Eur. Polvm. J. Vol. 20, No. I, pp.

61 64, 1984

0014-3057/8453.00 +0.00
Copyright ;C 1984 Pergamon Press ktd

Printed in Great Britain. All rights reserved

STUDIES ON BOUND WATER IN

POLY(VINYL ALCOHOL)
HYDROGEL

BY DSC AND

FT-NMR

T. HATAKEYEMA and A. YAMAUCHI

Research Institute for Polymers and Textiles, 1-l-4, Yatabe-Higashi Tsukuba, Ibaraki 305, Japan
H. HATAKEYEMA
Industrial Products Research Institute, 1-l-4, Yatabe-Higashi Tsukuba, lbaraki 305. Japan
(Received 18 March 1983)
A b s t r a c t - - T h e phase transition of water bound in poly(vinyl alcohol)(PVA) hydrogel was measured by

differential scanning calorimetry. The cross-link density calculated from the swelling ratio of PVA
hydrogel ranged from 3 x 10 -~ to 1 z 10 3 according to the total dose of 6Co 7-ray irradiation. From
the enthalpy of melting, it was tbund that water in PVA gel can be classified into at least three groups;
ca. I 1.5 tool non-freezing water, 5-6 tool freezing bound water, and the rest free water, corresponding
to each hydroxyl group of PVA. The characteristic properties of polymer hydrogel were attributed to the
large number of molecules of freezing bound water in the network. The amount of free water depended
markedly upon cross-link density; however, it was not apparent in PVA gel with cross-link density
>2.0 x 10 ~. The decreases in the nuclear magnetic resonance relaxation times of water and PVA were
related to the cross-link density and were found to level off at a cross-link density 2.0 x 10-4.

INTRODUCTION

EXPERIMENTAL

The interaction o f water with polymers having hydrophilic groups has been studied in the light o f various
concepts and using various experimental techniques
[1 13]. The different states o f " a s s o c i a t e d " or
" b o u n d " water have been distinguished from "free"
or " o r d i n a l " water. A m o n g the various techniques
used in measuring the interaction o f water with
polymer, we have extensively used differential scanning calorimetry (DSC) [9, 10, 14-16]. This technique
has enabled us to calculate quantitatively the a m o u n t
o f " b o u n d " water from the enthalpies o f melting and
crystallization o f water associated with polymer. We
have investigated the interaction o f water with polymers such as poly(hydroxystyrene) and its derivatives
and celluloses [9, 10, 14, 15]. A l t h o u g h these polymers
are water insoluble, they adsorb a certain a m o u n t o f
water. It is interesting to c o m p a r e the b o u n d water
held in a polymer gel with that a d s o r b e d in linear
polymer. Woessner et al. investigated N M R relaxation times o f water in agar-gel and pointed out that
the m o v e m e n t o f most o f the water molecules is
unaffected by the presence o f the agar molecules [1].
A small fraction o f water molecules ( < 1')o in a 10')/o
agar-gel) interact strongly with gel molecules [17].
W e s t m a n et al. interpreted the density data o f cellulose hydrogel in terms o f the two-state model o f gel
water in their series o f papers on cellulose gel [18-21].
In this study, we have chosen poly(vinyl alcohol)
(PVA) cross-linked by 6Co 7-ray irradiation, as it
represents a typical polymer gel. Properties o f water
in this gel were studied by differential scanning
calorimetry (DSC) and pulsed nuclear magnetic resonance spectroscopy ( N M R ) .
61

I. Material

Pure PVA powder with degree of polymerization of 2000

was obtained from Wako Chemical, Tokyo. PVA powder
was dissolved in distilled water and 7 wt')o solution was
obtained after dialysis according to procedures reported
previously [22]. PVA solution was filtered through a l0/~m
millipore filter and then placed in an autoclave, and heated
at 120C for 1 hr. A fixed volume of solution was put into
a glass tube and degassed under vacuum (10 SmmHg)
several times, and then sealed. A PVA solution in a glass
tube was irradiated with ~Co f-ray at a dose rate of 0.170
or 1.071 Mrad/hr for periods ranging from 7 to 18 hr. After
irradiation, the gels were weighed. Concentration (C) and
swelling ratio (SR) of the gel were defined as follows:
C = (weight of dry PVA)/(weight of water) x 100 (',,) (1)
SR = (weight of gel)/(weight of dry gel) x 100 ('~i) (2)
The exact content of PVA in the gel was determined by
weighing after heating at 150'C in vaeuo (10 2mmHg) in a
drying oven or by thermogravimetry.
2. Methods
Thermal analysis. A Perkin-Elmer model DSC-II
differential scanning calorimeter, equipped with cooling
apparatus, was used. The measurement of the melting and
crystallization of water in the gel was carried out as follows:
3~, mg samples of the PVA aqueous solution were sealed in
pans used for volatile samples, which had been treated in an
autoclave with a small amount of water at 120'C in order
to eliminate the reaction of water with the aluminium
surface during heating runs. The samples were kept at 395K
for 5 min to eliminate the effect of thermal history and then
quenched or cooled at a pre-determined rate to 200K.
Subsequent to cooling, the samples were heated to ambient
temperatures at the rate of 5K or 10K/min.

