Effect of molar size and solubility parameter of

solvent molecules on swelling of a gel: a

uorescence study
O

Pekcan* and M Erdogan

Department of Physics, Istanbul Technical University, Maslak 80626, Istanbul, Turkey
Abstract: Gels were swollen in various solvents with different molar volume V and solubility parameter
d. In situ steady state uorescence (SSF) measurements were performed for swelling experiments in
gels formed by free radical crosslinking copolymerization (FCC) of methyl methacrylate (MMA) and
ethylene glycol dimethacrylate (EGDM). Gels were prepared at 75C with pyrene (Py) as a uor-
escence probe. After drying these gels, swelling and slow release experiments were performed in
various solvents with different V and d at room temperature by time monitoring of the Py uorescence
intensity. The LiTanaka equation was used to produce time constant t
1
values. Cooperative diffusion
coefcients (D
c
) were measured and found to be strongly correlated to the molar volume of the solvents
used. Solvent uptake and degree of swelling were found to be dependent on the solubility parameter of
the solvent.
# 2000 Society of Chemical Industry
Keywords: uorescence; gel; solubility; molar volume; swelling
INTRODUCTION
The equilibrium swelling of gels in solvents has been
extensively studied.
13
The swelling kinetics of
chemically crosslinked gels can be understood by
considering the osmotic pressure versus the restraining
force.
48
The total free energy of a chemical gel
consists of bulk and shear energies. In fact, in a swollen
gel, bulk energy can be characterized by the osmotic
bulk modulus K dened in terms of the swelling
pressure and the volume fraction of polymer at given
temperature, whilst the shear energy which keeps the
gel in shape can be characterized by shear modulus G.
Here shear energy minimizes the non-isotropic defor-
mations in gel. The theory of kinetics of swelling for a
spherical chemical gel was rst developed by Tanaka
and Filmore
9
where the assumption was made that the
shear modulus G is negligible compared with the
osmotic bulk modulus. Later, Peters and Candau
10
derived a model for the kinetics of swelling in spherical
and cylindrical gels by assuming non-negligible shear
modulus. Recently, Li and Tanaka
4
have developed a
model where the shear modulus plays an important
role which keeps the gel in shape due to coupling of
any change in different directions. This model predicts
that the geometry of the gel is an important factor, and
swelling is not a pure diffusion process.
Several experimental techniques have been em-
ployed to study the kinetics of swelling, shrinking and
drying of chemical and physical gels, among which are
neutron scattering,
11
quasielastic light-scattering,
10
macroscopic experiments
12
and in situ interfero-
metric
13
measurements. Recently, we reported in situ
observations of solgel phase transition in free-radical
crosslinking copolymerization, using the uorescence
technique.
12,14,15
The same technique was also
applied for studying swelling and drying kinetics in
disc-shaped gels.
1618
In this work, swelling and slow release processes of
gels formed by solution free radical crosslinking
copolymerization (FCC) of methyl methacrylate
(MMA) and ethylene glycol dimethacrylate (EGDM)
have been studied. Pyrene (Py) is used as a uor-
escence probe to monitor swelling and slow release
processes during in situ uorescence experiments in
various solvents with different molecular sizes and
solubility parameters. In situ steady state uorescence
(SSF) experiments were performed for real-time
monitoring of swelling and slow release processes.
Our goal in the present work is to study the swelling
process in various solvents to determine the relation
between diffusion and solvent quality Cooperative
diffusion coefcients D
c
are determined and found to
increase from 3.610
5
to 6.910
5
cm
2
s
1
, de-
pending on the molar volume V of the solvent
molecule, indicating that the molar size of the solvent
molecule is strongly correlated to the diffusion in gels.
THEORETICAL CONSIDERATIONS
It is known that the kinetics of swelling of a polymer
(Received 4 February 2000; revised version received 6 June 2000; accepted 4 July 2000)
* Correspondence to: O

Pekcan, Department of Physics, Istanbul Technical University, Maslak 80626, Istanbul, Turkey
# 2000 Society of Chemical Industry. Polym Int 09598103/2000/$30.00 1641
Polymer International Polym Int 49:16411647 (2000)
network or gel should obey the following relation:
4
W(t)
W

= 1
X

n=1
B
n
e
t=t
n
(1)
where W(t) and W
?
are the swelling or solvent uptake
at time t and at equilibrium, respectively. W(t) can also
be considered as a volume difference of the gel
between the time t and zero. Each component of the
displacement vector of a point in the network from its
nal equilibrium location after the gel is fully swollen,
decays exponentially with a time constant t
n
which is
independent of time t.
Here B
n
is given by the relation
4
B
n
=
2(3 4R)

