VOL. 9, PP.

315-326 (1975)

J. BIOMED. MATER. RES.

I.

Wettahility of Hydrogels
Poly (2-Hydroxyethyl Methacrylate)

1JRAKK J. HOLLY and JIIGUEL F. REFOJO, E y e Research

Institute of Retina Foundation, Boston, Jlassachusetts 02114

Summary
The wettability characteristics of the contact lens material, PHEMA, with
respect to water have been determined by using the sessile drop, and the captive
air bubble techniques of contact angle goniometry. It is concluded that on
PHEMA gels water does not spread spontaneously. Large hysteresis has been
observed in the advancing and receding contact angles. This suggests that, this
hydrogel surface is capable of changing its free energy through reorientation of
the polymer side chains and chain segments depending on the nature of the
adjacent phase. The water content of the gels does not appear to have an effect
on water wettability in the hydration range investigated. The minor wettability differences among the various gels studied were most likely due to differences in surface structure and segmental mobility due to inherent variations
in the method of preparation. Small but consistent differences were found
between the contact angles measured by the captive bubble method and those
obtained by the sessile drop method, the former values being higher. These
differences may not be method-related artifacts and cannot be explained a t the
present time.

INTRODUCTION
I n the past decade hydrophilic soft contact lenses made mostly of
crosslinked poly (Zhydroxyethyl methacrylate) polymer, PHEMA,
have become increasingly popular.lr2 The PHEMA gel is also
expected to be biocompatible, i.e. antithr~mbogenic,~
so widespread
use as surface coating of durable synthetic materials for artificial
organs is predicted in the future. PHEhlA is but one of many
existing transparent hydrogels and it contains approximately 40Yo
water by weight a t equilibrium hydration. This equilibrium water
content of PHEMA gels can be varied between certain limits by
31.7

@ 1975 by John Wiley di Sons, Inc.

316

TTOLLY AN11 REFOJO

changing the conditions of polymerization and the density of crosslinking.

The fact that the polymer matrix of a hydrogel such as PHEMA
consists of macromolecules having numerous hydrophilic sites and
can thus imbibe considerable amount of water, leads people to assume
that PHEMA, as well as the other hydrogels, have hydrophilic
surfaces. It is, in other words, expected that a water drop placed on
a clean hydrogel surface will spontaneously spread. If the adhesion
of water to the gel surface were a t least as strong as the cohesion of
water, then indeed, water would completely wet the gel.
There has been no detailed study published, to our knowledge,
on the water wettability of hydrogels to confirm this assumption.
However, occasional statements in the l i t e r a t ~ r e ,and
~ experience
in handling such gels suggest that a t least some hydrogels may not
be completely wettable by water. We have decided t o investigate
the water wettability of hydrogels, since a basic knowledge of the
surface characteristics of such gels could provide understanding and
even help solving the often troublesome problems of surface contamination and deposit build-up of therapeutic and cosmetic hydrogel
contact lenses.
I n this first part of the hydrogel wettability study, the wettability
characteristics of PHEMA hydrogels prepared by various methods
and having different water content are reported. I n later reports,
the effect of water content and chemical composition and structure
on the mater wettability of various hydrogeis will be discussed. A
basic study of hydrogel surface and the hydrogel-water interface and
that of biopolymer adsorption a t the hydrogel-water interface are
also in progress.

MATERIALS AND METHODS

Preparation of the Hydrogels
All PHEMA hydrogels studied, except PHEMA IV, were prepared
by polymerizing and simultaneousiy crosslinking the hydroxyethyl
met,hacrylate monomer in solution with a redox initiator (Table I).
The polymerization was carried out between two clean soda-lime glass
plates separated by a silicone rubber gasket. I n some cases, where
indicated in the Table, the glass plates were siliconized prior to use
in order t o prevent adherence
of the gel to the glass.
L

