J Bagh College Dentistry Vol.

23(3), 2011 Evaluation the effect of modified

Evaluation the effect of modified nano-fillers addition on

some properties of heat cured acrylic denture base
material
Ihab NS, (1)
Moudhaffar M, (2)

ABSTRACT
Background: The poly(methylmethacrylate) (PMMA) shown to be lacking two properties which are strength and
radio-opacity. The aim of this study was to evaluate the effect of addition of modified nano-zirconium oxide (ZrO2)on
some properties of heat cured acrylic denture base material .
Material and method: (ZrO2) nanofillers were incorporated into (PMMA) denture base by free radical bulk
polymerization. (PMMA) nanoparticales were coated with a layer of trimethoxysilypropylmethacrylate (TMSPM)
before dispersed and sonicated in monomer (MMA) in different percentages 2%, 3%, 5% and 7% by weight. Then
mixed with acrylic powder as general conventional method. Two hundred fifty five (255) specimens were prepared
for this study they were divided into (6) groups according to the test used. The tests were impact strength,
indentation hardness, surface roughness, transverse strength, radio-opacity and microscope test, for each test five
subgroups (one control and four for nano-ZrO2). The size and shape distribution of nano-ZrO2 particles were
estimated using scanning electron microscope (SEM) and atomic force microscope (AFM) .
Result: Highly significant increase in impact and transverse strength occur in acrylic reinforced with 5wt%, but non
significant increase was observed at 7wt% when compared to control group. Non-significant increases in indentation
hardness and surface roughness appear with addition of modified nano-ZrO2 at different percentages. For radio-
opacity a highly significant increase had occurred with the addition of modified nano-ZrO2.
Conclusion: The maximum increase in impact strength, transverse strength and radio-opacity was observed in
denture base nano composite containing 5wt% of nano-ZrO2.
Key words: poly (methylmethacrylate), nano composite. (J Bagh Coll Dentistry 2011;23(3): 23-29).

INTRODUCTION
Poly (methylmethacrylate) (PMMA) is the The properties of polymer nanocomposites
most commonly used material in construction of depend on the type of incorporated nanoparticles,
denture base since 1930 . This material is not their size and shape, as well as the concentration
ideal in every respect and it is the combination of and interaction with the polymer matrix (3).
various rather than one single desirable of Nanoparticles were undergone surface treatment
properties that accounts for its popularity and with saline coupling agent and embedded into
usage.Despite its popularity which satisfy PMMA (4). Many attempts have been carried out
aesthetic, simple processing and easy repair, the to incorporate inorganic nanoparticles into
main problems associated with PMMA as denture PMMA. Alumina nanoparticles were coated with
base material are poor strength particularly under acryloxypropyldimethyl methoxysilane to get
fatigue failure inside the mouth, impact failure PMMA/alumina nanocomposite with increased
outside the mouth and lack of radio-opacity (1). mechanical properties over pure PMMA(5).
The PMMA used routinely today is radiolucent Calcium carbonate nanoparticles modified with
and cannot be imaged using standard radiographic stearic acid was incorporated into PMMA to
techniques, so in cases of accidental ingestion, improve the abrasion resistance of PMMA(6).
aspiration and traumatic impaction of dental Barium sulphate nanoparticles was added to
appliance, their detection very difficult and PMMA to enhance radiopacity (7) .This study was
require invasive procedures as advanced imaging conducted to use inorganic nanofillers that are
techniques. Delay in localizing or removing the added to heat cure PMMA and test the effect of
foreign body may be life threatening (2). Recently, this addition on radio-opacity and some
much attention have been directed toward the mechanical properties of heat cured acrylic
incorporation of in organic nanoparticles into denture base material
PMMA to improve its properties.
MATERIALS AND METHOD
Surface modification of fillers (ZrO2, BaTiO3)
The introduction of reactive groups onto
fillers surface was achieved by reaction of 3-
(1) Assistant Lecturer University of Baghdad, College of
dentistry, Prosthodontics department.
trimethoxysilyl propylmethacrylate TMSPM
(2) Assistant Professor University of Baghdad, College of (meth acryloxy propyl trimethoxy saline) with
dentistry, Prosthodontics department zirconium oxide and barium titanate nano fillers.