T. HATAKEYEMAet al.

62

A Rigaku--Denki thermogravimeter model TG equipped

with an i.r. ray heater was used to measure the evaporation
of water from the gel. The sample was placed in an open AI
cell and heated at the rate of 10K/min in a stream of N2.
Curves of weight loss and their derivatives were recorded
simultaneously.
Pulsed nuclear magnetic resonance spectroscopy. Proton
spin relaxation times were measured with a Nicolet NT-200
WB pulsed spectrometer, equipped with an NIC 1180
computer data system with a double-disk drive. The longitudinal (T0 and transverse (T2) relaxation times were measured at 200MHz. Tfs were measured by the 180-T-90
degree pulse technique. Tt values were obtained according to
the method suggested by Levy et al. [22] to correct for
nonhomogeneous magnetic fields which could produce incomplete inversion of the 180-degree pulse. T[s were obtained by the Carr-Purcell-Meiboom-Gill method. The
relaxation times were the mean of at least two separate
determinations. The temperature during all NMR experiments was 20 ___IC.
RESULTS AND DISCUSSION
Figure 1 shows the relationship between the swelling ratio and total dose applied to produce gelation.
The swelling ratio depends on the dotal dose not on
the dose rate, as shown by a curved line in Fig. 1. We
neglect the effect of dose rate on properties of each
gel in the following discussion. F r o m the swelling
ratio, we can obtain the cross-linking density (1/MJ
of polymer gel. We used Flory's simple equation [23]
for the calculation of 1/~/( as shown below, although
Peppas et al. [25, 26] proposed a modification of
Flory's equation in their reports on PVA gel
1

~ (ln[1 - v2,j + v~ + Xv2,~)

~=~"

f,,,/3_v_~)

(3)

where M~ = 8.8 x 10, V~ = 18, v = 0.788, X = 0.494,

according to Sakurada [24] and V2.s= final swollen
equivalent polymer volume fraction calculated from
the swelling ratio.
Figure 2 shows DSC melting curves of water
involved in PVA gel, as a function of the cross-linking
density (1/)1~). The melting pattern of ice in each gel
is complicated; two main peaks with several small
shoulders are observed. These small shoulders were
12

--

Dose rate
Mrod/hr

/300
J

280

Fig. 2. DSC melting curves of water in gel having various

cross-link densities (l/A~c).
affected by the repeated heating and cooling during
DSC runs. However, the pattern of main peaks and
peak temperatures did not vary with the thermal
hysteresis. As seen in this Figure, peak temperatures
of melting (Tp) and starting temperatures of melting
(T0 shift to lower temperatures as 1/Me increases. The
peak observed at the same temperature as pure water
was designated as Tpl, and that observed at a temperature lower than Tpl, as Tp2.
Figure 3 shows temperatures, Tp~, and Tp2 and Tf,
as a function of 1/~tc. The Tp~ peak disappeared at
about 1 / ~ c = 2.0 x 10 4 and the Tf peak dropped
discontinuously at the same 1 / ~ t value.
The peak area of the DSC melting curve was
converted into the enthalpy of melting using the peak
area of melting of a sample of pure water of known
weight. We neglected the possible polymorphism of
ice, using 334 J/g in the calculation of enthalpy. As
shown in Fig. 2, the melting curve can be divided into
two parts. However, exact separation of the melting
curves is difficult, since an asymmetric pattern is not
applicable for fitting by Gaussian, Lorentzian or
other distribution functions. Therefore, we adopted a
hypothetical approximation by assuming that the
peak area observed at a temperature > 273 K could
be attributed to free water and the rest of the area to
the b o u n d water. This assumption was based on a
report that two types of freezable water discontinuously existed in polymer gel [1]. This was also
supported by the previous studies of the b o u n d water
adsorbed on linear polymers [9, 10, 14].
By subtracting the weight calculated from the
enthalpies of free (Wfree) and b o u n d water (Wbou,d)
from the total weight of PVA gel (W0, we estimated
300

.9
- 8
E

280

ee

--

(D

3=

o3

4
--

"

"
L

I
0

20

I
40

i
60

Total dose (Mrad)

Fig. 1. Relationship between the swelling ratio and total

irradiation dose for a 7% PVA solution.

a4o

T,

10-4

10.3
I/'~c

Fig. 3. Relationship between temperatures of melting peak

(Tpl and Tp2) and starting temperature of melting (Tf) and
cross-link density (1/.~/c).

