d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

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journal homepage: www.intl.elsevierhealth.com/journals/dema

Effect of rigid rod polymer ller on mechanical properties of

poly-methyl methacrylate denture base material
Anne-Maria Vuorinen a, , Scott R. Dyer a,b , Lippo V.J. Lassila a , Pekka K. Vallittu a
a

Department of Prosthetic Dentistry & Biomaterials Science, Institute of Dentistry, University of Turku, Lemminkaisenkatu
2,
20520 Turku, Finland
b Department of Restorative Dentistry, Oregon Health & Science University, Portland, OR, USA

a r t i c l e

i n f o

a b s t r a c t

Article history:

Objectives. The aim of this study was to evaluate the mechanical properties of denture base

Received 9 October 2006

material with rigid rod polymer (RRP) particulate llers.

Received in revised form

Methods. Specimens were fabricated from autopolymerized polymethylmethacrylate den-

27 July 2007

ture base resin (Palapress Heraus-Kulzer) and RRP particles were used as llers (Parmax

Accepted 31 July 2007

Mississippi Polymer Technologies, Inc.). Five groups were tested: 0 wt% RRP, 10 wt% RRP,
20 wt% RRP, 30 wt% RRP, and 100 wt% RRP. Specimens were stored dry at room temperature for 2 days or in water at 37 C for 44 days before testing until failure at a three point

Keywords:

bending test (ISO 1567) for measuring exural properties. The surface microhardness, water

Dental materials

sorption, and solubility were also measured. Existence of interpenetrating polymer network

Polymers

(IPN) between ller and denture resin was examined using solvent treatment and scanning

Reinforcement

electron microscopy (SEM).

Mechanical properties

Results. Specimens with RRP ller revealed higher exural modulus, but the exural strength

Water sorption

decreased. Specimens with 30% RRP ller showed exural strength of 67.4 MPa, whereas

Solubility

specimens without llers gave strength of 93.9 MPa. The 100% RRP group revealed the highest
exural strength (305 MPa). Flexural strength of water-stored test specimens decreased in
most groups when compared to dry specimens. Microhardness increased as a function of
RRP ller. SEM micrographs revealed no IPN-network on the surface of RRP llers. Addition
of RRP llers decreased the water sorption, whereas solubility was not affected.
Signicance. This study revealed that although RRP polymer has good mechanical properties,
addition of RRP to denture base resin as llers did not increase mechanical properties. This
was explained by lack of IPN-formation between RRP llers and polymer matrix.
2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Polymethylmethacrylate (PMMA) is a non-resorbable polymer and its structure is based on a exible backbone of
carboncarbon chains with pendant methacrylate groups
(Fig. 1a ) [1]. PMMA has been used in dentistry since 1930s as
denture material and in medicine since 1950s as bone cement.

When used as a denture base material, the powder-like polymerized PMMA beads are mixed with methacrylate liquid
monomers containing a small percentage of dimethacrylate crosslinker. When PMMA-powder and MMA-monomer
liquid are polymerized a semi-interpenetrating polymer network structure (semi-IPN) is formed. The semi-IPN structure
contains one or more thermoplastic polymers mixed with

Corresponding author. Tel.: +358 2 333 8380; fax: +358 2 333 8390.
E-mail address: anmavu@utu. (A.-M. Vuorinen).
0109-5641/$ see front matter 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2007.07.003

