PolymerScience U.S.S.R. Voi. 32, No. 4, pp.

682-689, 1990
Printed in Great Britain.

0032-3950/90$10.00+ .00
1991PergamonPress pie

SCALING PATTERN OF SWELLING OF POLYMER

NETWORKS*
S. V . P A N Y U K O V a n d S. I. K U C H A N O V
Lomonosov State University, Moscow
(Received 22 December 1988)

Within the scaling theory a detailed analysis is made of the character of the swelling of network polymers
obtained by branched polycondensation and crosslinking of linear chains via the terminal groups. The
boundaries of the applicability of different theories describing the swelling of the networks have been
established and the theoretical dependences of the degree of equilibrium swelling and osmotic pressure of
the network on its density and the parameters characterizing its topology and the thermodynamic quality of
the solvent have been found.

Tins paper examines theoretically gels formed on swelling in a good solvent of networks of two
types. The first of them is obtained during f-functional homopolycondensation and the second on
crosslinking via the terminal groups identical chains of N units with the aid of a f-functional low
molecular weight crosslinking agent. A scaling analysis of the swelling of the networks of the second
of these types was earlier presented by de Gennes [1] in the case of complete conversion of the
functional groups. He showed that the gels formed on swelling of such ideal networks may be
represented as a set of tightly packed blobs each of which consists of a separate swollen chain
between two neighbouring nodes of the network [1, p. 171].
Below we consider the case more general and important in practice when networks may be
non-ideal, i.e. contain together with elastically active chains (e.a.c.) and active nodes also passive
material. The second difference from de Gennes approach [1] is that we constructed the scaling
pattern of swelling of both types of gels. Some of the results were initially derived strictly by the
renorm-group method [2] and below we give another simpler and more graphic derivation of them
starting from elementary scaling notions. It is easiest of all at first to demonstrate it with reference to
networks of the first type obtained in a concentrated polymeric system.
The topological structure of each of such classical networks besides f is characterized by a single
parameter---conversion Pg of the functional groups in the gel associated with complete conversion
of these groups P in a simple fashion [3]
eg = P(1-

82(f-1))/(1-~f),

8 = 1 _p+p~r-t.

(1)

For the osmotic pressure ~r of such a network swelling at the temperature T in a good solvent, for
a low density of it within the approximation of the self-consistent field (s.c.f.), we obtain the
expression [4, 5]
zr/T = B p 2 - ~'gp,

~'g=-fPg/2 - 1,

(2)

where B is the second virial coefficient of the interaction of the polymeric units renormalized with

*Vysokomol. soyed. A32: No. 4,744-750, 1990.

682

Swelling of polymer networks

683

reference to the solvent [6]. This magnitude was called in ref. [1] the excluded volume parameter,
the notation v is used. Here and below for simplicity the Boltzman constant ks = 1.
Theoretically of the utmost interest is the examination of critically branched networks [7]. Such
networks obtained close to the gelation threshold p = p* ~ ( f - 1) -a have a universal topological
structure. It is described by a single parameter z = p/p* - 1 ~ 1 connected according to relation (1)
with 1"gin simple fashion: zg = ( f - 1) r2/3(f - 2). Such a network may be represented as consisting of
tree-shaped fragments with the number of units 10 (of size a) in each of them concurring with the
number of apices of a randomly branched tree, the topological diameter of which is equal to the
mean topological size of the network cycle. In the conditions of synthesis for fixed z the geometric
size of such a fragment coincides with the radius of the correlations of density G0~'ay-a/2~-alo TM
which gives lo ~ ~.-2,> 1. The parameter ~"also determines the mean number of units in one e.a.c.
Le ~ 7-1 [8]. In the approximation considered for the radius of the correlation of the swollen
network we obtain the expression [4, 5]
~,-~-.a/(Tc'l') TM, "l'c~-- - r + 2 ( f - 2 ) B p / ( f - 1)r,

(3)

where the parameter rc by definition tends to zero on the spinodal. The region of applicability of the
s.c.f, approximation is determined in the space of any dimensionality d, as usual [9], from the
condition of smallness of the relative fluctuations of the density of the gel on scales of the order

((6p)2)
~---

(~)2

1 (~) 4

--~ad(,.l.cT)(4--d)/4"~-'-~

":~ 1.

