Complete denture retention.

Part II: Wettability studies on

various acrylic resin denture base materials
Ph. Mons&Ggo, D.C.D., D.S.O., D.E.O.,* A. Baszkin, Ph.D.,**
M. de Lourdes Costa, Ph.D.,*** and J. Lejoyeux, D.C.D., D.S.O., D.E.O.****
University of Paris 7, Faculty of Dentistry, Paris, France; and National Center for Scientific
Research, Chktenay-Malabry, France

The objective of this study was to characterize in vitro selected acrylic resin
denture base materials by water-contact angle measurements. The sessile drop
method and the underwater-bubble method were used. The results obtained from
these measurements are discussed in terms of contact angle and polymer-water
work of adhesion hysteresis. On polished heat-polymerized samples this hysteresis
results from the reorientation of superficial polymer chains. The combined effect of
increased sample roughness and of the entrapment of water droplets in the pores
of material gives rise to the highest contact-angle hysteresis observed on sand-
abraded samples. On the basis of physical analysis of the mechanism involved in
complete denture retention, developed in Part I of this work, it is believed that the
sand-abraded material is the most convenient for the retention of the complete
denture. (JPROSTHET DENT 1989;62:308-12.)

I n the first part of this article,l the physical basis of
the complete denture retention mechanism has been dis-
cussed. The role of the liquid meniscus between the den-
ture and the mucosa was demonstrated. The possible dis-
placement of its contact line on the denture under the
action of dislodgment forces, was shown to play a predom-
inant role in denture retention. The fundamental require-
ment for denture retention has been suggested to be the
contact angle hysteresis, namely, the difference between
the advancing liquid-solid contact angle (0~) and the
receding (@R)angle. The advancing contact angle is defined
as the angle that a liquid drop forms on a dry solid surface.
The receding angle is formed when the liquid recedes on the
previously wet solid surface.
The objective of this study was to characterize selected
acrylic resin denture base materials by the magnitude of
the hysteresis of their work of adhesion with water.
Because these materials are in contact with an aqueous
environment (saliva), the determination of the water-
polymer work of adhesion may characterize the wetting
properties of these materials by saliva.
MATERIALS AND METHODS
Acrylic resin denture base samples
Flat circular samples, 10 mm in diameter and 1 mm
thick, of the test denture base materials were prepared as
follows: Circles of wax (Moyco, Moyco Industries Inc.,
Philadelphia, Pa.) were cut out of a wax sheet, invested in
*Former Assistant Professor, Department of Prosthodontics.
**Senior Research Associate, C.N.R.S.
***Assistant Research Professor, Department of Pharmaceutics
Sciences, University of Coimbra, Portugal.
****Professor and Chairman, Department of Prosthodontics.
10/l/11674
a flask, and boiled out. The plaster, while hot, was coated
with a separator (Separating Fluid, Ivoclar, Liechtenstein).
Heat-polymerizing acrylic resin (“SR 360”, Ivoclar) and
autopolymerizing resin (Quick SR 360, Ivoclar) were pre-
pared, invested, and compression-molded according to the
recommendations of the manufacturer.
The obtained samples were then used as prepared
untreated surfaces or treated according to one of three
procedures: Some were sand-abraded (Corindon, Odoncia,
France), some polished (as in clinical practice), and others
coated with a photopolymerized varnish (Permalink, G.C.
Corporation, Tokyo, Japan). Ten test specimens of each of
these surfaces were then used in this study.
Before the contact angle measurements, the surfaces of
the samples were first cleaned for 5 minutes with a soft
cotton immersed in water saturated with a household soap
and then rinsed well with running hot water (30 C). They
were then immersed in an ultrasonic apparatus containing
a mixure of water and methanol (1:l v/v ratio) for 10 min-
utes. Water was then substituted for the water-methanol
solution and the samples were ultrasonically washed for an
additional 10 minutes. This operation was repeated in fresh
triple-distilled water. The resin samples were dried in an
oven at 40° C for 48 hours and stored in a desiccator at room
temperature. It is believed that this rinsing procedure helps
to obtain the clean surfaces necessary for the determina-
tion of reliable contact angle values.
Examination of the samples by means of a scanning
electron microscope (Cambridge Stereoscan 150) at mag-
nifications varying from x20 to X5000 showed that the
surfaces were clean and had no deposits.
Contact angle measurements
The contact angles were measured by two different
methods: (1) the sessile drop method using a thermostat-