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J Bagh College Dentistry Vol. 23(3), 2011 Evaluation the effect of modified

Table 1: Some of the materials that were used.

Material Trade Manufacturer
1. Zirconium (IV) oxide ZrO2 nanofiller 544760 Sigma-Aldrich Germany
2. Barium titanate BaTiO3 nano filler 467634 Sigma-Aldrich Germany
3. Trimethoxysilylpropyl methacrylate 98% Silane .440159 Sigma-Aldrich Germany
4. Toluene solvents GCC , U.K.
5. Heat-curing resin for denture . Superacryl plus Spofa Dental Czechoslovakia

Typical process was as follows nanofiller by analyzing the characteristic

30g of nano filler and 200ml pure toluene were vibrations of functional groups(4) .
placed into a flask then sonicated at ambient Pilot study
temperature for 20min (Figure 1.). After that, the Selection of proper percentage of zirconia
nano filler and toluene were placed into a flask nanofiller (ZrO2)
equipped with a magnetic stirrer(LABINCO, BV Percentages of 1%, 2%, 3%, 4%, 5% and 7% by
Model L-81) at room temperature. Then 1.5g of weight were used, percentages above 7% were not
silane (5% wt to nano filler) was added used due to change in the colour of acrylic.
dropwisely by sterile syringe under rapid stirrer. Transverse strength and impact strength tests were
The flask was covered by parafilm and the slurry used.Form the result obtained 2%, 3%, 5% and
was left standing in flask for 2 days. The solvent 7% were selected as a percentages of modified
(toluene) was removed by rotary evaporator under zirconia nanofiller that added to the polymer by
vacuum at 60°C at rotary 150 rpm for 30 min (RE weight.
510, Yamato, Japan). Selection of proper percentage of Barium titanate
BaTiO3 nanofillers
Percentages of 1%, 2%, 3%, 4%, and 5% were
added to acrylic by weight percentage above 5%
were not used due to change in the colour of
acrylic, the result showed a marked decrease in
the transverse and impact strength at the
percentage above 3%. Also the result showed that
percentage below 5% did not give adequate radio-
Figure 1: Probe sonication apparatus opacity (Figure 2.).Therefore, this material was
neglected in this study.
After that the modified nano filler was dried in Fracture surface of specimens were tested by
vaccum oven at 60°C for 20 hours (Gallen bamp, scanning electron microscope (SEM) and atomic
England). Then nano filler stored at room force microscope (AFM) show random
temperature before use.(4,8) . The infrared (IR) distribution of nano- BaTiO3 particles within the
spectra were performed (Shimadzu, FTIR-8400 S, nano cluster (aggregation), non- uniformity of the
Japan) to determine whether or not functional particles, this lead to decrease in the mechanical
groups of the TMSPM have been attached to the properties.( Figure 3.

1 4

2 5

ZrO2 percentage Amount of ZrO2 Amount of polymer Amount of monomer

0% 0 12g 6ml
2% 0.240g 11.760g 6ml
3% 0.360g 11.640g 6ml
5% 0.600g 11.400g 6ml
7% 0.840g 11.160g 6ml
Figure 2: X-ray examination of specimens reinforced with BaTiO3 nano fillers.

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J Bagh College Dentistry Vol. 23(3), 2011 Evaluation the effect of modified

Figure 3A: Specimens reinforced by 3wt% and 5wt% nano- BaTiO3 fillers ( SEM).

