Nature of Water in Synthetic Hydrogels

I. DUatometry, Specific Conductivity, and Differential Scanning

Calorimetry of Polyhydroxyethyl Methacrylate
H A I B A N G L E E , M U S H I K JHON,* J O S E P H D. A N D R A D E ~
Department of Materials Science and Engineering, University of Utah, Salt Lake City, Utah 84112
Received June 11, 1974; accepted December 30, 1974

Three classes of water may exist in certain hydrogels. We have previously labeled these
as X water (bulk water), Z water (bound water) and Y water (intermediate forms we call
interracial water). Bulk gel conductivity data for poly (2-hydroxyethyl methacrylate)
(PHEMA) were obtained. The activation energy for specific conduction was calculated.
A plot of the activation energy versus wt percent of water in the gel clearly indicated three
different zones, showing three possible classes of water in the gels. These results were con-
firmed by thermal expansion measurements. The high water content gels (50%) demon-
strated an extremely sharp volume change at 0C, indicating the presence of normal bulk
water. Lower water content gels (20%) showed no anomalous change in thermal expansion,
indicating that the water is bound. The medium water content gels exhibited intermediate
behavior. A semiquantitafive analysis of the three classes of water is presented. A further
verification of these results was obtained by differential scanning calorimetry (DSC) studies.
The low water content gel (20%) consists mainly of bound water, which exhibited no phase
transitions over the range - 1 5 to 24C. The high water content gels showed phase transi-
tions near 0C. The medium water content gels show gradual shifts of the phase transition
temperatures near 0C.

INTRODUCTION groups according to their experimental data

There is substantial interest in the develop-
ment of synthetic hydrogels for biomedical
applications (1-3). There has been some
interest in the possible correlation between the
nature of water in hydrogels and their bio-
medical properties (2, 3). As the blood com-
patibility of hydrogels is not necessarily a
simple function of gel water content (2, 3),
it is reasonable to suspect that the nature of
water in the gels and at the gel interface m a y
be important (3).
Drost-Hansen (4) has discussed a three
layer model for the structure of water near
certain water/solid interfaces. Aizawa el al.
(5-7) have proposed that water in natural
macromolecular gels be classified into three
* On leave from the Korea Advanced Institute of
Science, Seoul, Korea.
t To whom correspondence should be addressed. I ~ ( H E M A ) was obtained (Trans Chemic Indus-
from specific conductivity, dilatometry and
N M R measurements. Krishnamurthy et al. (8)
have indicated the existence of three states of
water in membranes of cellulose acetate by
N M R studies.
We have also suggested that hydrogels m a y
contain three classes of water: X water (bulk
water-like), Z water (bound water-like) and
Y water (intermediate forms which we have
chosen to call interfacial water) (9). To check
the validity of the hypothesis, dilatometric,
specific conductivity, and differential scanning
calorimetry (DSC) studies have been carried
out from --15C to room temperature for
poly(hydroxyethyl methacrylate) ( P H E M A )
gels of various wate~ contents.
MATERIALS AND METHOD
Commercial 2-hydroxyethyl methacrylate

225
Copyright ~ 1975 by Academic Press, Inc. Journal of Colloid and Interface Science, Vol. 51, No. 2, May 1975
All rights of reproduction in any form reserved.
226 LEE, JHON AND ANDRADE

-- (1/S)QHgVHg24(t -- 24)}(S/M~), [2]

