Journalof DentistryVol. 23, No. 5, pp.

313-318, 1995
Copyright Q 1995Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0300-5712/95 $10.00+ 0.00

0300-5712(94)00002-6

The effect of preparation conditions of acrylic

denture base materials on the level of residual
monomer, mechanical properties and water
absorption
A. Dotjan*,

5. Bek*, N. N. Cevikf- and A. Usanmazt

*Department of Prosthodontics,
University, Ankara, Turkey

Gazi University,

Faculty of Dentistry and tDepartment

of Chemistry,

Middle East Technical

ABSTRACT

Objectives and methods: The curing of several commercial powder/liquid

mixtures of acrylic denture
base materials was carried out at different temperatures and curing times. The levels of residual
mononer, tensile strength, percentage elongation before break and water absorption were measured.
Results and Conclusion: It was found that the level of residual monomer determined by gas-liquid
chromatography decreased with curing time and temperature increase. At the same time, the tensile
strength was improved and water absorption decreased.
KEY WORDS: PMMA, Residual monomer, Mechanical
J. Dent. 1995; 23: 313-318

(Received

properties,

10 May 1994; reviewed

Water absorption

22 July 1994; accepted 20 October 1994)

INTRODUCTION
The autoploymerizing acrylic resins are now commonly
used in processing dentures. For both autopolymerizing
and heat-cured acrylic resins, the level of the residual
monomer in the resin- and the mechanical properties1-12 are closely related to the curing conditions. It
is a general belief that tissue sensitivity to acrylic resin
denture-base materials depends on the level of residual
monomerg13,14,and increases with an increase in the
percentage of residual monomer in the resin. McCabe
and Baskerg have reported that methyl methacrylate
monomer is an irritant and sensitizer to tissues. Therefore, the level of the residual monomer must be controlled carefully when curing these types of materialslm7.
It has also been reported that a high level of residual
monomer is detrimental to mechanical properties of
the cured resin&. However, there is insufficient reported literature on the relationship between conditions of material preparations and the material properties of the cured resin.
Several physical and chemical methods have been
used to measure the level of residual monomer in
polfimethylmethacrylate) (PMMA) resin. The most accurate method is gas-liquid chromatography5. McCabe
and Basker showed by this method that the level of
the residual monomer is inversely related to the curing
time, i.e. the longer the curing time, the lower the

Correspondence
should be addressed to: Prof. Dr Arife Dogan, 10
Sokak No. 2, MutlukGy, Ankara, Turkey.

residual monomer level. Fletcher et aZ.7 reported high

levels of the residual monomer in thick polymer samples compared to thin ones. Austin and Basker3 compared the residual monomer level obtained by gas
chromatography (GC) and IR-spectral analysis (IR) for
12 specimens that had been cured for different curing
times. The results range from 0.24 to 6.33% for GC
and 0.33 to 5.50% for IR measurements. The agreement for each of the specimens was considered to be
acceptable. They also investigated the effect of sample
thickness, material preparation, sampling methods, etc.
All these factors have certain effects on the level of
residual monomer. For example, they found the residual monomer percentage to be seven times greater for
short curing cycle specimens compared to that in long
curing cycles. The effect of the curing cycle is also
studied by Harrison and Huggett15 for heat-cured
acrylic resins. They have determined the residual
monomer level after leaching most of it in water.
However, this will make the conclusion between residual monomer level and mechanical properties less
meaningful, because the residual monomer, in addition
to acting as a plasticizer in the polymer matrix, will also
cause the formation of more porosity that will also
affect the mechanical properties. Therefore, in our
study, we determine the residual monomer level without keeping the samples in water.
In this study, several commercial samples were prepared at different temperatures and curing times. The
autopolymerizing resins were prepared in a constanttemperature water-bath to keep the temperature con-

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J. Dent. 1995; 23: No. 5

sister-nand to dissipate the exothermic reaction to heat

by water, which has a higher thermal conductivity than
air. In most of the reported work, polymerization takes
place in air, and heat formed from the exothermic
reaction might cause a high level of porosity in the
material. The effect of curing temperature for autopolymerizing resin has also not been reported before. The
level of the residual monomer, tensile strength, percentage elongation before break and water absorption
were measured. Optimum conditions for imporved mechanical properties are proposed when considering
these results.
The effect of thickness of sample plate on residual
monomer content has been studied by Sadamori et ~1.~
and other workers3J7,and therefore will not be repeated in this work.