(4)

With violation of this condition to describe the swelling of the gel one may use the scaling theory.

Scaling analysis
According to it on scales much larger than ~ where the relative density fluctuations are low it is
necessary to start from the formulae of the s.c.f, approximation with renormalized (through
fluctuations on scales smaller than ~) values of the parameters
~i=~:,

t~=t~,

/3=BB~-~,

~1,

r=~r.

(5)

Such renormalization may be regarded as passage from units to new structural elements--blobs
the geometric size of which is ~ and the density and second virial coefficient are denoted respective
as PB and BB. The fourth of the relations (5) follows from the hypothesis of scale invariance [9] and
renormalization naturally does not change the osmotic pressure value. The first and fourth of
relations (5) may be written with reference to expressions (3) and (4) in the form

~= 1, Bb~, = ~Pb ~- 1,

(6)

where the last expression represents the condition of tight packing of the blobs. Depending on the
value of the parameter ~ which determines the conversion of the gel obtained by "polycondensation" of the blobs, different types of scaling patterns of the swollen networks are possible. Let us
look at two of them corresponding to the limiting structures of this large-scale gel of blobs.
The first (Fig. la) refers to the case ~- = 0 of free swelling when according to the relations (2) and
(6) we get ~ ~g~- 1 and the second (Fig. lb) to limited swelling in volume far less than equilibrium
when '~ 1 and ~g,~ 1. Consequently, the structure of the gel of blobs will be similar to the gel of
units, obtained in the first case far from the gel point and in the second close to it. In the last case to

684

S. V. PANYUKOV and S. I. KUCHANOV

(a)
(b/

s ~

Fic. 1. Scalingpatterns of swellingof criticallybranched networksof the firsttype in conditionsof free (a)
and confined(b) swelling.

compress in a good solvent such a critically branched network to tight packing it is necessary to
apply the pressure
r = Tpb ( Bb Pb - g) = Tpb = T~"--d.

(7)

The number of units of the blob g determines the average length le ~ g l / 2 of that part of the e.a.c.
which forms part of this blob. Therefore, each e.a.c, contains e ~ -1 blobs
(8)

~ = L~/l ~- (to~g) 1/2.

For ~ 1 and ~ a 1 from relation (8) follows respectively/~, ~ 1 and >>1 as shown in Fig. 1.
For a full scaling description of swelling of the networks it remains to present the dependences
linking the characteristics of the individual blob g and ~ with the parameters of the gel a, B,
p(u = B / a a and = pa d)
g~u,n~n~,

~-aum2dP nz,

ml

2d
4-3d

2
m2 -- 4 - 3 d '

nl-

2(d+2)
4-3d

5
n2 - 4-3-----d"

(9)

(10)

These formulae follow directly from the equations

g~.p~d,

~aul/(d+2)gV,

5
u = 2(d+2----~'

(11)

the first of which reflects the equality of the densities of the blob units and the whole system and the
second is obtained [10] by considering within the Flory approximation of swelling a randomly
branched tree-like molecule of the polymer with the number of units g.
The least possible density of the gel p* is reached on its free swelling. Its value
* = p*aa.-~u'm~, m3 = - d / ( d + 2 ) ,

s = (3d-4)/(d+2)

(12)

is found from the expression (9) with the condition g = l0 ~ ~.-2 when each e.a.c, contains according

Swelling of polymer networks

685

to relation (8) a single blob. Formula (12), an analogue of the Flory theorem on gels [1, p. 172]
corresponds to the fact that on free swelling a concentration of units is automatically established
corresponding to the threshold of the overlap of single randomly branched molecules with the
number of units g ~ l0 [11]. In the case of severely limited swelling ~* ~ ~ 1 the osmotic pressure
of the gel considered does not depend on its topology, i.e. the parameter ~', and is determined for set
u only by density in line with eqns (7) and (10)
2d
m4=3d_4,

zraa~-Tum'CP 'u,

5d
3d-4

n4

(13)

Passing to consideration of the swelling of networks of the second type it is necessary instead of a
unit to take as a structural element from which the blobs are formed a separate swollen linear chain.
Using the Flory method [10] we find the radius of such a blob R ~ ~ from the condition of the
minimum for R of its free energy
Fb(R)

R2

(aN1/Egl/4) 2 +

B(Nglin)z
Rd
.