d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

cross-linked polymer [2]. Resistance to impact fracture and

high exural strength are desirable properties of denture
base polymers. Mechanical properties of PMMA based denture
base materials are often insufcient for clinical use [3]. Consequently, several types of ber reinforced composite (FRC)
materials have been introduced specically for denture base
materials [410]. Some limitations of using unidirectional ber
reinforcements have been shown: need for extra manufacturing processes and anisotropic strength of unidirectional FRC
reinforced denture base [10].
Rigid rod polymers (RRP) are molecular chains specically
designed to create long polymers with restricted chain movement. Polyphenylenes are one kind of RRP. For polyphenylene
(Fig. 1b) each phenyl ring has a substituent derived from
a variety of organic groups. Pendant groups can be varied
including, e.g., hydrogen, methyl, tert-butyl or phenyl groups.
These types of aromatic carbocyclic or heterocyclic polymers
are sometimes also referred as a self-reinforced polymer,
because of the intrinsic high strength and modulus without
any reinforcing agent [11,12]. The reason for good mechanical properties is chain stiffness with a high proportion of
paraphenylene linkages and restricted rotational movement
along the main polymer chain [13]. The structure of RRPs is
high degree of order and orientation [11,12]. RRPs are usually
soluble only in strong protic acids such as poly(phosphoric
acid) [11,12]. Because of their phenyl-based structure, RRPs
are usually highly hydrophopic. Many types of RRP have been
developed and their properties have been studied [1117].

Fig. 1 (a) Structural formula of PMMA is based on exible

backbone of carboncarbon chains. (b) Structural formula of
rigid rod polymer.

709

Lammers et al. concluded that certain heat-treated rigid rod

polymer bers have a tensile modulus up to 360 GPa, a tensile strength above 4 GPa and compressive strength of 1.7 GPa
[16]. Morgan et al. concluded in their nanoindentation study
that RRP had surface hardness twice as high as traditional
engineering thermoplastics [13].
The general principles of polymerpolymer adhesion are
chemical bonding, mechanical interlocking, interpenetrating
polymer network (IPN) formation, and interaction of Van der
Waals or similar dispersion forces. In reinforced composites
adequate bonding of ller particles to the polymer matrix is
needed to transfer stresses from weak matrix to more durable
llers. If the llers are made of polymers, IPN could provide
such good bonding. The capability of monomers to dissolve
polymers in order to bond to each other through IPN bonding system can be evaluated using solubility parameter values
[2]. The better the match (i.e., the smaller the difference) of
the solubility parameters of polymer and monomer, the more
probability of formation of an IPN bond. The solubility parameter for MMA is 18.9 MPa1/2 and for PMMA 17.820.5 MPa1/2 [18].
Polymerized MMA-monomer and PMMA-polymer are known
to bond to each other through semi-IPN structure.
The rigid rod polymer ller used in this study, selfreinforced polyphenylene (Parmax , nowadays known as
PrimoSpire) is soluble in methylene chloride (solubility parameter = 20.0 MPa1/2 ). This means that the solubility parameter
of this RRP is close to the parameter value of methylene
chloride and also MMA [18]. Theoretically this would mean
that this polyphenylene based RRP could bond to an MMAmatrix with the help of the IPN-system [2,18]. The aim of
this study was to investigate the inuence of RRP llers on
exural properties of PMMA. The hypothesis was that RRP
llers increase the mechanical properties of denture base
polymer.

2.

Materials and methods

2.1.

Test specimen preparation

The test groups of this study are shown in Table 1. Bar

shaped test specimens (65 mm 10 mm 3 mm) were fabricated according to ISO 1567 from autopolymerized PMMA
resin (PMMA powder/MMA monomer liquid: Palapress ,
Heraus-Kulzer, Wehrheim, Germany). Powder-to-liquid ratio
for the resin mixture in group 1 was 10 g/7 ml. In group 2 it
was 10 g/8 ml, in group 3 10 g/9 ml, and in group 4 10 g/13 ml.
Specimens in group 5 were manufactured of RRP only (manufacturer Mississippi Polymer Technologies, Inc.). (Table 2 )
The powder was rst weighed and after that monomer liquid
was mixed into it. In groups 2, 3, and 4 part of the PMMApowder was replaced with RRP-powder. Higher monomer
liquid ratio was used with increased RRP quantity to ensure
proper blending of the powder mixture with liquid. Test
specimens were polymerized in a mold under a pressure of
300 kPa at a temperature of 80 5 C for 15 min in a pressure
curing device (Ivomat, Typ IP 2, Ivoclar AG., Schaan, Liechtenstein). Specimens made of RRP only (group 5) were made
by the compression molding system with a pressure of ca
138 bar, temperature of 315 C for 30 min of the manufacturer

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d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