2
n
(4R 1)(3 4R)
(2)
where R is dened as the ratio of the shear and the
longitudinal osmotic modulus, R =G/M. The long-
itudinal osmotic modulus M is a combination of shear
modulus G and osmotic bulk modulus K (M =K
4G/3) and a
n
is given as a function of R as
R = 1

n
J
0
(
n
)
J
1
(
n
)

(3)
where J
0
and J
1
are the Bessel functions.
In eqn (1), t
n
is inversely proportional to the
collective cooperative diffusion coefcient D
c
of a gel
disk at the surface and is given by the relation
5
t
n
=
3a
2
D
c

2
n
(4)
Here the diffusion coefcient D
c
is given by D
c
=
M/f =(K4G/3)/f, f being the friction coefcient
describing the viscous interaction between the poly-
mer and the solvent, and a representing half of the disc
thickness in the nal innite equilibrium which can be
experimentally determined.
The series given by eqn (1) is convergent. The rst
term of the series expansion is dominant at large t,
which corresponds to the last stage of the swelling. As
seen from eqn (4) t
n
is inversely proportional to the
square of a
n
, where a
n
values are the roots of the Bessel
functions. If n>1, a
n
increases and t
n
decreases very
rapidly. Therefore, for kinetics of swelling in the limit
of large t or if t
1
is much larger than the rest of t
n
(ref
4), all high-order terms (n_2) in eqn (1) can be
dropped, so that the swelling and shrinking can be
represented by the rst-order kinetics.
13
In this case
eqn (1) can be written as
W(t)
W

= 1 B
1
e
t=t
1
(5)
Equation (5) allows us to determine the parameters B
1
and t
1
.
EXPERIMENTS
EGDM has been commonly used as crosslinker in the
synthesis of polymeric networks. Here, for our use, the
monomers MMA (Merck) and EGDM (Merck) were
freed from the inhibitor by shaking with a 10%
aqueous KOH solution, washing with water and
drying over sodium sulfate. They were then distilled
under reduced pressure over copper chloride.
The radical copolymerization of MMA (80%v/v)
and EGDM (1%v/v) was performed in toluene
(20%v/v) at 75C in the presence of 2,2'-azobisiso-
butyronitrile (AIBN) an initiator. AIBN (0.26wt%)
was dissolved in MMA and transferred into round
glass tubes of 9.5mm internal diameter. Py was added
as a uorescence probe before the gelation process
during sample preparation. Here the Py concentration
was 410
4
M. All samples were deoxygenated by
bubbling nitrogen for 10min, and then radical
copolymerization of MMA and EGDM was per-
formed. The reaction time was 35min. The monomer
(MMA), crosslinker agent (EGDM) and toluene were
purchased from Merck. The gels were not pre-soaked
in toluene to remove unreacted monomers, and up to
5%monomers may have been present in the gels at the
beginning of the swelling experiments. After the gels
had been formed and dried in vacuum for 1h at room
temperature, they were cut into discs to use in swelling
and slow release experiments. Four different solvents
with different molar volume and solubility parameters
were chosen for swelling experiments. Spectroscopi-
cally pure grade ethyl acetate (EA), chloroform (CH),
dichloromethane (DM) and acetone (AC) were
purchased from Merck and used as received. Charac-
teristics of solvents are listed in Table 1.
Steady state uorescence measurements were
carried out using a Perkin Elmer model LS-50
spectrouorimeter. All measurements were made at
the 90 position, and slit widths were kept at 10nm. In
Table 1. Characteristics of solvents
employed
Parameter
Solvent
Acetone (AC) Chloroform (CH) Dichloromethane (DM) Ethyl acetate (EA)
a
0
(cm) 0.130 0.185 0.070 0.135
a
?
(cm) 0.160 0.250 0.095 0.165
W
?
(g) 0.168 0.312 0.110 0.166
t
1
(s) 4700 9799 1168 9942
d (MPa
1/2
) 20.3 19.0 19.8 18.6
V (cm
3
mol
1
) 73.53 80.17 64.00 97.89
D
c
(cm
2
s
1
) 6.0410
5
4.0210
5
6.9010
5
3.5710
5
1642 Polym Int 49:16411647 (2000)
O

