Huggins coefficient for the viscosity of polymer solutions

Karl F. Freed and S. F. Edwards

Citation: The Journal of Chemical Physics 62, 4032 (1975); doi: 10.1063/1.430327
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 Huggins coefficient for the viscosity of polymer solutions *
Karl F. Freed t
The James Franck Institute and the Department of Chemistry. The University of Chicago. Chicago. Illinois 60637

S. F. Edwards
Cavendish Laboratory. Cambridge, England CB3 OHE
(Received 4 February 1975)

A theory of the Huggins coefficient for the viscosity of polymer solutions (under e conditions) is
presented that is free of improper integrals. The theory is explicitly applied to the Gaussian chain
model and yields the value 7T,(2)/['(312)]' = 0.757, where, is the Riemann zeta function.

I. INTRODUCTION dilution limit. This estimate leads to a value of 0.76

The theory of the viscosity of polymer solutions has
primarily centered on the case of solutions at infinite
dilution and low frequencies which are subject to low
shear rates. 1 In this limit, the simple Rouse-Zimm
model provides an adequate representation of the ob-
served viscosities in 8 solvents.
The theory of the viscosity of polymer solutions at
finite polymer concentrations has been beset by a num-
ber of fundamental difficulties. 1-5 A major portion of
the efforts of this nature are directed towards the evalu-
ation of the so-called Huggins coefficient kH in the con-
centration expansion of the solution viscosity,
(1)
Here 710 is the viscosity of the pure solvent, [71] is the
infinite dilution polymer intrinsic viscosity, and c is the
polymer mass concentration. The theories of [71] re-
quire the consideration of a single chain, while those
for kH involve a pair of typical chains in analogy with
the treatment of second virial coefficients. Because of
the long ranged nature of the hydrodynamic interactions,
the average stress tensor acting on a chain, due to the
remaining chains, is proportional to r- 3 • 1 This leads
to some improper integrals for kH' which depend on the
surface of the system and are, consequently, of ques-
tionable validity. Saito has noted that these improper
integrals are a result of the use of the Stokes approxi-
mation to hydrodynamics, and has suggested the need
for a nonlinear theory to remedy this deficiency. 2
Petersonand Fixman5 have argued, on the other hand,
that the situation is somewhat analogous to that encoun-
tered in the theory of dielectrics. They have therefore
evaluated both the average stress and the average veloc-
ity gradient and have shown that the viscosity, as ob-
tained from the ratio, does not involve improper inte-
grals and is not dependent on the surface. They apply
the theory to hard spheres to obtain 0.691 for k H • For
a model of penetrable spheres their calculation results
in the value kH = 0.883.
Thus, there presently exists no completely satisfac-
tory theory for kH for chainlike molecules, say, of the
random coil nature. It should be noted, however, that
Brinkman6 has cleverly employed a very simple dimen-
sional method to estimate the concentration dependent of
(1) solely on the basis of the knowledge of its infinite
for k H •
Recently, we have presented a theory of polymer vis-
cosity7 in concentrated solutions. 8 It is noted therein
that the above mentioned improper integrals in the the-
ories of kH are suggestive of more serious divergences
in higher orders of perturbation theory in a manner that
is quite analogous to the well studied case of electrolyte
solutions, etc. By analogy with the Debye screening in
Coulomb systems, we showed how the hydrodynamic in-
teractions become screened in concentrated polymer
solutions. 8 The resulting specific viscosity has a
Rouse-like molecular dependence in the concentrated
solutions in contrast to the Rouse- Zimm behavior ob-
tained in infinite dilution when hydrodynamic interactions
are incorporated. In this paper we show that, when the
dilute limit of the previous work is employed, a theory
of kH is obtained which is free of improper integrals.
If a naive expansion in powers of the density were applied
to the integrals, before their evaluation, the results
would lead to improper integrals; a denSity expansion
after integration is, however, well defined. The theory
is applied to the Gaussian random coil chain and leads to
the value of 0.7574 for kH in a solvents which is identical
to the estimate of Brinkman. 6 ,9,10 We ignore any effects
of interactions, other than hydrodynamic, or their re-
sulting correlations between chains, and an estimate of
these effects shows them to probably be negligible in a
solvents. 10 It should be noted that the present theory
is not limited to the case of Gaussian chains, but the re-
striction to e solvents represents an essential simplifi-
cation. Apart from the straightforward treatment of
corrections for very small excluded volume, our inabil-
ity of evaluating kH in good solvents parallels the corre-
sponding lack of a fully acceptable theory for the corre-
sponding equilibrium property, the second virial coef-
ficient for the osmotic pressure. 1
II. CONCENTRATION DEPENDENCE OF POL YMER
VISCOSITY
Our earlier theory provides a completely general
method for considering the concentration dependence of
polymer viscosity.8 Rather than repeating the involved
mathematical equations, only their physical content is
reviewed. The final required formulas are quoted as re-
quired. The theory is a hydrodynamical one which con-
siders the fluid flow past an array of polymer molecules