Figure 3B: Specimens reinforced by 3wt% and 5wt% nano- BaTiO3 fillers (AFM)

A. B. C.
B
Figure 4.A, B, C: Nano fillers were well dispersed in the monomer by ultrasonication

General preparation of test specimens

Three different metal patterns were constructed by The suspension of the monomer with ZrO2 nano
cutting stainless steel plate in desired shape and filler was immedatly mixed with acrylic powder
dimension by turning machine according to the to reduce the possibility of particle aggregation
required test. For impact strength test, a bar and phase separation. The proportion for mixing
shaped specimen (80mm x 10mm X 4mm) length, for acrylic resin was (2.5g:1g) P/L. All materials
width, thickness respectively (9) .For transverse were mixed and manipulated according to
strength test, hardness test, and surface roughness manufacture’s instructions. The mixing was
test: a bar shaped specimen (65mm X 10mm X carried out in a clean and dry mixing vessel and
2.5mm) length, width, thickness respectively(10) mixed by a clean wax knife for 30 second. The
.For radioopacity test: a square shaped specimen mixture was then covered and left to stand until a
(30mmX30mmX3mm) length, width, thickness. dough stage was reached.
(11)
Mechanical and physical tests utilized to
Mould preparation examine properties
The conventional flasking technique for complete Evaluation of the mechanical and physical
denture was followed. properties of the prepared nano composite denture
Proportioning and mixing of the acrylic base was compared with convensional denture
Table 2: percentages and amounts of polymer, base (heat cure acrylic resin).These tests are:
monomer and zirconium oxide nanofiller powder . 1-Impact strength test
Addition of fillers Impact strength test was conducted following the
Addition of modified Zirconium oxide nanofiller procedure given by the ISO 179 with charpy type
powder (ZrO2) was done by weight in four impact testing instrument (Impact tester N. 43-1,
groups, includes 2%, 3%, 5% and 7% to INC. USA.). The specimen was supported
monomer. An electronic balance with accuracy of horizontally at it’s ends ad struck by a free
(0.0001g) was used (Sartorius BP 30155, swinging pendulum which released from a fixed
Germany). After the addition of ZrO2 nano filler height in the middle. A pendulum of 2 joules
to monomer, the fillers were well dispersed in the testing capacity was used. The charpy impact
monomer by ultra sonication, using a probe strength of unnotched specimen was calculated in
sonication apparatus(Soniprep-150, England) at KJ/m2.
120 W, 60 KHz for 3 minutes to break them into 2-Microscope test
individual nano crystals(12) as shown in the The fractured surface of the impact test specimens
(Figure 4.). were examined and photographed with 1-scanning

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J Bagh College Dentistry Vol. 23(3), 2011 Evaluation the effect of modified