Pekcan, M Erdogan
situ swelling and slow release experiments were both
performed in a 11cm
2
quartz cell at room tempera-
ture. Gel samples were attached to one side of the
quartz cell by pressing the disc with thin steel wire.
The quartz cell was lled with AC, CH, DM and EA
for separate swelling and slow-release experiments.
This cell was placed in the spectrouorimeter and
uorescence emission was monitored at a 90 angle.
Two different experiments were carried out for two
different positions of the gel samples for each set of
experiment (see Fig 1). In both experiments, identical
disc-shaped gels were used which were dried cut from
the cylindrical gels obtained from FCC. The thickness
of these disc shaped gels was around 0.13cm. In the
rst position, only the gel was illuminated by the
excitation light and the total uorescence emission I
p
caused by Py molecules comes from the Py molecules
immersed in the gel and desorbed from the swelling
gel. In the second position, the gel sample was shifted
slightly upwards so that only the cell with solvent was
illuminated by the excitation light. Here the uor-
escence emission I
d
from Py molecules desorbed from
the swelling gel was monitored. Figure 1(a) and (b)
show the rst and second position of the gels,
respectively. These experiments were repeated for
each solvent.
During the experiments the wavelength of the
excitation light was kept at 345nm, and Py intensities
was monitored at 395nm using the time drive mode of
the spectrouorimeter. No shift was observed in the
wavelength of maximum intensity of Py and gel
samples remained transparent during the experiments.
Desorption curves of Py molecules were used to obtain
pure swelling curves by subtracting the intensities
taken fromsamples at the positions given in Fig 1(a,b).
In swelling experiments, continuous volume transi-
tions are expected and these should result in a con-
tinuous decrease in I
p
during swelling. Here, one may
expect that as solvent uptake (W) increases, desorption
of Py molecules from the swollen gel will increases,
and as a result, Py intensity in the rst position (I
p
) will
decrease. However, during slow release experiments
one should expect an increase in I
d
, due to the in-
creasing amount of Py molecules released into solvent
in the cell.
RESULTS AND DISCUSSION
Pyrene intensities in the rst and second position of
the gel versus time are plotted in Fig 2(a, b, c and d) for
AC, CH, DM and EA solvents, respectively. The
curves in Fig 2 were obtained during in situ uor-
escence experiments described in Fig 1(a, b), where at
the beginning all Py molecules are in the gel and I
os
is
obtained. After solvent penetration starts, some Py
molecules are washed out from the swollen part of the
gel into the cell; as a result Py intensity I
s
from the
glassy gel decreases as swelling time increases. At the
equilibrium state of swelling, the Py intensity from the
glassy gel reaches the I
?s
value, where the solvent
uptake by swollen gel is W. Aschematic representation
of these swelling stages is shown in Fig 3 where the
intensity from the desorbed Py molecules is repre-
sented by I
d
. The relation between solvent uptake W
and uorescence intensity I
s
from the glass part of gel
is given by the relation
W
W

=
I
os
I
s
I
os
I
s
(6)
Because I
os
I
?s
, eqn (7) becomes
W
W

= 1
I
s
I
os
(7)
This relation predicts that as W increases I
s
decreases;
it is quite similar to the equation used to monitor
oxygen uptake by poly(methyl methacrylate) and
polyvinyl acetate) spheres.
19,20
Combining eqns (5)
and (7), the following relation can be obtained
ln(I
s
=I
os
) = lnB
1
t=t
1
(8)
If one imagines that the uorescence intensity curves
I
p
in Fig 2 originate only fromthe gels, then eqn (8) has
to be obeyed by the data. However, during the swelling
experiments, desorbing Py molecules also contribute
to the uorescence intensity,
16
which prevents us
observing pure swelling curves as shown in Fig 3. In
fact, the I
p
data in Fig 2 represent the total Py intensity,
during in situ swelling experiments; the following
Figure 1. Fluorescence cell in LS-50 Perkin Elmer spectrouorimeter.
Monitoring of (a) swelling (the rst position) and (b) desorption (the second
position) processes of the gel explained in the text. I
0
is the excitation
intensity at 345nm, and I
p
and I
d
are the emission intensities at 395nm.
Polym Int 49:16411647 (2000) 1643
Fluorescence study of gel swelling
relations are operative at different times
t = 0 I
op
= I
os
I
od
t > 0 I
p
= I
s
I
d
t = I
op
= I
p
I
d
(9)
where I
d
is the Py intensity from the desorbing Py
molecules as shown in Fig 3. Plots of I
d
versus time are
shown in Fig 2 below each I
p
curve obtained from the
experiments performed according to Fig 1(b). In Fig
2, I
d
increases as the swelling and desorption time
increases for all samples. Because I
d
is directly
proportional to the number of Py molecules in the
solvent, the behaviour of the I
d
curves in Fig 2 suggests
that Py molecules are slowly released from the gels.
To produce the pure swelling intensity (I
s
) curves, I
d
data are subtracted from the I
p
data for each swelling
experiment according to eqn (9) for AC, EA, CH and
DM, respectively. To conrm the correctness of the
pure swelling curves, data were digitized according to
eqn (8) and are plotted Fig 4, where linear relations are
obtained except at long time-regions. Long time-
deviations are explained by saturation of solvent
uptake. The short time-deviation for the CH experi-
ment may correspond to fast relaxation processes in
the gel at an early swelling stage.
16,18
Using eqn (8), a
linear regression of curves in Fig 4 provides us with B
1
and t
1
values. Taking into account the dependence of
B
1
on R one obtains R values, and from the a
1
R
dependence a
1
values were produced.
4
Then using eqn
(4) for n =1, cooperative diffusion coefcients D
c
were
determined for AC, CH, DM and EA swelling
experiments. Experimentally obtained parameters t
1
and D
c
, together with the solubility parameter d
21
and
molar volume V,
22
are listed in Table 1, where a
0
, a
?
and W
?
values are also presented for AC, CH, DM
and EA experiments. Here one should note that
Figure 2. Total P
y
intensity I
p
, and intensity from desorbing Py molecules I
d
, versus swelling and desorption time for the gel samples swollen in (a) AC, (b) CH,
(c) DMand (d) EA. The gel in the cell was illuminated at 345nm(at the rst position) during I
p
measurements; I
d
intensities were measured at the second position.
1644 Polym Int 49:16411647 (2000)
O