..''"
5
where A~Hg is the specific volume change of
o the mercury and A(bgel is the specific volume
change of the gel ; h and h are the height of the
x mercury column at the temperature t and
-IO 24C (the reference temperature), respectively;
-IS
S is the capillary cross sectional area (cm~);
QH, is the thermal expansion coefficient of
-20
mercury (13); VH~4 is the volume of the
Temperature (C) mercury in the dilatometer at 24C; and M,
is the mass of the sample. The data are re-
FIG. 1. The specific volume change A4,~X 103
producible within + 2 % .
(cma/g) versus temperature (C) for a 20% water
PHEMA gel.
B. The Specific Conductivity
tries, Inc., New York, N. Y.) and used as
received. The impurity content was 0.5% free The specific conductivity was measured with
acid and 0.3% diester. One percent by weight an impedance bridge (Electro Scientific Indus-
of ethylene dimethacrylate (EDMA) cross try, Inc. Model 291B), using a 1000 Hertz AC
linker was added unless otherwise noted. The signal. The use of alternating current avoids
redox initiator used was 10-3 mole of Na2S:Os polarization of the electrode in the conduction
and of (NH4)2S20~ (10-12). The monomer cell (14, 15). The design of the cell and other
was dissolved in the desired amount of distilled experimental details are available (15). Plati-
water, and the solution was polymerized in a num foil (A. D. McKay Co., New York) was
60C water bath for one hour. The impurity used for electrodes; the electrodes were not
levels present did not significantly affect the platinized.
physical properties discussed here. The gels
thus contained the amount of water present C. Differential Scanning Calorimetry
in the original monomer solution. They were The transition points of water in the gels
not equilibrated with water. A constant were determined with a Perkin-Elmer DSC-1B
temperature circulator with +0.02C control differential scanning calorimeter. The sample
accuracy was used as a temperature bath for (20 to 30 rag) was cooled from room tempera-
both specific conductivity and dilatometric ture to --20C at cooling rates of 1.25C/rain,
studies. Equilibrium temperatures were ob-
tained after equilibrating the gels for three
hours for each measurement.

A. Dilatometric Measurements
,a
The dilatometer (5) was filled with the ~_o-5
sample and mercury. Thermal expansion
~, -I0
measurements were determined at tempera-
~3
tures ranging from --15C to 24C. The total -15
volume change, A~tot, is given by the following
-20
equations (5) :
Temperature (*C)

FIG. 2. The specific volume change A,I,gX 10~

A~g~1 = A~tot - - AqPHg, (cm~/g) versus temperature (C) for a 25% water
= { (h - h o) PHEMA gel.
Journal of Colloid and Interface Science, Vol. 51, No. 2, May 1975
 NATURE OF WATER IN HYDROGELS 227

l0 ~ - - - - "--~1 1 r- i ~ - - F ' -

.90
~_o-5
x
g -10
,O,
(3 <1
-15 -15

-20 -20

-115
_1
-I0
I
-5
_ I
0
I
5
I_
I0 115 2~ 215 _,; _,; -5
,
o
,
5 ,; ,'~ io ;5
Temperature(C) Temperature (*C)

FIG. 3. The specific volume change M% X 103 FIo. 4. The specific volume change h%. X 103
(cm~/g) versus temperature (C) for a 30% water (cm3/g) versus temperature (C) for a 40%' water
PttEMA gel. PHEMA gel.

involves a volume change of --8.27% (16) or

2.5C/min and 5C/rain for the various
--91.1 X 10-3 cm 3 g-1 at 0C.
P H E M A gels. Scanning speed had no signifi-
These dilatometric studies suggest that
cant effect on the temperature of transition.
three general states of water m a y exist in
Heating curves were also obtained and some
hydrogels and that the transition temperature
hysteresis was noted (15).
of X water is 0C (Figs. 4 and 5), that of Y
water may range from --15 to 0C and Z
RESULTS water shows no transition over the range from
A. Dilatometric Measurements --15 to 24C (Fig. 1). The data indicate the
P H E M A network contains about 200-/0 of
The specific volume change of the gel, Ao, bound or Z water. If we make the assumption
was obtained from the dilatometry measure- that the transition near 0C is due mainly to
ments by Eq. [-2]. Hysteresis in thermal nonbound or X water, then the amount of
expansion of the P H E M A gels from --15 to normal or X water and interfacial or Y water
24C is shown in Figs. 1 to 5. The specific in the gels can be determined from Eqs. [-3-]
volume for each gel decreases upon cooling. and [-4] :
The gels containing 25% or more water (Figs. X ' ~ (Aqs,el/A~)-100 [-33
2 to 5) showed a hysteresis in thermal expan-
sion over the temperature range of --15 to 20 t i i i i i J i i

24C. One sees that the 20% water gel shows

no transition (Fig. 1), probably indicating that
most of the water is "bound" (Z water).
The 250-/0 water gel shows a slight hysteresis,
the heating path discontinuously joining the
cooling path in the vicinity of 0C (Fig. 2). 2 0
The hysteresis increases as the water content
of the hydrogel increases (Figs. 3 and 4). The 4 .5f
-10
hysteresis is most pronounced in the high water
content hydrogel (50% water). The extremely 15 .115
t
-lO -5
I
0
I I
5 IlO 115
f
20
I
25
sharp specific volume change near 0C for the Temperature(QC)
higher water content gels (40% and 50% FIG. 5. The specific volume change Aq,o X 103
water) is probably due to "normal" water (cm3/g) versus temperature (C) for a 50% water
(X water). The transition of ice to water PHEMA gel.
Journal of Colloid and Interface Science, Vol. 51, No. 2, May 1975
228 LEE, JHON AND ANDRADE