(14)

Such minimization together with the expression generalizing the first of the relations (11) gives a
set of two equations
N g l i n ~ P ~ d,

~-aul/(d+2)glinVNVt~n ,

for

Ulin=d+2,

(15)

yielding scaling expressions for the number of linear chains glin in the blob and its size
dlhin - 1

glin ~ umlt~mNqli",

ql -- - -

1 --

dv

3d -

1 - du

(17)

3d- 4

nl = 1 - d r '

m2

(16)

q2= u-______u_

~.aum2~pn2Nq2,

d
ml = ( d + 2 ) ( 1 - d u ) '

4(d- 1)

--

(d+2)(1-du)'

n2

1- dv

(18)

Putting glin ~ ~.-2 in formula (16) we obtain a generalization of expression (12)

P*~'um3CN q3,
s = 2 ( d r - 1),

(19)

m 3 = - d / ( d + 2)

q3 = 1-dVli n = - 2 ( d - 1)/(d+2),

(20)

and substituting expression (17) for ~ in formula (7) gives the dependence of ~- on the density of
networks of the second type
raa~- Tu"'dpn'N q',

n4

dv
dr- 1

q4

1)

m 4 = dl(d+2)(dv-

d(1.'lin- v)
dr- 1

--

d
3- d- - 4

(21)

(22)

The formulae (16)-(22) were more effective in the special cases ~'-~ 1 or N ~ 1, respectively, than
the known Flory--de Gennes results for ideal networks [1], or to the expressions (9), (10), (12) and
(13) that describe swelling of the networks of the second type. Now let us look at change in the
scaling pattern of swelling of the gel for 7 4 1, N>> 1 as its all-sided compression progresses.
Here, with increase in there are two characteristic regions of universal behaviour. In the first of

686

S.V. PANYUKOVand S. I. KUCHANOV

them ~* ~(I)'~(I)lin* where the formulae (16)-(22) apply the gel represents a set of tightly packed
branched blobs each of which itself represents a dilute solution of coils of swollen linear chains
(Fig. 2). As the compression of the gel proceeds their dimensions do not change but there is fall in
the size of the blobs and increase in their concentration. Finally, for a density value
(I) ~ (I)lin* ~ um3Nq3the number of chains in the blob glin [eqn (16)] becomes of the order of unity.
With further compression of the gel in the region ~lin* ~ ~ 1 the above considered "branched"
blobs disappear and in their place de Gennes "linear" blobs appear [1, p. 86], the tightly packed set
of which constitutes the scaling pattern of such a swollen network (Fig. 3). In this second region of
universality the chemical crosslinks between chains do not show up at all and the behaviour of the
gel is simply analogous to their semidilute solution. The formulae known in this case for the number
of units g = Ngli n in such a linear blob and its size ~ are obtained from the formulae (16) and (17) if
one puts v = V~in.Relation (21) passes in the case d = 3, as it ought, to the known de Gennes law [1,
p. 84]. It is also not difficult to see that passage to it actually occurs in a continuous way for ~ ~ i . *
on the surface of the crossover between the two regions of universality which is obtained from the
expression (16) for glin ~ 1.
In the case of swelling of ideal neworks the first region (branched blobs) is absent and on swelling
of the networks of the first type naturally the second region (linear blobs) is not realized. The
pattern described above corresponds to the case when over the whole range of change in density
the system is described by scaling laws. In reality, however, situations are possible when with
increase in ~ scaling patterns are replaced by the s.c.f, theory.

Regions of applicability of the s.c.f, and scaling

For networks of the first type the inequality (4) is never fulfilled as may be readily noticed from
the expression
(23)

~ dP-l(~]a) 4 - a = U(d-a)/4dP (d-8)/4,

2'J
~ li

./
FIG. 2

FIG. 2.

FIG. 3

Scaling patterns of swelling of critically branched networks of the second type.

FIG. 3.

De Gennes scaling pattern of free swelling of ideal networks.