Table 1 Groups and results of the study

0%-RRP Group 1
Flexural strength (MPa) dry
Flexural strength (MPa) wet
Modulus (GPa) dry
Modulus (GPa) wet
Surface hardness dry (VHN)
Surface hardness wet (VHN)
Water sorption (wt%)
Solubility (wt%)

93.9 (3.5)a
93.5 (9.5)a
3.3 (0.1)a
3.6 (0.4)a
22.0 (1.0)a
23.0 (1.9)a
2.30 (0.03)a
0.68 (0.04)a

10%-RRP Group 2

20%-RRP Group 3

73.1 (4.4)b
62.9 (9.4)b
3.9 (0.3)a
3.8 (0.6)a,b
23.0 (1.7)a
23.0 (1.3)a
2.22 (0.04)a
0.54 (0.14)a,b

30%-RRP Group 4

64.3 (9.5)b
65.6 (5.6)b
5.1 (0.7)b
4.7 (0.6)c
28.0 (2.2)b
25.0 (2.2)b
2.08 (0.01)b
0.60 (0.04)a,b

67.4 (5.6)b
59.2 (6.7)b
6.9 (0.5)c
4.6 (0.3)b,c
26.0 (2.4)c
25.0 (1.5)b
2.00 (0.01)b
0.60 (0.01)b

100%-RRP Group 5
305.0 (4.4)c
293.5 (9.4)c
7.5 (0.2)c
7.4 (0.2)d
56.0 (3.2)d
52.0 (1.0)c
0.94 (0.09)c
0.08 (0.06)c

Mean exural strength, exural modulus, surface microhardness, water sorption and solubility of dry and wet groups. ANOVA was performed
(p < 0.001). Superscript letter indicates homogenous subsets by each row (Tukey p < 0.001).

of the RRP. After polymerization the test specimens surfaces

were nished with 1200 and 2400 grit silicon carbide grinding paper (Struers A/S, Rodovre, Denmark) using a grinding
machine (LaboPol-21, Struers A/S, Rodovre, Denmark). Specimen dimensions (width, height, and length) were measured
at three points on each side in order to ensure dimensions of
the test specimens. The test specimens were either stored dry
at room temperature for 2 days or in water at 37 C for 44 days
before the three point bending test.

2.2.

Three point bending test

The exural strength and exural modulus were measured

according to ISO 1567 standards using span length of 50 mm
and crosshead speed of 5.0 mm/min. All specimens were
tested until failure in air in a Lloyd material testing machine
(model LRX; Lloyd Instruments, Fareham, England) and the
results were recorded with PC-computer software (Nexygen,
Lloyd Instruments, Fareham, England). Flexural strength (S),
i.e., highest stress, and exural modulus (E) were calculated
from the formulas:
S=

3FL
2bd2

where S is the stress (MPa), F the load or force at break or at

yield (N), L the span of specimen between supports (50 mm), b
the width (10 mm), d the thickness (3.3 mm)
E=

3F1 L3
4bd3 D1

F1 is the force at point D1 (N), L the span of specimen between

supports (50 mm), b the width (10 mm), d the thickness

Table 2 The amounts of the used materials in the

groups of this study
Group
0%-RRP
10%-RRP
20%-RRP
30%-RRP
100%-RRP

Amount of
PMMA (g)
10.0
9.0
8.0
7.0
0

Amount of
RRP (g)
0
1.0
2.0
3.0
100%

Amount of
MMA (ml)
7.0
8.0
9.0
13
0

The amounts of PMMA-powder (g), RRP-powder (g) and MMAmonomer liquid (ml) in the groups of this study.

(3.3 mm), D1 the deection at linear region of load-deection

curve (m)

2.3.

Surface microhardness

The surface microhardness test (Vickers test) was made after

the three point bending test, followed by wet polishing the
test surface with 4000 grit silicon carbide grinding paper. In
the microhardness test, the force used was 19.6 N and loading
time 5 s. In each group three test specimens were used and 10
measurements for each specimen were done.

2.4.