TABLE I -5.00 ~ - t ~- i J J I~---

APPROXIMATE CONTRIBUTION OF " X , Y, AND Z " WATER I

TO THE TOTAL WATER CONTENT (W) -350 ~ 2
oF P~E~A GELS
(ALL VALUES ARE Wt. %) -4.00 ~ 3
4
W 20 25 30 40 50 -4.50 Y 5
X 0 0 0 8.3 18.4
Y 0 5 10 11.7 11.6
Z 20 20 20 20 20

and
Y _W- X - Z, [43
where X is the percentage of normal water in
3 o 3.4o 350 ~.6o 3.70 3.so
the gel; AcI,~ is the volume change of ice to
I/T x IO3
water at 0C; Y is the percentage of interracial
water in the gel; W is the total percentage of FIe. 6. Specific conductivity versus reciprocal tem-
water in the gel; and Z is the percentage of perature for PHEMA hydrogels as a function of
water content. 1 = 70, 2 = 60, 3 = 50, 4 = 40, 5 = 30,
bound water in the gel. The amount of " n o r m a l " 6 = 20% H20.
water in the gel was obtained using Eq. [.3]
with A~g~z values taken from Figs. 4 and 5 and
Plots of specific conductivity versus tempera-
AO~. value from Ref. (11). Also the amount of
ture for P H E M A gels of different water
interracial water was obtained using Eq. [.4],
contents are presented in Fig. 6. Log K is
assuming that 20% of the gel was bound
linearly proportional to 1/T for temperatures
water. The results are shown in Table I, where
higher than the transition temperatures. Cne
the amount of interracial water appears to
can obtain the apparent activation energy for
reach a near constant value for gels of 40 to
specific conduction for each different gel (Fig.
50% water content.
7) from the slope of the straight lines in Fig. 6.
There is apparently no bulk or normal water
One can analyze Fig. 7 in terms of three classes
in the gel until the m a x i m u m interracial (Y)
of activation energies (5-7) which m a y corre-
water content is reached; after that point all
spond to the activation energies of " n o r m a l "
additional water in the gel behaves as bulk or
X water.
i i ,

B. Specific Conductivity 6c
According to absolute reaction rate theory, ~o

the specific conductivity, K, can be written -~

as follows (6, 17). ~"~
:~ 40

K = const {z(Ne)2/Wh} exp (--AEa/er), [-5]

30
where z, N, e, R, AEa, and h are ionic valence,
Avogadro's number, electronic charge, gas 2o

constant, activation energy, and Planck's I I I I I I

20 5Q 40 50 60 70
constant, respectively. Equation [.5-] can be H20,o
rewritten as (6, 17),
FIo. 7. Activation energy for conductivity versus
log K = c o n s t - (AEa/2.303RT). [.6] water content for PHEMA hydroge]s.
Journal of Colloid and Interface Science, Vol. 51. No. 2, M a y 1975
 NATURE OF WATER IN HYDROGELS 229