Swelling of polymer networks

687

obtained with the aid of formula (3). Consequently, to describe the swelling of such networks it is
always necessary to adopt the above developed scaling approach.
In considering swelling of networks of the second type an important role is played by the
parameter N* ~ u 2/(d-4) determining the characteristic number N* of units of the chain starting
from which the effects of excluded volume become manifest in it. The link presented between N*
and u is derived from the condition z = 1 where z = u N (4-d/2) is the known parameter of the theory
of perturbations for linear chains [6]. Let us first look at the most interesting case u ~ 1, N*-> 1 of
closeness of the system to 0-conditions where the physical picture of swelling of the gel will depend
on the ratio of the magnitudes N and N*.
For networks with sufficiently short chains N ~ N* the parameter is written in the form
~, u(d--4)/4 t~.)(d-8)/4 N -d/4.

(24)

To demonstrate this it is necessary to replace B, a and p in the definitions of (3), (4) and (11), g, x
and g by the corresponding magnitudes
Blin -- B N 2,

Rlin = aN 1/2, 01in = p/N

(25)

for new structural elements----chains and also to use the first of the relations (15). To find the
magnitude
Blin in (25) one may use the invariance of the parameter z of a chain of complete length
g N relative to the choice of structural elements
z = B (gN)(4-d)/2[a d = Bling(4-d)/2]Rlin d.

(26)

Comparison of expression (24) with (23) shows that with increase in the number N of units in the
chains the degree of screening by them of the volumetric interactions rises.
The result of this effect is that in sufficiently concentrated systems ~ -> ~* = u (d-2)/(a-a) for d = 3
there exists the range N*~>N,>N**~-u(d-a)/d~ (d-8)/a in which the density fluctuations are
practically unimportant and one may use the s.c.f, concepts. For networks with
N ** ~ N,~ N l i n * ~ u - 1~ - 1 ( N l i n * is found from the condition ~ ~ Rli n ) the s.c.f, theory described by
the relations (2), (3) and (25) applies and in the case Nlin* , N ~ N * we have the known picture of
Gaussian blobs in the semidilute solution of linear polymers [1, pp. 132; 12].
At a low concentration ~>qb** the scaling theory describes swelling of any networks with N,~ N*
since for them the condition (4) of applicability of the s.c.f, for these values is not fulfilled.
Networks with N , > N * are considered below with the aid of a different approach.
Thus, within the framework of a scaling analysis one may formulate the criterion of applicability
of the concept of blobs underlying this analysis and independent of the traditional GinzburgLandau condition x ~ 1. Such a criterion is the value of the free energy of one blob Fb large as
compared with T. Only in this case can the blobs be regarded as elementary statistical units. Within
the Flory theory the magnitude Fb determined by expression (14) taken at the point of its minimum
with reference to formula (16) has the form
Fb ~ T ( N * *IN) d/(3d-4),

(27)

valid for any relation between N and N*. As follows from expression (27) the criterion Fb "> T agrees
with the condition x ~ 1 of applicability of the s.c.f, theory.
Formula (27) for glin ~>1, where glin is determined by expression (16) may be represented in a
different form
F b ~- T ( g l i n / g l i n * ) (8 - d )/2(d+ 2), glin* ~" (N *]N )2(4 --d)/(8 - d).

(28)

688

S . V . PANYUKOV and S. I. KUCHANOV

On swelling of networks in an athermal solvent u~-1 in the case d < 4 we have N*~-1, glin* < 1
and according to the formula (28) Fb~> T. Consequently, here one must always use the results of the
above presented scaling analysis. With worsening of the quality of the solvent u < 1 as above two
cases N ~ N * and N < N * must be considered separately. N>>N* according to formula (28) the
magnitude glin* ~g1, i.e. swelling is described by the scaling pattern. In the opposite case N < N *
(glin* ~,1) to it correspond only gels with glin*~glin (t~'~(I)**) while on fulfilment of the formal
inequality glin<glin* (when O,> O**) swelling is described by the s.c.f, theory.
Refined scaling
The above considered simple scaling pattern of the swelling of polymeric networks obtained as
part of the Flory approach qualitatively agrees with the results of strict renorm-group calculation
[2]. The difference consists only in the non-concordance of the numerical values of some critical
indices (mi, ni, qi, $). This difference may be eliminated by elementary modification of the
formulae linking the size of the blob ~ with the parameters u, g and gli,. All the other intermediate
formulae remain unchanged. For simplicity we shall confine ourselves below to in practice the most
important case d = 3.
For networks of the first type instead of the second relation (11) one may use an analogous
expression [13]
~ _ a(B/a 3)0.16g0.45.