4032 The Journal of Chemical Physics, Vol. 62, No. 10, 15 May 1975 Copyright © 1975 American Institute of Physics

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 K. F. Freed and S. F. Edwards: Viscosity of polymer solutions
(or other obstacles) which have internal structure and
dynamics. The exact hydrodynamic equations can be
represented in terms of a multiple scattering type ex-
pansion in a fashion that is similar to that which can be
applied to describe the multiple scattering of the fluid
within a single chain. [c.r. Eq. (32.14) of Yamakawa. 1]
The asymptotic fluid velocity is then the sum of the un-
perturbed fluid velocity, the velocity perturbation aris-
ing from single chains, pairs of chains, etc., with the
condition that successive perturbations of the fluid flow
be due to different chains. An average is performed
over the polymer configurations, as usual, and a formal
density expansion of the polymer viscosity is obtained
from the effective Navier-Stokes equation for the aver-
aged polymer solution.
Two qualitatively different types of contributions to the
viscosity can be identified. The first involves incoherent
processes in which there are no correlated scatterings of
the fluid by the polymers. One simple type of correlated
term involves, say, the string of scattering events
ABAB, where A denotes scattering by chain A, etc.
This term and all its higher order analogs are of the
same kind of mathematical form as those which enter
into the equilibrium excluded volume problem to intro-
duce the long range correlations along the chain that
make the mathematical solution of the problem so in-
tractable. 11 In the absence of ordinary electrostatic in-
teractions between the chains, the correlations in ABAB
type scattering events arise from correlations induced
by the hydrodynamic interactions. As the intrinsic vis-
cosity comes from the incoherent processes like
ABCD ... , where no two chains in the sequence are iden-
tical, 8 it is clear that at very low but finite polymer con-
centrations the dominant additional contribution to the
polymer viscosity must arise from the incoherent scat-
tering of the fluid by pairs of chains. Thus, a calcula-
tion of the Huggins constant for e solvents only requires
the retention of the incoherent terms.
Since the intrinsic viscosity is attributed to those in-
coherent processes, where the same chain does not enter
twice in any individual scattering sequence, it is clear
that all the density dependence is due to the multiple ap-
pearance of chains. The simplest incoherent terms are
of the form ABA, ABCA, ABACA, •.. , for Band C rep-
resenting different chains. These incoherent terms are
readily separated from the coherent ones when the scat-
tering sequences are represented in the pictorial form
of paper II. 8
Although the distinction is not required herein, for the
interested reader we note that the incoherent terms are
represented by those diagrams in Fig. 1 of paper Irs
which do not have any wavey lines that cross each other.
In paper II,8 these incoherent terms are retained to all
orders in the polymer concentration. It is shown there 8
how this leads in concentrated solutions to the screening
of the hydrodynamic interactions and a concomitant tran-
sition from a low concentration Rouse-Zimm-like vis-
cosity to a high concentration Rouse-like viscosity which
is proportional to the molecular weight M of the. chain.
From the standpoint of a given polymer chain, the net
effect of these incoherent terms is the introduction of an
J. Chem. Phys., Vol. 62, No. 10, 15 May 1975
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4033
effective concentration dependent hydrodynamic interac-
tion (Oseen tensor) within the chain. In lowest order this
arises because, say, bead i on chain Q perturbs the fluid
flow which is incident on chain f3. The perturbed flow
from (:l then impinges on bead j on the original chain Q,
thereby leading to the effective concentration dependent
indirect hydrodynamic interaction between i and j on Q.
The totality of the incoherent scattering processes leads
to a polymer solution viscosity which is solely express-
ible as that due to individual chains with a concentration
dependent intrachain hydrodynamic interaction.
Before presenting the expression for the viscosity, it
is useful to digress to make some minor alterations in
paper r" to restore a greater level of correspondence
with other theories 1 in the limit of infinite dilution. In
paper 17 we employ the continuum limit wherein sums
over individual beads are replaced by integrals 1 over the
continuous chain contour variable s, where 0:$ s :$ Land
L is the total chain length. Integrals of the form foL ds
x foLds' j(s - s') for long chains (L- 00) are now asymptot-
ically evaluated as 2L L~I/2 d(s - s') j(s - s'), rather than
the form used in paper I with integration limits ± Land
without the factor of 2. This change implies that the
Fourier (Rouse) modes conjugate to (s - s') are given by
q=2rrk/L with Ik 1=1,2, ... , L/Z and Z the Kuhn effective
step length. This slight alteration and the use of sums
over the Rouse mode indices k, rather than the more
approximate integration over q, leads to the association
of the friction coefficient per unit length !'o with the usu-
al Rouse bead friction coefficient !, via !'o = r,/Z.
Gi ven these slight modifications, the methods of papers
I and II imply that the concentration dependent polymer
specific viscosity can be written as7 • 8
(e) ,=?1..:::..!l!J. Z2 NA I~ cUj (2)
TJsp - eTJo 3rrTJoMA qo q2K(q, e)
in the integral form, or
_ Z N A L f'- 2
2
TJsp(C) -6 2 M L..J [k K(2rrk/L, e)]
-1
(3)
rr TJo A""l
in the more precise summation form. In (2) and (3) TJo
is the solvent viscosity, NA is Avagadro's number, MA
is the "monomer" molecular weight, qo=2rr/L is now the
minimum Rouse modewavevector, and K(q, e) is the av-
eraged full intrachain hydrodynamic interaction for the
Rouse mode with wavevector q. For instance, at infinite
dilution K(q, 0)1 is computed by converting the familiar
expression
(K1J(c =0» =(r,-1 0 0 1+ (1 - /i o ) (8rrTJoRot1
(4)
to continuous notation
(K(ss' ;0» 1 = [1;;;1 o(s - s') + (6rrTJot 1 (IR(s) - R (s') 1-1)] (5)
and then by taking the Fourier transform to convert the
result to Rouse mode variables
K(q,O)= I: d(s-s')exp[iq(s-s')](K(ss';O» (6)
[In (4) RIJ is the vector connecting beads i and j, while
 4034 K. F. Freed and S. F. Edwards: Viscosity of polymer solutions