WATER WETTABILITY OF PHEPtIA GELS

317

TABLE I
Methods of Preparation of PHEMA Gels
6%
Ethylene
Ammonium
10%
PHEMA HEMAb EDMA MAAb Glycol Water Persulfate DMAEAd
Gel. NO.^ (ml)
(ml)
(ml)
(ml)
(ml)
(ml)
(ml)

I
I1
I11
IV"
V"
VIC
VIIC

22
6
6
20
6
6
6

11
11
0.7
0.7
2
1
0.2
0.2
b
b
2
0.2
0.2
(bulk polymerized with 0.191 g isopropyl percarbonate)
b
2
__
0.2
0.2
0.1
b
1
2
0.2
0.2
0.2
2
0.2
0.2
b

&Conditionsof polymerization: Gel I, 3 hr a t 60C; gels 11, 111, V, VI, VII,

1 4 hr a t 75C and an additional 4 hr a t 90C. Gel IV, 2 hr a t 45C and 1 hr at
W C , all in a circulating air oven.
b Commercial HEMA monomer contains about 0.1 yo ethylen dimethacrylate,
EDMA, and about 3.0y0methacrylic acid, MAA. In these syntheses, the commercial HEMA was vacuum distilled and the main portion of the distillate used
for the polymerization without further purification or analysis. The distillation
removes inhibitors and polymers already formed during storage but leaves
EDMA and MAA approximately in the same proportion as in the raw material.
Only PHEMA V and VII contains additional crosslinking agent while PHEMA
VI contains additional acid moieties in the polymeric network.
c Glass plates were Siliclad treated.
d 2-dimethylaminoethyl acetate.

The resulting gels were submitted to prolonged washing to leach

all the soluble by-products, then were stored in distilled water with
frequent changing of water for a t least one month prior to the
measurement. PHEMA IV was bulk polymerized with a free radical
initiator (see Table I) between siliconized glass plates, then swollen
to equilibrium and washed as thoroughly as the other PHEMA gels
were.
PHEMA hydrogels with equilibrium water content ranging from
32y0 to 43y0 have been prepared by varying the amount of crosslinking agent in the polymerization mixture, and by varying the
reference degree of sw-elling (i.e. initial monomer dilution) in the
polymerization process. 2

HOLLY AND REFOJO

318

Wettability Measurements
The wettability of the PHEMA gels and that of the hard contact,
lens material, poly(methy1 methacrylate), PMMA, were determined
at room temperature by contact angle goniometry using two techniques. I n the sessile droplet technique (water-in-air) the gel was
enclosed in an environmental chamber (Model B-100 Ram&Hart,
Inc., Mountain Lakes, New Jersey) with transparent windows, the
excess water was blotted from the gel surface with a clean, lipid-free
filter paper, and the gel was equilibrated with air saturated with
water vapor. A drop of water was placed on the gel surface and its
size was slowly increased to obtain the advancing contact angle or
decreased until the drop receded in order to obtain the receding
contact angle value (Fig. l a ) .
I n the captive bubble technique, the whole gel was immersed in
water in a plastic chamber built for this purpose, and a small air
bubble was placed on the bottom side of the gel by a curved capillary
pipette. The bubble was slowly increased or decreased in order t o
obtain the receding or advancing contact angle values, respectively
A/WATER-IN-AIR

AA

=//=//

AIR

GEL / / = N

AIR

AIR

=
B/AIR-IN-WATER

=// =// GEL N =//

ADVANCING te,)

RECEDING

(en)

Fig. 1. Schematic diagram of contact angle measurements.

WATER WETTABILITY O F PHEMA GELS

319

(Fig. Ib). The contact angles were directly read on a NRL Contact
Angle Goniometer (Model A-100 Ram6-Hart, Inc., Mountain Lakes,
New Jersey, to 1 degree accuracy.