MATERIALS

AND METHODS

The powder/liquid denture materials chosen for this

study are given in Table I. The organic solvents used
were of spectroscopic grade and they were used without further purification. Water was triple distilled and
deionized. The purity of water was tested by conductivity measurements.
The powder/liquid mixtures were prepared according to the respective manufacturers instruction. They
were mixed in proportions recommended by the manufacturer. Heat curing samples were cured at boiling
water temperature for 30,40 and 50 min. The autopolymerizing samples were cured in constant temperature
(20, 25 and 30 C) water-baths, which have been
equipped with an electronically controlled heater, for
30 min. The curing times and temperatures were adjusted accurately (+ 0.1 s and f O.OPC) to the desired
values. The mixed resins were packed into a plaster
mould designed to produce 6 x 3 x 0.5 (+ 0.1) cm sample size plates which were used for all measurements.
The Fourier Transform Infrared (FTIR) spectra of
reference monomer and liquid samples in methanol
were taken in a NaCl cell, and those of powders and
cured polymer samples from KBr pellets using FTIR
Spectrophotometry (Nicolet, Model FFP-510, Madison,
WI, USA).

The specimens for residual monomer determination

were prepared by using a 2.5 mm engineering twist drill
with 250 r.p.m. drilling velocity. Drilling velocities of
100-500 r.p.m. were tested, to determine if either the
drilling velocity or heat produced from drilling resulted
in any depolymerization or break in polymer chains.
However, no effect was observed from experimental
results for one test specimen. Therefore, all drillings
were done at 250 r.p.m. velocity. The drill cuttings were
collected and weighed, then placed in a round-bottom
250 ml extraction flask equipped with a condenser. The
sample weight was approximately 1 g (+ 0.1 mg) and
the extraction solvent was 20 (+O.l) ml methanol. The
extraction was carried out at the boiling temperature of
methanol for 6 h using a heating mantle. After the
extraction was completed, the polymer residues were
filtered off, and the methanol solution saved for the
residual monomer analysis. Further extraction of residual polymer showed no more residual monomer extract. The extraction was repeated for three experimental samples of each material in Table I, with five specimens per sample and ten specimens of material B, per
sample to test for statistical differences between samples.
The residual monomer analyses were done by
gas-liquid chromatography (GLC) (10% Carbowax 20
M packed column HP 5890 model Hewlett Packard
GLC, Neyrinz, Geneva, Switzerland). The oven temperature was set at 70C for 1 min, then raised to 80C at a
heating rate of SC/min. and kept at that temperature
for 5 min. The injection and flame ionization detector
temperatures were at 150C. Nitrogen gas was used as
the carrier gas at a flow rate of 345 kPa. The detector
output was linked to a chart recorder, with a chart
speed set at 5 mm/min. The results were also evaluated by a connected computer that gives percentage
area corresponding to each observable peak. A 1 ml
extract was injected each time and a standard methanol
solution of monomer was used as reference (Aldrich
Chemical Co. Ltd, Milwaukee, WI, USA). The reference curves were obtained for monomer. The internal
standards (known amount of monomer) were used in
the sample solution to obtain very accurate results free
of all types of systematic errors.

Table 1. Denture materials used

Notation sample

Manufacturer

A QC-20 Heat Cured

Conventional processing
B Paladon 65 Heat Cured
Conventional processing
C SR-lvocap Heat Cured
Injection technic
D Meliodent Autoploymerizing
At room temperature
E Palapress Autopolymerizing
At room temperature

De Trey Division Dentsply Ltd,

Weybridge, Surrey, UK
Kulzer & Co. GMBH Bereich Dental,
Hamburg, Germany
lvoclar AGFL Schan,
Liechtenstein
Bayer UK Limited, Newbury,
Berkshire, UK
Kulzer & Co. GMBH Dental Division,
Hamburg, Germany

