 and scales like
(III. 8)
(e) In the limit qR
II
< 1 we have the diffusion mode of
the whole chain. This corresponds to
(III. 9)
At qRII =1, this does not croSs over smoothly with the
internal modes. The physical interpretation of this ef-
fect is the following: the chain moves inside the tube by
a reptation process, described in Ref. 3. We can verify
that the contribution of the internal modes to the trans-
lational diffusion (OD
t
) scales like D
t
The contribution
of the fundamental mode to D
t
is related to the first
mode amplitude by the reptation formula
(I1I.1D)
Note that D
t
is not equal to RVe, but is smaller. We
derive from the elastic free energy (III. 2) by the
equipartition theorem. The result is

and thus we find
T

t Tlfill
in agreement with Eq. (II. 7).
IV. ASPIRATION OF A CHAIN IN A CONICAL PORE
In static conditions it is well known that a single chain
cannot enter in a pore of diameter D much smaller than
the spontaneous chain radius R
FS
' The confinement free
energy is
(
D) (R)5/3
F=Tj RF -T if
(N.1)
Let us conSider, however, the possibility of sucking a
chain inside a tapered tube by a suitable flow of solvent.
This is shown in Fig. 4, where we consider a slightly
tapered tube, with a constant (small) tapering angle .
We assume that the solvent is pumped towards the nar-
row end of the tube; if the flow velocity at pOint x along
the axis of the tube is v, the corresponding flux is J
vD 2 and the pressure gradient is
56
-J
~ . ______ 4L __________ ~
FIG. 4. Aspiration of a chain in a conical pore by a solvent
flow (J).
(IV. 2)
where D = EX, and we again ignore all coefficients.
A stationary chain in the tube is subjected to two
forces:
(a) the sucking force which we derive from Eq. (II. 7),
 ~ 61TTj R v ~ N D 3 ap =!!. Tj.J
s s" g ax g D
(IV. 3)
(b) the elastic force derived from (IV. 1),
 =_ aF ~ I.. (RF3)5/3 ~ ! ! . TE
e ax X D g D
(IVA)
Equating these two forces we see ,that the factors N/gD
drop out and we are left with the condition
J =J ~ .I.- E
e Tjs
(IV. 5)
It is quite remarkable to find that the critical flux J
is independent of the molecular mass. Also when J =J
e
the balance of forces is satisfied for all x inside the
tapered tube, because <l>s and <1>. have the same depen-
dence on x.
Instead of discussing a critical flux, it is more prac-
tical to estimate the pressure P needed to suck in the
chains. If Dm is the diameter at the narrow end (x =x
m
),
we require a pressure difference
When J = J
e
this becomes
T
APe = ~ X const.
min
(IV. 6)
(IV. 7)
For all pressure differences Ap <: APe the chains will not
enter the narrow region: they will be stopped at a dis-
tance x=RF/E. But when AP>APe the chains will be
sucked in. Typically, if D
min
= 100 A, APe from Eq.
(IV. 7) should be of order 1/10 atm; thus the experiment
may be feasible. The observation that the threshold
APe is independent of the molecular mass (provided that
the chains are confined, i. e., R F D
min
) would provide
an interesting check on all our description. We em-
phasize again that the pore should be nearly cylindrical
(E small). At large E other effects related to the exis-
tence of longitudinal flow gradients may become essen-
tial. Pores of small, controlled D can be obtained by
particle track etching in sOlids,12 but tapered pores
seem harder to make.
IC. K. Colton, C. M. Satterfield, and C. S. Lai, AICHE J.
21, 289 (1975).
2M. Daoud and P. G. de Gennes, J. Phys. (Paris) 38, 85
(1977).
3p . G. de Gennes, Macromolecules 9, 587 (1976).
4p. Pincus, Macromolecules 9, 386 (1976).
5p. Pincus, Macromolecules 9, 386 (1976).
6p. Debye and A. Bueche, J. Chem. Phys. 16, 573 (1948).
7J . Kirkwood, J. Polym. Sci. 12, 1 (1954).
BSee , for example, L. Landau and E. Lifshitz, Fluid Mechan-
ics (Pergamon, London, 1959), Chap. 2.
9J . Happel and B. J. Byrne, Ind. Eng. Chem. 46, 1181 (1954);
R. M. Sonshine and H. Brenner, Appl. Sci. Res. 16, 273
(1966); H. Wang and R. Skalak, J. Fluid Mech. 38, 75 (1969).
tOp. E. Rouse, J. Chem. Phys. 21, 1272 (1953).
liE. DuboiS-Violette and P. G. de Gennes, Physics 3, 181 (1967).
12R. Fleisher, P. Price, and R. Walker, Rev. Sci. Instrl'm.
34, 510 (1963).

Dynamics of Confined Polymer Chains

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