electron microscope (SEM). 2-Atomic force of ZrO2 nano filler reinforcement on micro
microscope(AFM). For SEM, five specimens geometry of the test surface. This device is
were examined,one representing the control ,four supplied with surface analyzer (sharp stylus)
representing 2wt%,3wt%, 5wt %,and 7wt% ZrO2 made from diamond. Maximum distance that can
nanocomposite , they were sputter-coated with be move is 11mm .Two measurements were done
uniform 2µm layer of gold in a vacuum on different areas of each specimen (the same
evaporator for 2 min at 25 mA to enhance image selected area of each specimen), and an average of
resolution. Fracture surface was examined in the two readings was calculated.
back scattered electron mode with an operating 6-Radio-opacity test
voltage of 2KV. For AFM ,two specimens were Aluminum step wedge was constructed by
examined, one representing 5wt%,and the other cutting pure Aluminum plate into desired shape
representing 7wt% of ZrO2 nanocomposite were and dimension which consist of 10 stepper
examined.The thickness of the specimen should beginning with 1mm thickness of aluminum with
be 2 mm to be put under the probe of the 1mm increment in each step reaching to 10mm at
scanning. the 10th steps (11) .The specimens of different
3-Transverse strength concentration are arranged over a wax plate of
The test was achieved using instron testing 10mm thickness. The addition of wax to simulate
machine (instron corporation, 1122, canton mass), the absorbing and scattering media of soft tissue.
each specimen was positioned on bending fixture, An aluminum step wedge was fixed beside the
consisting of 2parallel supports (50)mm apart, the specimens for standardization of the density of the
full scale load was 50kg, and the load was applied film.The wax plates, specimens and Aluminum
with cross head speed of 1mm/min by rod placed step wedge were kept over the exposure side of a
centrally between the supports making deflection 35X43cm cassette type KODAK GREEN 400.A
until fracture occurred . chest x-ray meachine (Siemens polydoros Lx and
4-Surface hardness test Sx 65/80 with videomed DI, Germany), 1 meter
Surface hardness was determined using durometer between the source of x-ray and specimens,
hardness tester from type shore D, (hardness machine was operated at 53 kv and 5m As,
tester-th 210, time group Inc. Italy) which is exposure time is 0.35 second, as it is used for
suitable for acrylic resin material. The instruments normal chest radiography .The processing was
consist of blunt-pointed indenter 0.8mm in done according to manufacture’s instructions by
diameter that tapers to a cylinder 1.6mm. The using KODAK RPX-OMAT processor. A light
indenter is attached to a digital scale that is transmission densitometer (Densonorm21i,
graduated from 0 to 100 units; measurements pehamed,France) was used to measure the
were taken directly from the digital scale reading. difference in the image density of all specimens
Five measurements were done on different areas which contain different concentration ZrO2 nano
of each specimen (the same selected area of each filler in comparison with standard acrylic resin
specimen), and an average of five reading was and aluminum step wedge. (Figure 5). Five
calculated. measures in different areas of each specimen was
5- Surface roughness test done, and the mean of them was calculate.
The profilometer device (Surface roughness tester
SRT-6210, England) was used to study the effect

0% 7%

2% 5%

3% 4%

Figure.5: x-ray examination of specimens

reinforced with ZrO2 nanofiller

RESULTS modified nano-ZrO2 ,PMMA and PMMA/ZrO2

The results of infra red (IR) Spectra were nano composite help to clarify the interaction of
obtained by analyzing the characteristic vibrations nano-ZrO2 with TMSPM in one side, and
of functional groups in TMSPM, nano-ZrO2 , between TMSPM with PMMA on other

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J Bagh College Dentistry Vol. 23(3), 2011 Evaluation the effect of modified

side.Trimethoxy silypropylmethacrylate(TMSPM) (C=O, C-O)].The result of IR spectra, (Figure 7.)

can couple the ZrO2 particle to the resin matrix indicate of chemical bonded TMSPM with
(PMMA).The result of IR spectra,( Figure 6.) PMMA [change the shape of adsorption peak of
indicate of chemical bonded TMSPM on the ZrO2 (C=C)]
surface[change the shape of adsorption peaks of

Mo
Figure 6: IR spectrum of TMSPM, ZrO2, modified nano zirconia fillers.

Figure 7: IR spectra of PMMA, modified nano-ZrO2 and PMMA/ZrO2 nanocomposite.