RESULTS
A slow, monotonous variation of cont,act angle with time was
often observed in the first few minutes after placing the water
droplet on the gel. The advancing contact angles decreased somewhat due to gradual spreading while the receding angles increased
to a lesser extent (Fig. 2). Such time variation was also observed

L
0'

I
1 2

I
10

20

1
30

TIME IN M I N U T E S

Fig. 2 . Time dependence of water contact angle on PHEMA gels measured in

the water-in-air system.

HOLLY AND REFOJO

320

for the contact, angles measured by the captive bubble technique

(Fig. 3).
Table I1 contains the mean of the contact angle measurements
a t a given time (at 30 min both for advancing and receding contact
angles after the formation of the water droplet or air bubble), followed
by the standard error of the mean. Both the values obtained with
the sessile drop and the captive bubble techniques and the difference
bet,ween these two for the advancing and receding angles are listed.
As can be seen from the Table and also from Fig. 4, there are signifi-

90

80

70
(0

u 6G
[I
(3

50

U
-I

(3

2 40
4:
l-

2
z

30

0
0

20

10

1 1

1 2

10

I
20
TIME

30

IN M I N U T E S

Fig. 3. Time dependence of watei contact angle on PHEMA gels measured

in the air-in-water system.

70.4 + 0 . 4

84.3 f 2 . 0
62.0 f 0.9
58.1 f 1 . 2
77.7f1.4
59.8 f 1 . 6
76.9 f 1 . 9
61.0 f 3 . 3

Advancing

49.0 f O . 5

8 . 8 f 1.1
14.4 f 0.8
15.6 f 0.8
20.3+0.8
16.7 f 0 . 5
15.4 f 0.6
20.8 f 0 . 4

Receding

In degrees f standard error of the mean (n 2 6).

1.5

42.9
41.7
40.0
38.9
37.7
36.1
31.7

PHEMA I
PHEMA I1
PHELMA I11
PHEMA I V
PHEMA V
PHEMA VI
PHEMA VII

PMMA

H~0(7,)

Gel

Water in-air contact angle

75.6 1 0 . 5

80.0 f 1 . 7
71.7 & 2 . 3
68.2 f 2 . 5
81.210.9
1.9
64.7
82.0 j= 2 . 6
65.8 f 1 . 2

Advancing

51.3 ~ k 0 . 6

22.7 f 1 . 5
21.7 f 0.8
21.3 f 0 . 7
26.2f1.7
24.8 =t1 . 1
20.0 f 0.7
18.2 f 0.9

Receding

Air-in-water contact angles

TABLE I1
Contact Angle in Air-Water-PHEMA Systems

+5.2

-4.3
+9.7
+10.1
+3.5
+4.9
+5.1
+4.8

+2.3

f7.3
+5.7
+5.9
+8.1
$4.6
-2.6

+13.9

Difference Difference
in advancing in receding
contact
contact
angle
angle

!3

*
E!
c
2
8
cb
3
F
cl

.%

322

HOLLY AND REFOJO

cant differences between the contact angles obtained by these two

techniques, the captive bubble values being consistently higher for
both the advancing and the receding contact angles.
The contact angle of water obtained with the various PHEMA
gels are plotted as a function of gel hydration in Fig. 4. The hard
contact lens material PMMA (equilibrium water content = 1.5%)
is also included for comparison.
Two interesting observations can be made when considering these
contact angle data. First, the advancing contact angle on all the
gels is unexpectedly high. For example, some of the PHEMA gels
are even less wettable than PMMA. Secondly, there is a large
difference between advancing and receding angles for all the gels,
i.e. the contact angle hysteresis is unusually pronounced.

IPHEMA

VII

I
I
I

I
I

I
I

I
I
I

WATER

+ * ''
I

* *

COlIENT IN PER CENI

Fig. 4. Water contact angles on PHEMA as a function of the gel water

content. (0)
measured by the captive bubble technique. (0)
measured by
the sessile drop technique. The values obtained for PMMA are represented by
add
for the two methods, respectively. Solid shapes represent the
receding angles.