A. Dogan eta/.: Acrylic denture base materials on level of residual powder/liquid

mixtures

315

Tensile strength and percentage elongation before

break for several samples cured under different conditions were measured on an Instron mechanical tester
(Tensile Testing Machine, Table Model-1102. Instron
Corp., Canton, MA, USA). The measurements were
carried out with 10 specimens of each sample (e.g. B,,
C,, etc.) prepared under identical conditions, and mean
values and standard deviations were reported.
For the measurement of water absorption, specimens
(6 x 3 x 0.5 (t-0.1) cm) were kept in triple distilled
water at 25 ( f 0.5)C for about 2 months. They were
weighed (with +O.l mg accuracy) at intervals of 15 min
for the first 2 h, every 30 min for 6 h, and then every 24
h. The excesswater on specimens was removed before
weighing by blotting with a filter paper. Measurements
were performed on three specimens and mean values
were calculated.

RESULTS
Infrared (IR)-spectral

1
loo

investigation

I
boo

I
3ooo

2500

zoo0

15co

xno

500

Wavenumber (cm)
Fig. 1. FTIR spectrum of liquid (a), powder (b) and cured polymer
(cl.

The FTIR spectra of powder, liquid and cured form of

the materials in Table I were investigated. The spectra
of different commercial samples were identical. Therefore, one example of a liquid, powder and cured mixture is shown in Fig. 1. The spectra of the liquids were
identical to those of methyl methacrylate monomer and
those of powders were identical to those of PMMA
which have been polymerized by radiation via vinyl
groups addition. The IR-spectral peaks at 1643 cm-i
corresponding to vinyl groups is observed in the spectrum of the monomer (8&. la), but not in the spectrum
of the polymer (F&J. Ib,c). The FTIR spectrum of the
cured samples (Fig. Ic) shows peak broadening as an
indication of high-molecular-weight, crosslinked polymer formation. The carbonyl (C = 0) peak at 1750
cm- is observed in all spectra. The concentration of
the residual monomer was too small to be observed
from this spectra.
The FTIR spectra of the heat-cured and the autopolymerizing powder/liquid samples were the same. The
FTIR spectra of heat-cured and autopolymerizing
powder and those of liquid samples did not give any
peak when differentiated. Therefore, the accelerators
that may exist in autopolymerizing samples are IR
inactive or have very small concentrations that are
under the detection limit of IR spectra.

showed no significant differences. Statistical analysis

revealed that the differences in mean values for each
material are significant. For example, when the t-test
was applied to two mean values closest to each other
(e.g. E, and E, in TubZeII), the results obtained were
t = 3.00, d.f. = 8, P > 0.02.
The level of the residual monomer decreased from
2.44% to 0.96% for QC-20 heat cured (sample A, to
A3), when curing time was increased from 30 to 50
min. Similar decreases in the level of the residual
monomer with increasing curing time were also
observed for other samples. The amount of reduction
for an additional 20 min of curing time is considerable.
The decreases in residual monomer levels with an
increase in curing time for heat curing samples are
plotted in Fig. 2. In all cases,straight lines (Y = 0.99 for
A and B samples; Y= 0.94 for C samples) were observed
within the range studied. The residual monomer levels
at 50 min curing time are quite similar for different
samples.
The reduction in residual monomer level for autopolymerizing samples with an increase of temperature
from 20 to 30C is relatively small.

The levels of residual monomer

Mechanical properties

The levels of the residual monomer are tabulated in

Table 11. The values given are the means ( f SD) of five
specimens (10 for BJ for each sample of A,, A,, etc.
prepared under identical conditions. The statistical calculations for sample B,(t = 1.83, d.f. = 9, P > 0.05)

The tensile strength and percentage elongation for

some samples are shown in TabZeIII. All the measurements have been repeated for 10 specimens of each
sample (e.g. 10 specimens of A,, etc.) for statistical
evaluation, and mean values are reported. The stan-

316

J. Dent. 1995; 23: No. 5

Table II. Curing conditions and average residual monomer levels (*SD)
each sample and 10 for B3)
Sample