Mean values, standard deviation; standard error,

maximums and minimums of the tests result are
presented in Table 1-5. Table 4: Descriptive data of hardness test.
Table 1: Descriptive data of impact strength. Control 2% 3% 5% 7%
Control 2% 3% 5% 7% Mean 84,62 85,01 85,22 85,34 85,71
Mean 8,9 9,25 9,3 9,7 8.775 SD 0,875 1,249 0,785 1,113 0,872
SD 0,210 0,513 0,349 0,453 0.1419 SE 0,277 0,395 0,248 0,352 0,276
SE 0,066 0,16 0,110 0,143 0.0449 Min 82,8 82,9 84,1 83,1 84,4
Min 8,5 8,75 8,75 9 8.5 Max 85,5 86,4 86,4 87,3 87,1
Max 9,25 10,25 9,75 10,25 9
Table 5: Descriptive data of radio-density
Table2:Descriptive data of transverse test.
strength test. Control 2% 3% 5% 7%
Table 3: Descriptive data of surface Mean 1,471 1,311 1,26 1,14 0,972
roughness SD 0,008 0,012 0,011 0,011 0,008
Control 2% 3% 5% 7% SE 0,002 0,004 0,003 0,003 0,002
Mean 116 120 124 132 115 Min 1,46 1,29 1,24 1,13 0,96
SD 2,429 4,383 7,598 6,97 1.78 Max 1,48 1,33 1,27 1,16 0,98
SE 0,768 1,387 2,404 2,208 0.566
Min 112,8 111,6 115,2 117,6 112.8 SEM and AFM examination of specimens
Max 120 128 141 142 117 reinforced by 2wt%, 3wt% and 5wt% nano
Control 2% 3% 5% 7% zirconia showed well dispersion of nano-
Mean 2,337 2,33 2,339 2,342 2,345 ZrO2.While examination of specimen reinforced
SD 0,235 0,268 0,256 0,190 0,079 by 7wt% nano zirconia showed aggregation of
SE 0,074 0,084 0,081 0,060 0,025 nano-ZrO2. (Figure 8).
Min 1,84 1,74 1,96 2,04 2,24
Max 2,68 2,62 2,81 2,64 2,49

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J Bagh College Dentistry Vol. 23(3), 2011 Evaluation the effect of modified

Figure 8: Specimens reinforced by 5wt% and 7% nanoZrO2 filler.(SEM)

DISCUSSION were added, this result may be due to that the nano-
The addition of modified nano-ZrO2 to ZrO2 particles have very small size and well
improve mechanical properties and to achieve dispersion, also surface roughness test is concerned
maximum radio-opacity with minimum effect on with outer surface and not with inner surface of
mechanical properties. Zirconia (ZrO2) was used composite so when small percentage of nano-ZrO2
because it is excellent biocompatible material also particles were added to acrylic resin only few
because of being white is less likely to alter particles will be involved with the surface of the
esthetic. Silanization of the nano-filler particles specimen. Many studies have been conducted on
yields a better dispersion, eliminate aggregation radio-opacity of denture base resins, decrease in
and improve its compatibility with organic radiographic densities mean increase in radio-
polymer. the addition of modified nano-ZrO2 opacity. Therefore, the transmission densitometer
powder increased the value of the impact strength show reduction in radiographic density with
and transverse strength compared to control group, increase in amount of added modified nano-ZrO2
5wt% group has the highest impact strength and powder, while the control group shows the highest
transverse strength, but increasing the percentage mean of radiographic density (low radio-opacity),
of modified nano-ZrO2 to 7wt% lowered the impact the increase in radio-opacity is statistically highly
strength and transverse strength due to significance, there was an increase in the relative
agglomeration nano-ZrO2 . The increase in impact radio opacity with the increasing of modified nano-
strength at 5% due to the interfacial shear strength ZrO2 concentration. This is oboviously due to the
between nanofiller and matrix is high due to presence of radio-opaque modified nano-ZrO2
formation of cross-links or supra molecular powder in the polymer matrix which absorbs more
bonding which cover or shield the nanofillers radiation than polymer matrix and appears more
which in turn prevent propagation of crack. Also radio-opaque. The radio opacity that occurs due to
the crack propagation can be changed by good the present of modified nano-ZrO2 powder may be
bonding between nanofiller and resin matrix (13) related to the high atomic number of Zr compared
,and the increase in transverse strength that occur to the chemical constituent of acrylic which has
with addition of 2-5wt% ZrO2 nanoparticles due to low atomic number. The absorption of X-ray by an
good distribution of the very fine size of element is dependent chiefly on the cube of its
nanoparticles enable them to enter between linear atomic number.
macromoleculars chains of the polymer, segmental
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