SEM-examination

The test specimens were rst wet polished with 4000 grit
silicon carbide grinding paper, followed by diamond paste
polishing (Struers polishing cloths, diamond paste 1 m,
Struers A/S, Rodovre, Denmark) to create a nal polish
on the specimen. Specimens were cleaned in water in
an ultra-sound cleaning device for 10 min. Specimens then
were immersed into solvent tetrahydrofuran (THF) (SigmaAldrich, Laborchemicalien GmbH, Seelze, Germany) for 30 s to
separate cross-linked and non-cross-linked polymer phases
on the surface and to show possible signs of IPN structures. Specimens were sputter coated with gold using a
coater (BAL-TEC SCD 050 Sputter Coater, Balzer, Liechtenstein). After coating, SEM micrographs were taken and
visually analyzed. One test specimen per group was examined.

2.5.

Water sorption and solubility

The water sorption of the test specimens was measured after

1, 2, 5, 7, 14, 21, 30, 37, and 44 days with the scales (AT261
DeltaRang Mettler Toledo). Test specimens that had been
stored in water dehydrated in air in an oven (Ehret) at 120 C
for 43 h to calculate sorption and solubility. Sorption and solubility were calculated from the formula below:
wt%so =

mw mdh
100%
mdh

wt%sl =

md mdh
100%
mdh

where md is the conditioned mass of the specimen, in micrograms (g). mw is the mass of the specimen, in micrograms

d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

711

Fig. 2 (a) Flexural strength of test specimen in various groups. (n = 6). (b) Flexural modulus of test specimen in various
groups. (n = 6). (c) Surface microhardness of test specimen in various groups.

(g), after immersion in water. mdh is the reconditioned or

dehydrated mass of the specimen, in micrograms (g).

2.6.

Statistical analysis

Data were statistically analyzed with analysis of variance

(ANOVA) with statistical software SPSS (Statistical Package
for Social Science, SPSS Inc., Chicago, IL, USA) using the factors of quantity of RRP and storage condition as dependent
variables and exural strength, exural modulus and surface
microhardness as independent variables. Tukeys post hoc test
was used to determine the differences between the groups
(p < 0.001).

3.

Results

3.1.

Three point bending test

Mean exural strength and exural modulus for dry specimens are shown in Table 1. Two-way ANOVA revealed that RRP
quantity signicantly affected (p < 0.001) the exural strength
and the exural modulus. Water storage signicantly affected
(p < 0.001) the exural strength in groups 2, 4, and 5 and the
exural modulus in group 4.
In group 5, the RRP test specimen revealed the best exural strength (dry: 305.0 4.4 MPa water-stored: 293.5 9.4 MPa)
and the exural modulus (dry: 7.5 0.2 GPa (dry) water-stored:
7.4 0.2 GPa). In group 1, the PMMA test specimens had
the exural strength of 93.9 3.5 MPa and a exural modulus of 3.3 0.1 GPa. By adding RRP llers to the PMMA,
the exural strength decreased. The exural strength in
all groups except group 3 and the exural modulus in
all groups except group 1 decreased slightly in the water

stored specimens compared with those stored dry. Flexural strength and exural modulus are shown in Fig. 2a and
b. Typical deection curves of dry specimens can be seen
in Fig. 3 .

3.2.

Surface microhardness

Summary of microhardness values in Vickers hardness number are shown in Table 1 and Fig. 2c. ANOVA revealed
signicant differences between the groups (p < 0.001). Specimens of group 5 were approximately two times harder than
specimens made fully of PMMA. Water storage had a tendency to decrease the microhardness slightly except in group
1.

Fig. 3 Typical load-deection curves for materials tested.

Numbers refer to test groups (see Table 1).

712

d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

4.

Fig. 4 SEM micrograph of surface of test material showing

A: polymer matrix, B: IPN layer, C: PMMA bead and D: RRP
ller. Original magnication 500, bar 50 m, tilt 45 .

3.3.

SEM-examination

SEM micrographs revealed differently cross-linked polymer

layers around PMMA beads suggesting the existence of an IPN
layer which was not seen between RRP llers and polymer
matrix. (Fig. 4)

3.4.