308 SEPTEMBER1989 VOLUME62 NUMBER3

COMPLETE DENTURE RETENTION: PART II
, (A)
h
/////////////////////////////
Potymer
Fig. 1. Sessile drop technique for advancing @A and
receding 0~ contact angle measurements.
ically heated contact angle apparatus and (2) the under-
water bubble method.
For measurements of the sessile drop contact angle, a
device built by “Societe Bouty”, Paris, was used. This ap-
paratus, used for extensive studies of polymer surface
energetics,2, 3 is described as follows.
1. The dark room chamber is double enclosed; temper-
ature is controlled by an external liquid-circuit thermostat.
The chamber has two opposite windows and is installed on
a plate that may be moved in two horizontal directions at
right angles to the windows. The sample holder inside the
chamber is fixed above a small dish filled with liquid. This
allows saturation of the air phase with the vapor and thus
avoids evaporation of the liquid drop during the measure-
ment.
2. An exterior screw permits rotation of the sample
holder and measurement of contact angles on various sites
of the sample surface.
3. A microsyringe is fixed at the top of the chamber by
which a liquid drop of known volume may be placed on the
surface of a tablet. The microsyringe may be displaced in
two opposite directions, thus ensuring deposition of the
drop along the surface of the sample.
4. A cathetometer with X15 magnification, equipped
with a goniometer that provides the contact angles.
The advancing contact angles (0~) of sessile drops were
measured directly. The volume of the drop was 6 ~1and the
measurements were carried out at room temperature (20’
C). The advancing contact angles for the liquids used in this
study were generally independent of time in the range of 1
to 10 minutes. Readings, therefore, were made 2 to 3 min-
utes after placement of the drop on the surface.
To measure the receding contact angles (6~) a small
amount of the drop volume is extracted by a syringe and the
value of the new contact angle is taken.
Fig. 1 is the schematic representation of the advancing
and receding contact angle measurements of liquid drops
on solid surfaces.
The underwater contact angle measurement is useful for
characterization of polymers used in biomedical applica-
tions because the surfaces remain hydrated. These angles
were measured by using the method developed by Andrade
et a1.4The contact angle apparatus consists of a traveling
THE JOURNAL OF PROSTHETIC DENTISTRY
(W
//////////I//// POlY mer
-I -
-- - water -
__ __ -
-.-
Fig. 2. Schematic representation of underwater air-
bubble contact angle OR measuring teehnique (A) and of
typical profile of underwater air bubble (B).
goniometer with Xl5 eyepiece, a variable-intensity light
source, and a micrometer-adjustable X-Y tray vertically
mounted on an optical bench. The tray supports a Plexiglas
(Rohn and Haas Co., Philadelphia, Pa.) container in which
a Teflon (Du Pont Co., Wilmington, Del.) plate is sus-
pended. The polymer sample is held on the underside of the
Teflon plate with small Teflon clips. The container is then
filled with the triple-distilled water. The plate with the
polymer sample is lowered into the container until the
sample is completely immersed. An air bubble with a vol-
ume of approximately 0.2 ~1 is formed on the tip of a mi-
crosyringe and, when released, it rises to the polymer-water
interface. The receding contact angle is measured inside
the water interface. Schematic illustrations of this tech-
nique are shown in Fig. 2.
The accuracy of contact angle-values for both methods
was closer than 2 degrees. The reported values are the mean
values of at least six measurements on different spots on
the same sample. All reported results were rounded off to
two significant figures.
RESULTS
Sessile drop contact angle data (e, and t-)R)and the hys-
teresis of polymer-water work of adhesion (.IWadh) for the
309
 MONSiiNtiGO ET AL