water (X water), that of "bound" water (Z bound water, perhaps with ice-like behavior,
water), and that of Y water. A sharp dis- while in the high water content gels it is
continuous change in the log K vs 1/T curve largdy determined by nonbound water with
near 0C indicates that the high water content normal water behavior. Because the ion
gels (1-4 in Fig. 6) have significant amounts mobility in ice (18) is small in comparison to
of "normal" or X water. that in water, the contribution of bound water
Even though 10-3 mole of initiator salts were to the conductivity in the latter case may be
used for polymerization of monomer, the acti- very small.
vation energy value, 2.7 Kcal/mole for gels We are aware of the controversy in the
of 60 to 70% water content in Fig. 7 is of the literature on proton and ion mobility in ice
same order of magnitude as the activation (22). The arguments presented above are
energy for proton transport in aqueous solu- largely qualitative in nature and are given
tions, 2.5 to 2.8 Kcal/mole (18). merely to show that the concepts of bulk,
The general expression for the ionic conduc- bound, and intermediate water in gels are
tivity (19) in water and ice is reasonable with respect to conductivity data.
Even though the exact nature of the charge
~i = nzeU~ = Cie-A~"ll~r, 1-73
carriers in the gels are not known (protons,
where a~ is the ionic conductivity; i is 1 or sodium ions, and ammonium ions are probably
2 referring to water and ice, respectively; predominant), the qualitative argument given
n is the number of charge carriers; Ui is the above is valid whether we consider protons
ion mobility, and C~ is the constant. Therefore, (U1/U2 ~ 104) or small univalent ions (U1/U2
>~ 1@). More direct methods are available to
0"I U1
quantitativdy determine the classes of water
~z Us in hydrogels (15, 23).
C1
= - - e(AEa)$--l/Rr, E83 C. Differential Scanning Calorimetry (DSC)
C~
The thermal behavior of hydrogels due to
where (&Ea)2_l= AEa2--&Eal. The fre- physical or chemical changes during heating
quency factors, C1 and C~ are approximatdy or cooling can be studied by DSC. DSC curves
equal because the fundamental vibration fre- directly give the heat evolved or absorbed
quencies of ice and water (16, 20, 21) are during a phase transition, thus permitting a
almost the same; the volume change from ice direct thermal analysis (24). The endo-
to water should not significantly affect C~. thermic energy (cal/sec) as a function of
Equation [-83 can be written as: temperature is presented in Fig. 8 for 5 gels
Ut/U2 = 103'~ e (~E")2-1mr, of different water content, pure water, and a
sample of 60% water gel in contact with pure
because the proton mobility in water, U1, is of water. One sees that no change is detected
the order of 103 times higher than in ice, Us in the 20% water gel, confirming that most of
(18). The ion mobility ratio is probably the water must be "bound" or Z water. The
greater than 104 (18). The activation energy other gels (above 20% water) show a definite
difference between gels with 20% water and phase change below 0C on cooling, and it is
60% water, as given in Fig. 7, is 4 Kcal/mole interesting to see that the transition tempera-
which is near the value of 4.1 Kcal/mole for tures shift upwards toward 0C as the water
the activation energy difference for proton content of the gel increases. Pure water shows
transport between ice and water. This fact the expected sharp transition at 0C. To
suggests that in the low water content gels determine the effect of cross-linker in PHEMA
the conductivity is largely determined by gels, the monomer solution was also polymer-
Journal of Colloid and Interface Science, Vol. 51, No. 2, May 1975
 230 LEE, JHON AND ANDRADE

ized without adding cross-linker. The other

T -~/--
~ - - ~ - - - -- -
@ 20% Water
30% Water
40% Water
conditions were the same as described in
experimental procedures. The DSC data are
shown in Fig. 9.
~ 5 0 % Water The transition points of gels with cross-linker
I--
@ @ 60/ Water were at lower temperatures than those of the
V"- /~ 100% Water (Pure Water)
La-
(g) 60% Water gel+ I00% gels without cross-linker. This shift may be
Water (TwoPhase due to the differences in the amounts of the
System)
three classes of water in these gels.
I-
DISCUSSION
LL/
Our results are in qualitative agreement
with those of Aizawa et al. on agar gels (5, 6),
and of Baresova (25) on polyhydroxyethyl
UJ methacrylate gels. Our data provide evidence
that various forms of water exist in P H E M A
hydrogels. The water probably consists of a
fraction which is significantly affected by the
TEMPERATURE (C) polymer network (Z water), a fraction rela-
tively unaffected by the network (X or normal
FIG. 8. DSC thermograms for PHEMA (1% cross water), and an intermediate fraction (Y water).
linker added) hydrogels of different water contents,
for pure water, and for a 60% water gel/'pure water The Y fraction appears to reach a limiting value
system. of about 12% of the total gel. The X fraction
increases with increasing water content above
35 to 40% water.
, , (~)'
I --Y-- P H E M A gels are observed to be complex
systems with regard to the role of water, as
@--'~ ~- @ 20% Water well as with respect to their network structure
o t ] (b) 30% Water (10, 11, 26-28). The homogeneity of the gels
@ 40% Water
@ 50% Water depends on the concentration of water in the
~
o (e~ 60% Water starting mixture. The polymerization process
@ /J (~ I00% Wate~(PureWater)
(~ 60% Woler get+ 100%
yields either a homogeneous and optically