Ai
A2
A3

B,
B2

B3
Cl
c2

C3
Di
D2
D3
El
E2

E3

for samples in Table / (five specimens for

Curing temperature
PC)

Curing time
(mid

% Residual
monomer

Heat cured 100

Heat cured 100
Heat cured 100
Heat cured 100
Heat cured 100
Heat cured 100
Heat cured 100
Heat cured 100
Heat cured 100
Autoploymerizing 20
Autopolymerizing 25
Autopolymerizing 30
Autopolymerizing 20
Autopolymerizing 25
Autopolymerizing 30

30
40
50
30
40
50
30
40
50
30
30
30
30
30
30

2.44 i 0.02
1.51 + 0.01
0.96 + 0.03
3.28 f 0.02
2.45 + 0.02
0.92 + 0.01
2.03 + 0.02
1 .16 + 0.01
0.98 f 0.03
2.33 i 0.02
2.06 + 0.04
1.89 + 0.02
1.52 + 0.01
1.49 + 0.02
0.94 + 0.02

dard deviations of the measurements as shown in Table

111 are relatively great, but typical for these types of
measurements. In general the mechanical properties of
different commercial samples are not much different
from each other. For example, the percentage elongation before break is almost the same for all samples.
The differences between the mean values of percentage elongation for most-sample groups are not statistically significant (e.g. for each pair of B,, B,; C,, C,;
and E,, E,, the values are almost the same). However,
the differences for the means of tensile strength are
significant. For example, if the tensile strength mean
values of D, : D, which have the closest value are
compared, the t-test results are t = 15.13, d.f. = 18,
P < 0.001.

Water absorption
The results in terms of percentage decrease in the first
30 min and maximum percentage increased attained

for samples stored in water at 25 & 0.5C, are tabulated

in Table W. In the first 30 min of storage in water, a
slight decreasein weight for most sampleswas observed.
The weights then started increasing gradually, reaching
a constant value at 20-25 days, then remaining at that
constant value for the rest of the time. The changes in
weight were plotted against time, and constant weights
reached were used for calculation of percentage. The
three specimens of each sample studied gave almost
exactly the same values.

DISCUSSION
The residual monomer level decreased for longer curing times of heat-cured samples and curing at higher
temperatures for autopolymerizing samples. Although
it is very hard to predict a tolerable level of residual
monomer for tissue sensitivity for each individual, the
level of residual monomer should be very low (e.g.

t
40

1
30

Time (min)
Fig. 2. Percentage

residual monomer level against curing time. Materials:

0, A; l , B; A, C.

I
50

A. Dogan et a/,: Acrylic denture base materials on level of residual powder/liquid

mixtures

317

Table /il. Tensile strength (T) (+ SD) and percentage elongation (E) (+ SD) for some samples
in Tab/e // ( the values are means of 10 specimens for each sample that is prepared under
identical conditions)
Sample

4
5,
63
Cl
C*
C3
5,

52
53
El
E2
E3

T (MPa)

%E

26.9 + 1.1
35.8 + 0.8
56.6 + 2.1
44.7 f 1.4
49.5 i 1.o
57.1 + 2.3
25.1 + 0.9
31.9 + 1.l
50.0 i 2.1
38.1 f 0.9
48.9 + 0.8
54.6 i 1.7

4.9 + 0.4
5.0 j 0.5
6.1 jz 0.4
5.0 10.4
5.0 * 0.5
7.5 j 0.6
4.9 10.4
5.5 * 0.5
6.1 i 0.6
5.0 * 0.3
5.0 * 0.4
5.4 * 0.5