Table I. Contact angles (sessile drop method) and water-solid works of adhesion of heat-polymerized acrylic resin
(mean values + SD)
Advancing contact Receding contact Hysteresis of the
angle BA (degrees) angle OR (degrees) Contact angle solid-liquid work
hysteresis Ed - 82 of adhesion
Surface x SD ?i SD (degrees) AWadh mN/m

Heat polymerized resin 64 2.1 48 1.5 16 17

(untreated)
Sand-abraded beat polymerized 95 2.6 67 1.9 28 35
resin
Polished heat-polymerized 78 2.3 46 1.1 32 35
resin

Table II. Contact angles (sessile drop method) and water-solid works of adhesion of autopolymerized acrylic resin
(mean values + SD)
Advancing contact angle Receding contact angle Contact angle Hysteresis of the
63~(degrees) 8R (degrees) hysteresis solid-liquid
eA*R work of adhesion
Surface z SD E SD (degrees) AWadk mN/m

Autopolymerized acrylic resin 65 2.4 52 1.3 13 14

(untreated)
Sand-abraded autopolymerized 90 2.7 69 1.6 21 26
acrylic resin
Polished autopolymerized 75 1.8 52 1.1 23 26
acrylic resin

heat and. autopolymerized acrylic resins respectively are
presented in Tables I and II.
The hysteresis of the polymer-water work of adhesion are
calculated for each polymer sample from the following ex-
pression:
(1) AWadh = ~~(COS eR - co8 0~)
where yi is the water surface tension (72.2 mN/m).
Table III summarizes the contact angle values for heat
and autopolymerixed acrylic resin samples after treatment
with the photopolymerixed varnish.
Finally, Table IV shows the underwater bubble-method
contact angles on the studied polymers and the resin-water
works of adhesion calculated from the expression:
(2) Wadh = y1 (1 + cos 0)
DISCUSSION
Heat #olymerized resin
The contact angle data (Table I) clearly indicate that the
untreated heat-polymerized samples are more hydrophilic
(9~ = 64 degrees) than the polished (6~ = 78 degrees) and
sand-abraded ones (94 = 95 degrees).
The value of the contact angle obtained on the polished
polymer samples agrees with that reported by Craig et al.5
for poly(methy1 methacrylate) used for dental purposes
(9, = 76 degrees f 1 degree). It was slightly lower than the
value measured by Andrade et al6 on pure poly(methy1
methacrylate surfaces (9~ = 89 degrees). Kilani et al7 re-
ported a lower contact angle value (0.4 = 64 degrees + 3.6
degrees) for poly(methy1 methacrylate) manufactured for
dental uses. However, in their study, polymer was cast
against glass and the smooth surfaces obtained were much
different from the samples made with current dental tech-
niques.
The significant differences in contact angle values (Table
I) must be analyzed in terms of the advancing-receding
contact angle hysteresis induced by these surfaces. Contact
angle hysteresis is influenced by surface heterogeneity,
surface roughness,8 surface deformation,4 and chemical
contamination of water. In addition, contact angle hyster-
esis of polymer surfaces can be induced by the mobility and
reorientation of surface polymeric chains.2*s-g
The rigid poly(methy1 methacrylate) material exhibits
little or no deformation at room temperature. Because the
highly deformable materials cause only a small hysteresis,
the possibility of polymer deformation resulting in the ob-
served hysteresis has to be ruled out.
Contamination of the studied surfaces may produce a
change in the water surface tension that, in turn, would in-
duce an error in the measured contact angle values. The
origin of this contamination may be of chemical nature
(migration of the residual monomer from the polymer bulk
to the surface) or of microbial nature (formation of metab-
olites). However, in the application of the angle measuring
techniques, the liquid drop was left in contact with the