V Water (Two Phase

System)
clear gel (up to about 40 wt. % water in the
starting mixture), or a heterogeneous, turbid
gel if the initial water content exceeds about
40wt. %.
It is generally believed that P H E M A gels
of 40% water or less are homogeneous systems
(10, 11,26-28), while such gels containing
over 40% water are heterogeneous, possibly

1
-20 -16 -t2 -8 -4 0 4
two-phase systems exhibiting "microsyneresis"
(27, 28) and thought to have a "micro-
mesomorphic" .Structure (29). At water con-
TEMPERATURE (C) tents of about 40% or less, the polymer
network does not exhibit a microphase sepa-
Fla. 9. DSC thermograms for PHEMA (no cross
linker added) hydrogels of different water contents, ration and thus appears optically homogeneous
for pure water, and for a 60% water gel/pure water on visual inspection. As this phenomena is
system. somewhat independent of covalent cross-link
Journal of Colloid and Interface Science, VoL 51, No. 2, May 1975
 NATURE OF WATER IN HYDROGELS 231
concentration (11, 26), it has been attributed 8. KRISHNAMURTHY, S., MCINTYI~E, D., AND SANTEE,
to noncovalent cross-links due to polymer/ E. R., JR., J. Polym. Sd. 11, 427 (1973).
9. JaoI% M. S., aI,n) ANI)RADE, J. D., J. Biomed.
water interactions (11, 26). It is thus reason-
Mater. Res. 7, 509 (1973).
able to suspect that it m a y be related to the 10. REroJO, M. F., J. Polym. Sci. A-1 5, 3103 (1967).
nature of water (or types of water) in the gels. 11. P,mrojo, M. F., J. Appl. Polym. ScL, 9, 3417
(1965).
SUMMARY 12. YASUDA,H., GOCHIN, M., AND STorm, W., JR.,
J. Polym. ScL A-1 4, 2913 (1966).
The nature of water is a synthetic hydrogel 13. WEAST, R. C., Ed., "Handbook of Chemistry
has been studied by applying three different and Physics," 51st ed., The Chemical Rubber
techniques: dilatometry, specific conductivity, Co., 1971.
14. BETrELagI~, F. A., "Experimental Physical
and differential scanning calorimetry. The
Chemistry," p. 323. W. B. Saunder, Company,
results obtained by the three techniques agree Philadelphia, PA, 1971.
with each other and support the hypothesis 15. LEE, H. B., The nature of water in a synthetic
that there exists three classes of water in hydrogel: poly (2-hydroxyethyl methacrylate),
hydrogels. The data suggested that approxi- Ph.D. Dissertation, University of Utah, June,
1974.
mately up to 20 wt. c7o of the hydrated gel is 16. MOELW'ZN-HuGHES,E. A., "Physical Chemistry,"
water bound to the polymer network. A pp. 464 and 748. Pergamon Press, London, 1961.
semiquantitative analysis of three classes of 17. GLASSTOrm, S., LAIDLER, K. J., AND EYRING, H.,
water in the gels was obtained from the dila- "The Theory of Rate Processes," Chap. I0,
tometric results. McGraw-Hill, New York, 1941.
18. BocmtlS, J. O., AND REDDY, A. K., "Modern
Electrochemistry," Vol. 1, p. 471, Plenum Press,
ACKNOWLEDGMENTS New York, 1970.
This work was supported by the U. S. Atomic 19. VAN VLACK,L. H., "Materials Science for Engi-
Energy Commission, Contract AT(11-1)-2147. We neers," p. 277, Addison Wesley, New York,
thank Dr. R. H. Boyd and Dr. K. Biliyar for the use 1970.
of the differential scanning calorimeter, and Dr. S. W. 20. FRANKS, F., "Water," Vol. 1, p. 135, Plenum
Kim, Dr. S. Ma, Dr. S. Paek, and Dr. D. Lentz for Press, New York, 1972.
many helpful discussions and assistance. We also 21. Amxm, I., AND HAm~XS, G. G., "Chemical
thank Dr. Edward Eyring and his group, University Kinetics: Principles and Selected Topics," p. 63,
of Utah, for the loan of the AC Bridge. McGraw-Hill Book Co., New York, 1966.
22. MAIDIQUE,M. A., VON HI~PEL,A. L., ANDWEST-
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Journal of Colloid and Interface Science, Vol. 51. No. 2. May 1975