in (5) IR(s) - R(s') I is the distance between contour

points sand s' along the chain.] At finite concentration, 2
..L [1 _..L -
ca ca
(1..)2
ca
+ ... ]
'
0 < y / ca < 1
the full K(ss';c) is first evaluated without invoking the y -
popular preaveraging approximation in order to correct- y2+cay- l_~C_(:cy+... l<y/ca,;;oo
ly introduce the indirect hydrodynamic interactions to
all orders. After this has been accomplished, K(ss';c)
1
Since the minimum value of Iq I is 21T/L, the maximum
can then be averaged over polymer configurations. value of a c is
Perhaps this should be termed the post-averaging ap-
(15)
proximation. The final result for Gaussian coils is
given in paper If to all orders in concentration via l2 where r~ = (V /N) is the average volume available per

1;)-1 +"32 J(21T)3 3 2

chain and (fi2) =L1, so the inequality in (15) holds for di-
d k k 1/3 1 lute solutions. In fact, screening enters when (15) is not
K(q, c) =(1 (k 21/6)2 +q2 -1/o-k.....2-_-~....,~"'"O)'"'(-k,-c~) (7)
obeyed. When (15) is used, it is easily shown that the
with terms from the fo"'c dy integral are all of higher order in
concentration and that the lower limit in the f;c dy in-
(8) tegral in the leading terms throughO(c) can be set to zero
without error to that order. This gives
(16)
III. THE HUGGINS COEFFICIENT which tends to (9) as c- 0, as it must.
In order to evaluate the Huggins coefficient, it is only When (16) is substituted into (2) or (3), a term in
necessary to evaluate ~~O) to lowest order in polymer [1- a(q) c(2)"1/2 +O(c 2 )] appears in the denominator, but
concentration c. This is readily accomplished by using to first order in c, this may be expanded to give
the infinite dilution value [1 +a(q) C(2)"1/2 HJ(c 2)] in the numerator. In the more
precise discrete notation, Eqs. (16) and (3) give
(9)
which comes from (5) and (6) for the Gaussian coil. In N 15/ 2 LI/2 ~ 32 (N )215L ~ 2 2
(9) we have taken the nondraining limit of 0, as this 1;-1_ 1/sp(c)=..!.:..iM (6 )112 L:k- / +C"it
A 1T "=1 A
-6 L:k- +0(C )
"=1
considerably simplifies the subsequent evaluation of the (17)
integrals in (8) and (7). Employing (9) and the change of Upon noticing that the c-independent term in (17) is the
variables nonfree draining intrinsic viscosity [1/(0)] of the Rouse-
y =[61q I/k2Z]1/2 (10) Zimm model, (17) implies the Huggins coefficient is

converts (8) into kH = 1T1;(2)/[1;(3/2)]2 = 0.7574 , (18)

where I; (p) is the Riemann zeta function

~~O) =_ 8clkNA(!.)1/21~ y2dy(1 +y4)"I+O(C2)
A1TMA 6 0

(11)