0.45% as given by Austin and Basker3). In order to

achieve such a low residual monomer level, the curing
time should be more than 50 min.
At boiling water temperature, benzoyl peroxide (initiator in powder) decomposes (above 6oC), giving free
radicals which start and propagate further polymerization. However, the boiling water temperature is also
close to the boiling temperature of methyl methacrylate (100.8C at 101 kPa), which will change into gas
form and produce bubbles in a polymer matrix when
trapped in it. This type of gas formation will also be
enhanced by exothermic heat production during polymerization. The gas bubbles in the polymer matrix
form voids, increase porosity17 and develop high internal stress. The details of porosity formation have been
reported by Wolfaardt et al.. Entrapped residual
monomer in the polymer matrix will also leave voids
when removed from it. Therefore, mechanical properties which are closely related to internal stresses and
voids in the polymer matrix will also be related to the
level of residual monomer. As an example, the residual
monomer percentage in sample B, (3.28%) is larger
than that in sample C, (2.03%), and their corresponding tensile strengths are 26.9 and 44.7 MPa, respectively. Both samples are heat cured for 30 min, and
FTIR spectra showed no structural differences even
though they are made by different companies. Thus, for

a given sample, the tensile strength increases when the

residual monomer level decreases. This behvaiour
should be expected because of the plastisizer effect of
unpolymerized monomer in the polymer matrix. The
results obtained in this work are in agreement with the
suggestion of Brauer6. The data in Table 111show that
there is an improvement in tensile strength with an
increase in curing time, which also causes a decrease in
residual monomer level.
Poly(methy1 methacrylate) is insoluble in water
therefore the first weight decrease cannot be attributed
to the dissociation of resin in water. The residual
monomer near the surface of the resin probably diffuses into water, causing a decrease in the weight of
the samples. The reason for no weight decrease for
some samples containing a higher percentage of residual monomer may be explained by the nature of residual monomer in the polymer matrix. If the residual
monomer is not close to the surface of the specimen,
entrapped in the inner layers of resin plate, it cannot
diffuse out into water in a short time. Even if it diffuses
out later, the amount of water absorption into the
polymer will be high enough to compensate for the
weight lost caused by the residual monomer diffusion
from the resin to the water. As a result, a weight
increase instead of weight decrease was observed.

Tab/e IV. Water absorption of some samples in Table I/ (the values are means of three
specimens of each group)
Sample

Ai

A2
B,
B3
C,
D3
E3

% Weight decrease in
first 30 min

Trace
0.61
0.71
0.46
Trace
0.41
0.08

% Water absorption
at 60 days

2.70 + 0.005
2.15 + 0.004
2.75 + 0.007
2.19 * 0.01
2.61 + 0.008
1.95 * 0.009
2.43 i 0.008

318

J. Dent. 1995; 23: No. 5

There is a parallel relation between the level of the

residual monomer and the percentage water absorption.

For example, in this study, both values are

highest for the B, sample. Similarly, if we compare the

values for A, and A,, the percentages of residual
monomer were 2.44 and 1.51; the corresponding percentage water absorption was 2.70 and 2.15.
The percentage water absorption is higher for A,
than for A,, and B, was higher than B,. This can be
related to the curing time. As the curing time increases, the crosslinking increases, giving a harder polymer with less porosity. This could make the diffusion
of water into polymer matrix more difficult.

The absorption and desorption of water by acrylic

resins has been investigated in detaillsm21.This is a
diffusion process with a diffusion coefficient reported
by Braden of 5.4 X 10M9 cm2 s-i at 22.5 C. Water
will diffuse into voids in the polymer mass. Therefore,
when the level of residual monomer is high, the number of voids in the resin after leaching off the residual
monomer will be high and water intake will also be
high11,9-21. This is supported by data given in Tables II
and n/. For the same material (e.g. A, : A, or B, : Ba),
when the percentage of residual monomer is high (TabZe II>, the percentage of water absorbed is also high
(Table IV).

CONCLUSIONS
1. FTIR spectra determinations showed that there
were no material or structural differences between the

denture base materials used in this study. The activator

used in autopolymerizing resin in all samples studied
could not be verified by FTIR.
2. For heat-cured resins, the longer curing times
improved the tensile strength and decreased the level
of residual monomer. However, the percentage elongation does not change much.
3. For autopolymerizing resins, the level of residual

monomer decreased with an increase in temperature

when the curing time is kept constant. The constanttemperature water-bath used in this study is very important for obtaining relatively pore free resin that has
lower residual monomer content and low water absorption.
4. The percentage of water absorption is higher for
samples containing higher levels of residual monomer.

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Austin AT, Basker RM. Residual monomer levels in

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