310 SEPTEMBER 1SSS VOLUME 62 NUMBER 3

COMPLETE DENTURE RETENTION: PART II

Table III. Advancing contact angles (sessile drop Table IV. Under water bubble method contact angles
method) on varnished acrylic resins (mean values + SD) and corresponding solid-water works of adhesion of heat
polymerized resins (mean values + SD)
Advancing Receding
contact contact @RAfter
angle 6A angle 8~ Initial I hr
(degrees) (degrees) Resin-
contact immersion water
angle 6~ in water
Surface i SD x SD (degrees) (degrees) a~,“,iO,~
Wadh
Heat-polymerized resin treated 63 1.9 52 1.7 Surface % SD % SD mN/m
with a photopolymerized
varnish Heat-polymerized resin 54 1.8 $2 2.0 115
Sand-abraded heat polymerized 64 1.2 47 1.1 Sand-abraded heat- 37 2.1 19 i .;C? 1:10
resin varnished with a polymerized resin
photopolymerized varnish Polished heat-polymerized 44 1.41 41 :i ! 124
Polished heat-polymerized resin 64 2.1 46 1.9 resin
varnished with a
photopolymerized varnish
Autopolymerized resin 61 2.3 53 1.8 hour). In these instances, we have observed values as low
varnished with a as 19 degrees. Although water sorption’desorption always
photopolymerized varnish occurs with acrylic resins regardless of surface conditions,
Sand-abraded autopolymerized 62 2.2 53 2.0
the ratio of sorption is accelerated on rough materials. Thus
resin varnished with a
photopolymerized varnish
the high increase in hydrophiiicity of the abraded material
Polished autopolymerized resin 62 1.7 52 1.4 (Wadh = 130 mN/m) may be explained by the high water-
varnished with a photo- uptake exhibited by these materials. This is confirmed by
polymerized varnish the SEM observation,‘* which reveals the presence of pores
Total 63 2 50 4 in the surface of the abrased material
On the other hand, the increase in 01 and AWadh of the
polished samples cannot be explained by the increase of the
polymer surface less than 2 minutes. Moreover, the ex- roughness. Since the polishing procedure considerably re-
tremely careful rinsing procedure made it highly improb- duces their initial roughness, one would expect a decrease
able that either chemical of microbial contamination oc- in the 0~ and AWadh values. The observed opposite effect
curred. requires, therefore, further discussion.
The surface heterogeneity factor may play its role in the The most probable explanation of the observed phenom-
increase of the contact angle hysteresis. In this case the enon would involve the reorientation of the superficial
advancing contact angle would depend on the fraction of polymer chains brought about by the polishing procedure.
the surface occupied by a low surface-energy phase; the re- As mentioned, the mobility of polymer superficial chains
ceding angle would be influenced by a high surface-energy may take place as a result of the change in the local envi-
phase.s Even though the SEM observations on the polished ronment of the polymer adjacent phase. This restructuring
surfaces revealed the presence of beads immersed in the of the polymer surface is time-temperature dependent. In
material bulk, it seems unlikely that they provoke surface the case of poly(methy1 methacrylate), which is a rigid
phase separation. Poly(methy1 methacrylate) is known to polymer with a relatively high glass-transition temperature
be an amorphous polymer and there is no reason to consider (Tg = 115” to 125” C), a considerable increase in temper-
that its surface may be different from its bulk. ature is necessary to provoke the rotation of its backbone
The high contact angle exhibited by the sand-abraded chains.
polymer is not surprising. Indeed, the increased surface The local-temperature increase during the polishing
roughness produced by the treatment gives rise to the 0.4 procedure may induce this rotation mechanism. Moreover,
and AWadh increase. The effect of the increased surface even at temperatures slightly higher than room tempera-
roughness on the increase in @Aand AWadh values has been ture, the rotation of the lateral methyl ester group (0 chain)
observed by many authors. lo-l3 It would therefore explain with respect to the ester C = 0 bond is possible. In the cis
higher 0~ and AWadh values of the abraded surfaces as form, the ester methyl groups and the polymer backbone
compared with the untreated heat-polymerized material. chains are all directed on the same side of the C = 0 bond;
When the sand-abraded material is immersed in water, in the trans form, the ester methyl groups are turned
and when air under water contact angles are measured around the C = 0 bond and direct themselves away from
(Table IV), the average contact angle is 37 degrees after 20 the polymer backbone.lO
minutes of immersion. This value is much lower than that In contact with the hydrophobic air phase, the methyl
of untreated polymer (54 degrees). Moreover the 8~ values groups would orientate themselves t,oward air, In contact,
decrease when the samples are immersed extensively (1 with water, they would reorientate themselves toward the