(a) (m

WATER. WETTABILITY OF PHEMA GELS

323

DISCUSSION
It is well known that the polymeric network of the PHEMA
hydrogel contains sufficient number of binding sites for water, e.g.
hydroxyl groups, so that the resulting energy of water-polymer
interaction is sufficiently high to overcome, a t least partially, the
hydrophobicity of the nonpolar parts of the polymer backbone.
When the polymer segments of such a gel is subjected to the
asymmetric molecular force field a t the gel-air phase boundary,
it is energetically more favorable for the polymer chain segments
to orient in such a way as to expose the hydrophobic side groups
or the nonpolar parts of the polymer backbone toward the gaseous
phase arid to bury the polar sites in the aqueous phase within the
gel. This is so because the molecular force field of the water molecules in the gaseous phase is much weaker than in the liquid phase.
Thus the gel surface appears hydrophobic in spite of the numerous
hydrophilic sites on the polymer molecules forming the matrix of
the gel. This must be why such large advancing contact angle
values are obtained with water on PHEMA hydrogels.
When such a PHEMA gel surface having the most hydrophobic
configuration possible is immersed in water, its structure becomes
unfavorable since it would have high interfacial tension against
water. So the polymer segments reorient again taking up conformation similar to that in the gel interior in order to achieve minimal
interfacial tension. This is why the receding contact angle of water
is so much smaller on PHEMA gel than the advancing contact angle.
The surface structural changes cause the large hysteresis of the water
contact angle.
The extent to which a gel surface may become hydrophobic by
reorientation and conformational changes, depends 011 the chemical
structure of the polymer in the gel matrix and also on the mobility
of the individual chain segments. I n PHEMA swollen in water,
there is evidence of a secondary structure in addition to the covalently
linked primary structure. This secondary structure is a result of
water-induced ordering of polymer segments in the network. 6-8
Such a secondary structure formation may not be extensive a t the
gel-air interface resulting in increased segmental mobility. As
judged by the magnitude of the advancing water contact angle,
some of the PHEMA gels have a surface more hydrophobic even

324

HOLLY AND REFOJO

than that of PMMA, a considerably more hydrophobic polymer.

The receding water contact angle on PMMA, however, is much
larger than on PIIEMA gels, i.e. water contact angle hysteresis is
much smaller with PMMA (Fig. 4). This is no doubt due to the
surface structure of PMMA which is frozen when compared to the
relatively mobile surface structure of PHEMA gel where the polymer
segments are plasticized by water.
Even if the surface structure of PHEMA gel could be immobilized
in the hydrophilic conformation that occurs when the gel is immersed
in water, the hydrogel would not, be completely wetted by water.
This is shown by the finite receding contact angle of water. This
is not too surprising, if one considers that the PHEMA homopolymer
is not hydrophilic enough to be water-soluble, although its monomer,
2-hydroxyethyl methacrylate, is soluble in water.
Most of the conformational change takes place rapidly a t the gel
interface as shown by the consistency of the contact angle data
obtained by the sessile drop and the captive bubble techniques.
However, the time variation of the contact angles observed to last
several minutes could be due to further, relatively slow changes in
polymer conformation near the equilibrium state.
We have no explanation to offer for the consistent differences
observed between the contact angles measured by the captive bubble
technique and by the sessile drop technique. Similar differences
were also found for PMMA which also contains a small fraction of
water. Generally the contact angle values obtained in the air-inwater system were larger except for two cases: 0 E for PHEMA
V I I and @ A for PIIEMA I, and for both cases their errant behavior
can be attributed to some unusual circumstances connected with
the gel samples. (PHEMA VII was transgressed with numerous
fine cracks that developed during swelling due to the internal stresses
in this highly crosslinked gel.)
The equilibrium water content of the PHENIA gels does not
seem to play a role in determining wettability. The conditions
of gel preparation as they influence surface structure and mobility
seem to be more important. This appears to be strange, since
surface segmental mobility certainly depends on crosslink density,
which in turn is a function of the extent of equilibrium hydration.
It is important to remember, however, that the overall bulk crosslink

WATER WETTABILITY OF P H E M A GELS

325

density may bear littl reelation to surface crosslink density and

segmental entanglement structure.