Studies on bound water in PVA

3O

g
o
E
20

IK

o
E
<

LO

- _ _ ~ o . ~

0
10-4

10-3

p/,E,~

Fig. 4. Amount of water attached to each monomer unit of

PVA as a function of cross-link density (1/~,).
the weight of non-freezing water (Wno,-freezi,g)as follows:
~ / t - - ( m b o u n d -~ mfree ) =

When-freezing

(4)

We have classified the summation of Wbo,,d and

Wo,,n_fr~e~,,gas a kind of total bound water which is
affected by the polymer.
Figure 4 shows the moles of water corresponding
to free, bound and non-freezing per monomer unit of
PVA. Here, we calculated the number of water
molecules (Mol) using the following equation;
44 (Weight of each class of water)
Mole = - x
(5)
12
(Weight of dry gel)
where 18 and 44 represent the molecular weights of
water and the monomer unit of PVA, respectively.
The amount of free water decreases rapidly as 1/~/,
increases and disappears at 1/M~ = 2 x 10 -4. In contrast, the non-freezing water remains at 1-1.5 molecules, over the whole range of l/&~ examined. The
value is similar to that reported by Katayama et al.
[27] who estimated the number of molecules of
non-freezing water in polyacrylamide gel to be 1-2,
from NMR measurements. The number of bound
freezable water molecules is 5-6 in 1/#c region where
the free water is found. This number decreases in the
region where 1/~, is > 2 10 -4. This value can be
defined as the "critical point" of cross-link density
affecting the structure of water.
2.00

J50

I.O0

0.50

--

0.20

--

015

--

0.10

--

0,05

10 - 4

i0 -3
I/M c

Fig. 5. Relationship between spin-lattice (T0 and spin-spin

relaxation times (T2) and cross-link density (l/h,Scc).

63

The spin-lattice relaxation (7"1) and the spin-spin

relaxation (T2) times are shown in Fig. 5 as a
function of 1/Me. The T~ value (ca. 0.9 sec) of water
bound in the gel having the l/M,. value of the critical
point (Me = 4.0 103) corresponds to about 1/4 of
that of pure water. Theoretically, if the cross-link
density of the gel was sufficiently large, as reported
previously [1], the T~ value could be expected to
decrease at first with increasing 1/M'c and then to
increase after reaching the minimum value. However,
the l/M"c region dealt with in this experiment seems
too small to have such a minimum value of/'1. The
value decreases with increasing 1/.4/7, as expected.
As reported previously [10, 16], the mean number
of molecules of non-freezing water associated with
linear polymer was found to be 0.7 to 1.5. On the
above estimation, the crystalline region of polymer
matrix was neglected assuming that water molecules
diffuse only in the amorphous region of polymer. The
fact that the number of molecules of non-lYeezing
water in PVA gel is 1-1.5, independent of the density
of cross-linking, suggests that the non-freezing water
in polymers is not affected by the higher order
structure of polymers. Short range interactions, such
as hydrogen bonding, leading to the association of
water molecules with particular groups of the polymer, seems to be the main factor in determining the
number of non-freezing water molecules.
The free water was not observed in polymer gels
having M smaller than the critical value
(Me = 4 103). This corresponds to a degree of polymerization ca. 87 and a chain length of 260A,
assuming the molecular chain is fully extended. Of
course the molecular chains are entangled randomly
in the real polymer gel and the cross-linking distance
is far less than this value.
The amount of freezing_bound water is almost
constant regardless of 1/Mc, when the free water
coexists in the gel. The number of moleules of bound
water, 5 6, is large when this value is compared with
that for linear polymer, 0.1 to 0.2. Therefore, it is
reasonable to consider that the three dimensional
structure of the polymer chain affords a space where
water molecules are assembled and crystallized. The
water in the space is affected by the neighbouring
non-freezing water which directly interacts with the
hydroxyl groups of PVA. Irregularity is necessarily
introduced into the crystalline lattice. The ice of
bound water is in an unstable state. That 7~. is lower
than 273 K suggests that this ice does not have the
hexagonal packing of ordinal ice. It is noticed that the
enthalpy of melting bound ice should be lower than
that of ordinal ice if we consider the irregular structure of this ice, and therefore, it is inappropriate to
use 334 J/g for the calculation of enthalpy. However.
at present we have no direct method of isolating the
bound ice captured in the polymer network. The
number of water molecules (mole number) may inevitably have a certain error owing to the above method
of calculation.
We conclude that water in the PVA gel can be
classified into at least three types: ca. t - l . 5 m o l
non-freezing water, 5-6mol freezing bound water
and the rest free water, corresponding to each hydroxyl group of PVA. The characteristics of polymer
hydrogel are attributable to the large number of

T. HATAKEYEMAet al.

64

molecules o f freezing b o u n d water in the network.

The a m o u n t o f free water depends m a r k e d l y o n
cross-link density.

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