(29)

Passing to an analysis of networks of the first type, instead of the second, from the relations (15) it
is necessary to use the expression
(30)

~ Rlin (Bli n//lin 3 )0.16 glinO.45,

obtained by replacing in the expression (29) the parameters of the unit a, B and g by the
corresponding parameters Rlin, Blin and glin of the chain. The expressions for Blin and Rlin will differ
for short N < N * and long N~>N* chains. In the first case they are given by the expression (25) and
in the second by the relations
Bli n ~ Rlin 3,

Rlin ~ a(B/a 3)'2N'6.

(31)

The first of them corresponds to the second virial coefficient of a solution of solid spheres the
radius of which is equal to the size Rli n of the isolated chain in a good solvent [1, 14].
In conclusion, we give for comparison the numerical values of the critical indices obtained within
the Flory approach (first line) and refined scaling: for networks of the second type with N>>N*
(second line) and for networks of the second type with N < N * and of the first type (third line).
ml
-1.2
-1.7
-1.4

nl
-2.0
-2.9
-2.9

ql
-1.6
-2.3
-2.1

m2
-0.4
-0.6
-0.5

n2
-1.0
-1.3
-1.3

q2
-0.2
-0.4
-0.4

m3
-0.6
-0.6
-0.5

s
1.0
0.7
0.7

q3
-0.8
-0.8
-0.7

m4
1.2
1.7
1.4

n4
3.0
3.9
3.9

q4
0.6
1.3
1.1

Translated by A. CRozv
REFERENCES
1. P. DE GENNES, Idei skeilinga v fizike polimerov (Scaling Ideas in Polymer Physics) 368 pp., Moscow,
1982.

Swelling of polymer networks

689

2. S. V. PANYUKOV, Zh. eksp. teoret. 94: 116, 1988.

3. S. I. KUCHANOV, Protsessy studneobrazovaniya v polimernykh sistemakh (Processes of Gelation in
Polymeric Systems) Pt. 1, p. 61, Saratov, 1985.
4. S. V. PANYUKOV, Zh. eksp. teoret, fiz. 90: 169, 1986.
5. S. I. KUCHANOV, S. V. KOROLEV and S. V. PANYUKOV, Adv. Chem. Phys. 72: 115, 1988.
6. I. M. LIFSHITS, A. Yu. GROSBERG and A. R. KHOKHLOV, Usp. fiz. nauk 127: 353, 1979.
7. W. BURCHARD, K. KAJIWARA and M. GORDON, Macromolecules 6: 642, 1973.
8. G. R. DOBSON and M. GORDON, J. Chem. Phys. 43: 705, 1965.
9. A. Z. PATASHINSKII and V. L. POKROVSKII, Fluktuatsionnaya teoriya fazovykh perekhodov
(Fluctuation Theory of Phase Transitions) 381 pp., Moscow, 1982.
10. J. ISAACSON and T. C. LUBENSKY, Phys. Lettres 41: 469, 1980.
11. S. V. PANYUKOV, Pis'ma v ZhETF, 46: 472, 1987.
12. T. M. BURSHTEIN, A. M. SKVORTSOV and A. A. SARIBAN, Struktura rastvorov polimerov. Skeiling i
modelirovaniye na EVM (Structure of Polymeric Solutions. Scaling and Computer Modelling) Puschchino,
1981.
13. S. V. PANYUKOV and S. I. KUCHANOV, Tez. dokl. conf. "Sintez, struktura i svoistva setchatykh
polimerov" (Summaries of Reports to Conference "Synthesis, Structure and Properties of Network
Polymers") p. 12, Zvenigorod, 1988.
14. P. J. FLORY, Principles of Polymer Chemistry, N.Y., 1971.