CONCLUSIONS
I n conclusion, we may state that since water does not spread
on PHEMA spontaneously, this methacrylic hydrogel has a hydrophobic surface even when in equilibrium with saturated water vapor.
However, when immersed in water, the gel surface becomes less
hydrophobic. Thus a thin water film would be less apt to rupture
over a PHEMA surface than the large advancing angle would seem
to indicate. The polymer chains a t the gel surface appear to have
sufficient mobility to reorient and the type of interface resulting
from these conformational changes depends on the nature of the
adjacent phase.
Such high surface mobility attributes special properties to the
PHEMA hydrogel surface. It has moderate to low surface free
energy in air, while the gel-water interfacial tension is less than for
solids of comparable surface free energy. This is probably the
reason why lipids and other low energy surface contaminants, i.e.
denatured proteins and lipoproteins, are not more of a problem with
the hydrogel lenses especially if their surface is continuously covered
with tears.g
I n order to reduce unwanted interaction with surface active
biopolymers and lipids, the hydrogel-water interfacial tension could
be further decreased by preparing gels with hydrophilic surface
groups that would cause minimal changes in the interfacial water
structure. Such a material should be quite biocompatible according
to the minimum interfacial tension hypotheses of biocompatibility
of Andrade and others.lOJ1
The knowledge of the surface chemical properties of the hydrogel
lenses is fundamental for the scientific formulation of more effective
cleaning, sterilizing, and wetting solutions and for the preparation
of new hydrogel contact lens materials with improved surface properties. Either through the adsorption of macromolecular wetting
solution components or by some change of the gel surface composition,
mobility, and structure, a minimal interfacial tension against water
may be achieved while retaining the mechanical strength of the gel.
A low gel-water interfacial tension would result in less adsorption and

326

HOLLY AND REFOJO

denaturation of tear proteins, negligible lipid adsorption, and lipidprotein interaction which all interfere with visual acuity and are
difficult to remove. It would also improve the gel wettability
by the tears resulting in higher stability for the tear film overlying
the hydrogel lenses.
This study was supported by Special Research Fellowship No. 1 F03 EY550088-01, in part by Research Grant No. EY-00208, and by PHS Grant No.
EY-00327, all from the National Eye Instit.ute, and in part by the Massachusetts
Lions Eye Research Fund, Inc. The capable assistance of Fee-Lai Leong is
also gratefully acknowledged.

References
0. Wichterle and D. Lim, U.S. Pat. 3,220,960 (1965) Re 27,401 (1972).
M. F. Refojo, Surv.Ophthal., 16, 233 (1972).
J . D. Andrade, Trans. Amer. Soc. Artif. Intern. Org., 19, 1 (1973).
A. S. Hoffman and G. Schmer, Paroi Arterielle, 1(2), 95 (1973).
M. F. Refojo and H. Yasuda, J. A p p l . Polymer Sci., 9, 2424 (1965).
M. F. Refojo, J . Polymer Sci., A-1, 5, 3101 (1967).
T . C. Warren and W. Prins, Macromolecules, 5, 506 (1972).
B. D. Ratmer and I. F. Miller, J . Polymer Sci.,A-1, 10, 25 (1972).
F. J. Holly, in T h e Preocular Tear F i l m and D r y E y e Syndromes, Int. Ophthal.
Clin., F. J. Holly and M. A. Lemp, Eds., Little, Brown and Co., Boston,
1973, p. 279.
10. J . D. Andrade, M e d . Instrum., 7 , 110 (1973).
11. J. V. Maloney, D. Roher, E. Roth, and W. A. Latta, Surgery, 66,775 (1969).
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Received Sept'ember 9, 1974