Pekcan, M Erdogan
Figure 3. Schematic representation of
the swelling processes in the gel during
solvent uptake. Fluorescence
intensities from Py molecules are also
presented:(a) gel before swelling where
I
os
is the uorescence intensity from
glassy gel at t =0;(b) swollen gel in
which I
s
and I
d
present the uorescence
intensities from glassy gel and
desorbed Py molecules at t >0 and W
is the solvent uptake;(c) highly swollen
gel where I
?s
and I
?d
are the
uorescence intensities at t =? and
W
?
is the solvent uptake at t =? (here
I
p
represents the total Py intensity).
Figure 4. Linear regression of the I
s
data according to eqn (8). B
1
and t
1
values were obtained fromthe intersections and slopes of the plots in (a), (b), (c) and (d)
for the gels in AC, CH, DM and EA, respectively.
Polym Int 49:16411647 (2000) 1645
Fluorescence study of gel swelling
measured t
1
and D
c
values are found to be strongly
dependent on the molar volume V of the solvent and
not on the solubility parameter d.
It is important to note that penetration of solvent
molecules into gel substantially depends on the
hydrocarbon employed. Now the challenge is to
determine whether kinetic effects associated with the
solvent viscosity Z or thermodynamic effects (poly-
mersolvent interactions) are responsible for the
swelling of the gel. No correlation has been found
between Z and t
1
values. Here it is convenient to test
whether the solvent quality ie polymersolvent inter-
action, is responsible for the swelling processes or not.
Solution theory predicts that the polymersolvent
interaction parameter w is related to solubility par-
ameter d and molar volume V via the relation
23
w =
V
RT
(
p
)
2
(10)
where R is the gas constant, T is the temperature and
d
p
is the solubility parameter of the polymer. It is seen
in Table 1 that there is strong correlation between t
1
and V, ie it takes longer for a larger molecule to
penetrate into the gel.
When the network is swollen by absorption of
solvent, the chains between network junctions are
required to assume elongated congurations, and
exert a force akin to the swelling process. As swelling
proceeds, this force increases and the dilution force
decreases. D
c
is the measure of the force of retraction
in a stretched network structure. Here, as the gel swells
faster (small t
1
), a higher force of retraction is applied;
as a result D
c
values increase as in DM. However, slow
penetration of solvent molecules into the gel result in
smaller D
c
values as in EA. In Fig 5, D
c
is plotted
versus V, where a strong correlation between these
parameters is seen. In Fig 6(a, b), the variation in the
nal (a
?
) and initial (a
0
) disc thickness (a
?
a
0
) and
the nal solvent uptake (W
?
) are plotted versus
solubility parameter d of the solvents. It is seen that
there is correlation between these parameters, ie as
(dd
p
) approaches zero, (a
?
a
0
) and W
?
values
present increase (where
p
=18.57 MPa
1/2
was taken
for PMMA). From here one can conclude that solvent
uptake is strongly correlated to the polymersolvent
interaction parameter w. In other words, for the best
solvent (CH), the degree of swelling of the gel is
largest.
Here, the basic conclusion can be reached that the
swelling process of gels is associated with the thermo-
dynamic effects, ie polymersolvent interactions,
where both the molar volume V and the solubility
parameter d play important roles in the process.
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?
a
0
) and (b) W
?
versus solubility parameters d of
solvents AC, CH, DM and EA.
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Polym Int 49:16411647 (2000) 1647
Fluorescence study of gel swelling