Substituting (11) into (7) and again setting /;"1_ 0 gives,
after using the change in variables y =(l/6Iq 1)1/2 k,
(12)
with
a;: a(q);: 21TNA15/2 /MA (61q )1/2 • I (13)
The integral in (12) converges and is bounded by K(q, 0)
of (9), i. e., 0 < K(q, c) ~ K(q, 0). If (12) were expanded
in powers of c, the higher order integrals would, how-
ever, all ultimately diverge since (12), with the o(c 2 )
terms neglected, is not an analytic function of c; it di-
verges for nonphysical negative values of c.
The leading concentration dependence of (12) canreadi-
lV. DISCUSSION
In the presence of interactions between chains and
within chains, i. e., in non-6 solvents, the above calcu-
lation must be modified accordingly. However, in this
case there are additional contributions to kH which re-
sult from the fact that successive scatterings AB are
no longer incoherent due to the correlations between A
and B which are induced by the chain-chain interactions.
This introduces terms linear in c into ~~O)(k, c) which
are of the form of the spatial Fourier transform of
1 N
"2 L:[(1'0:.G·1'8)-('T0:)·G·(1'B)] , (19)
0:#1
where the averaging in the first term involves polymer
distributions for a pair of interacting chains a and f3 and
'T 0: and G are given in paper II. 8

ly be obtained by taking

i:
Although the second virial coefficient for the os-
motic pressure vanishes at the 6 point, there is no
[00 dy;: [XC dy + dy (14) guarantee that (19) also vanishes there, as (19)
measures a different average than does the virial
and employing the convergent expansions coefficient. However, it can be anticipated that (19)

J. Chern. Phys., Vol. 62, No.1 0, 15 May 1975

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 K. F. Freed and S. F. Edwards: Viscosity of polymer solutions 4035

should be negligible, if nonzero, at the e point. 10 In-
deed, a crude approximation to (19) can be obtained by
employing a generalized Kirkwood superposition approx-
imation to the two-chain-four-bead correlation function
in (19) and then by replacing the individual two-chain-
two bead correlation function by their averages over all
the beads on the chains. This displays (19) as propor-
tional to [{f"I1)4 -1], wherej,,11 is the single chain con-
tact probability which is unity for noninteracting chains. I
Thus, this simple approximation supports the neglect of
(19) at the e point.
It is of interest to note that the general expression for
the zero-frequency viscosity (2) is obtained from ~~O)(k,
c) by taking the small k limit,
(20)
which is the manner in which the viscosity is extracted
from the effective hydrodynamic equation in our previous
papers. Equation (20) is the long wavelength limit where
hydrodynamics must be a valid description. The result
(11) might therefore appear to be at variance with hydro-
dynamics, Le., with Eq. (20). However, from (7) it is
clear that the k values of relevance to K(q, c) are those
for which k- (Iq 16/1)1 /2 • Since the minimum value of
Iq I is 2rr/L, this means k~[(2rr)6/lLF/2, or wavelengths
:S [Ll(2rr/6)]1/2. Thus, (11) probes the high k, short
wavelength, nonhydrodynamic limit behavior of ~~O)(k, c).
. *This research is supported by Grant GH-43165 from the Na-
tional SCience Foundation and has benefitted from MRL(NSF)
facilities at the University of Chicago.
t Camille and Henry Dreyfus Foundation Fellow.
1For a thorough review and further references, see H. Yama-
kawa, Modern Theory of Polymer Solutions (Harper and Row,
New York, 1971).
2N. Saito, J. Phys. Soc. Jpn. 5, 4 (1950); 7, 447 (1952).
3J. Riseman and R. Ullman, J. Chern. Phys. 19, 578 (1951).
4H• Yamakawa, J. Chern. Phys. 34, 1360 (1961).
5J. M. Peterson and M. Fixman, J. Chern. Phys. 39, 2516
(1963).
6R . C. Brinkman, J. Chern. Phys. 20, 571 (1952).
1S. F. Edwards and K. F. Freed, J. Chern. Phys. 61, 1189
(1974), paper I.
8K. F. Freed and S. F. Edwards, J. Chern. Phys. 61, 3626
(1974), paper II; and (to be published).
9G• C. Berry, J. Chern. Phys. 46, 1338 (1967).
lOR. Simha and L. A. utracld., Reol. Acta 12, 455 (1973).
11 K• F. Freed, J. Chern. Phys. 55, 3910 (1971); Adv. Chern.
Phys. 22, 1 (1972).
12Equation (7) differs from (4.7a) of paper II in the appearance
of the factor of ~ from the angular average that was omitted
in the latter. Equation (8) differs from (4. 7b) of paper by
the over-all factor of 2 from the H f~dsds/integrals.
as noted above, and with the replacement of the monomer
density p of (4.7b) by cNA/MA•

J. Chem. Phys., Vol. 62, No. 10, 15 May 1975

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