Water sorption and solubility

Addition of RRP llers decreased the water sorption of

the denture base polymer. Water sorption of specimens in
group 1 was 2.30 wt% (Table 1), whereas the specimens in
group 5 showed sorption of 0.94 wt%. ANOVA revealed signicant differences between the groups (p < 0.001) in water
sorption. Water immersion was carried until a plateau (saturation) was achieved in the sorption curves (144 days),
which is illustrated in Fig. 5 . Solubility was not inuenced by the incorporation of RRP llers. However, specimens
made fully of RRP revealed lower solubility than other
specimen groups. Mean solubility values are shown in
Table 1.

Fig. 5 Weight change (%) plotted against storage of time in

water with various quantities of RRP llers in denture base
polymer.

Discussion

This study demonstrated the effect of polyphenylene-based

RRP llers on the static exural properties of denture base
polymer. Addition of particulate RRP llers increased the
exural modulus and surface microhardness but decreased
the exural strength compared to the unlled denture base
polymer. Flexural strength of specimens made fully of RRP
was high (305 MPa) conrming the fact that RRPs have good
mechanical properties.
SEM-examination of differently cross-linked phases in
the materials tested revealed that no IPN-based adhesion
between RRP llers and denture base polymer occurred. SEMexamination showed a clear zone where an IPN layer ought to
exist between PMMA beads and surrounding matrix. Formation of the IPN layer is based on the capability of the monomer
of the resin matrix to dissolve the ller particles. In the case
of PMMA, the solubility parameter of PMMA and monomers of
the resin, predominately MMA, are close to each other and the
surface of the PMMA bead can be dissolved. In the case of RRP
llers MMA was not able to dissolve the ller surface and no
IPN layer was formed. According to the hypothesis of the study,
it was expected that RRP ller particles with higher strength
and stiffness could have increased the mechanical properties of the denture base polymer. This would have required
adequate adhesion between the reinforcement and surrounding polymer matrix. Because of the lower strength of denture
base material which included RRP llers, it was estimated
that no adequate interfacial adhesion between the RRP llers
and denture base polymer matrix existed. This hindered load
transfer from the matrix to the reinforcing llers. However,
stiffness was increased by the addition of RRP ller to the
PMMA-polymer matrix.
Water sorption and solubility were measured from threepoint bending test specimens. Polymethylmethacrylate, like
other polymers, absorbs water slowly over a period of time
[1]. This is because of the polar properties of the molecules.
Water sorption affects the exural strength and exural
modulus of dentures. Vallittu et al. studied the effect of
water sorption on the exural properties of ber-reinforced
denture base polymers [19]. In the same study they had
a test group for unreinforced denture base resin. They
concluded that the exural modulus of the unreinforced
test specimens decreased signicantly (p < 0.001) and also
the transverse strength decreased. According to ISO 1567standard, water sorption of denture base polymer should not
exceed 32 g/mm3 for heat-cured or chemical-cured materials [20]. Water sorption and solubility of reinforced denture
base polymer, namely glass ber-reinforced composites have
been studied [19,21,22]. These studies showed that the water
sorption and solubility of unreinforced PMMA and PMMA reinforced with glass ber are in accordance with International
Standards Organisation specication No. 1567. Increasing
inorganic llers in restorative composites lowers the amount
of water-absorbable polymer, which further lowers water sorption of the composite. The use of polymeric llers of RRP
in denture base polymer showed a decrease in water sorption. This is likely to be due to the hydrophopic nature of
RRP.

d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 708713

One difculty encountered during specimen fabrication

was the uniform dispersion of RRP ller in the PMMA matrix.
Consequently, variations in some mechanical properties were
not related to the quantity of RRP. For instance, surface microhardness was higher in the group containing 20 wt% of RRP
than in the group with 30 wt%.

5.

Conclusion

Within the limitations of the present study, the following conclusions were made: The results suggest that RRP llers have
an effect on the mechanical properties of denture base polymer. Flexural strength was lowered and exural modulus and
surface microhardness increased. Water sorption was reduced
by adding RRP llers to denture base polymer.

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