THE JOURNAL OF PROSTHETIC DENTISTRY YI I


polymer bulk. Thermodynamically such a situation is jus-
tified because the most favorable organization of the poly-
mer surface in contact with air would imply its lowest sur-
face energy. The contact of the polymer with the polar
water phase would induce the rearrangement of the oxy-
gen-containing groups (C = 0) resulting in their reorienta-
tion toward the surface (cis-form position).
The results of contact angle measurements confirm the
above analysis. Not only does the eA value of the material
increase (from 64 degrees to 78 degrees) after polishing but
also all of the AWadh values double in relation to that of
the raw heat-polymerized material (Table I). In the same
way, the value of the polymer-water work of adhesion in-
creasesfrom 115 mN/m for the untreated resin to 124 mN/
m for the polished surface (Table IV). The high value of
AWadh on polished surfaces (35 mN/m) agrees with that
reported by Andrade et al6 who found this hystereis to be
equal to 31.6 mN/m.
It should also be noted that the increase of temperature
during the polishing procedure probably favors the volatil-
ization of the residual monomer.
Autopolymerized resin
The results of the contact angle measurements on the
autopolymerized resins (Table II) are similar to those ob-
tained with the heat-polymerized samples. However, the
hysteresis of the water-polymer work of adhesion is in all
cases lower than for the heat-polymerized samples. The
rotation of superficial polymer chains (/3chain rotation) on
polished samples seems,however, to be hindered in relation
to cross-linking of the material.
Varnished autopolymerized and
heat-polymerized resins
The results summarized in Table III clearly demonstrate
that all of the samples have almost identical contact angle
values independent of their nature and treatment. Indeed,
the varnish renders all surfaces identical by completely
shielding the influence of the polymer surface on the con-
tact angle. Effectively the SEM micrographs ‘of the var-
nished surfaces show that they are very smooth and almost
alike.14 They exhibit a moderate hysteresis of the contact
angle (13 degrees 2 4 degrees) and relatively low hystere-
sis of the solid-liquid work of adhesion (AWadh = 14 mN/
4.
CONCLUSIONS
In the first part of this article, the physical criteria that
have to be fulfilled to obtain good denture retention were
described. This retention would depend mainly on the
variation of the meniscus contact angle between the
salivary film and the denture under the effect of the
dislodgment forces. In this respect the most convenient
denture base material would be that exhibiting the highest
312
MONSJkNliGO ET AL
contact angle hysteresis, such as high advancing contact
angle (9~) and low receding contact angle (0~).
The results of this in vitro study clearly show that sand-
abraded heat-polymerized resin would fulfill this condition
better than other studied materials.
The 9~ value of this material is 90 degrees and the 0~
value is 67 degrees. After immersion in water, the entrap-
pment of water droplets in the pores of the abraded mate-
rial increases hydrophilicity and decreases the 9~ value to
37 degrees (mean 6)~value corresponding to the immersion
time of 20 minutes).
These results need to be supplemented by other in vitro
studies. In particular, the contact angle measurements of
liquid mixtures that can mimic the salivary film (solutions
containing mucin or mixtures of mucin and other proteins)
would be of great importance.
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Reprint requests to:
DR. PHILIPPE MONS~NE~X
14 EWJLEVARD VITAL BOUH~T
92200 NEUILLY
FRANCE
SEPTEMBER 19S9 VOLUME 62 NUMBER 9