Powder Technology 299 (2016) 19–25

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Powder Technology

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Nanohybrid dental composite using silica from biomass waste

Mohammed Noushad ⁎, Ismail Ab Rahman, Adam Husein, Dasmawati Mohamad
School of Dental Sciences, Health Campus, Universiti Sains Malaysia, 16150 Kubang Kerian, Kelantan, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The application of nanohybrid silica from rice husk as fillers for dental composites has been explored. Spherical
Received 31 August 2015 nanohybrid silica with morphology ideal for use as fillers in dental composites having a low specific surface
Received in revised form 1 March 2016 area of 30 m2/g was extracted from rice husk by a simple precipitation method using non-toxic chemicals. Exper-
Accepted 20 May 2016
imental dental composites with two different filler/matrix ratios (Composite A: 40/60 and Composite B: 50/50)
Available online 20 May 2016
were fabricated, followed by their mechanical properties and surface roughness testing. Dental composite B
Keywords:
showed a flexural strength of 107 MPa, flexural modulus of 6.2 GPa, compressive strength of 191 MPa, Vickers'
Nanocomposites hardness of 39 HV1 and surface roughness of 0.057 Ra. The results indicate that rice husk is an inexpensive source
Resins of silica for as fillers in nanohybrid dental composites.
Mechanical properties © 2016 Elsevier B.V. All rights reserved.

1. Introduction At present the silica used in the fabrication of dental composites is

The clinical longevity of dental amalgam remains superior as com-
pared to tooth-colored materials, which possess median survival rates
below 7 years [1]. However, the demand for tooth-colored restorations,
environmental concerns and the adverse clinical reactions to amalgam
restorative materials have accelerated research into the development
of dental composite materials [2]. Nonetheless, when used as an alter-
native to amalgam, these resin based composites (RBCs), consisting of
fillers in a polymer matrix, must provide sufficient mechanical and
physical properties to withstand occlusal forces, such as high strength,
adequate wear resistance and low polymerization shrinkage which
may determine the clinical success of the restoration [3]. Current re-
search on dental composites has been more focused on the filler content
and polymerization [4].
Several fillers have been used in dental composites, of which, silica is
the most common. Silica particles of varying size, shape and content
have been used to improve the properties of dental composites. It is
widely used as fillers in many commercial dental composites, like
Heliomolar, Filtek Z250, Filtek Z100, Filtek Supreme Body, Filtek Su-
preme Translucent, Grandio, Grandio Flow, etc. [2]. The silica content,
size and shape varies from one type of dental composite to another,
some containing silica nanoclusters as well [5–7]. A study by Curtis et
al. [5] suggested that nano-sized particles and “nanoclusters” provided
distinct mechanical properties as water uptake and subsequent strength
loss was modified by the size, morphology and resulting surface area of
the fillers.
⁎ Corresponding author.
E-mail addresses: malcolmex13@yahoo.com (M. Noushad), arismail@usm.my (I. Ab
Rahman), adam@kck.usm.my (A. Husein), dasmawati@kck.usm.my (D. Mohamad).
synthesized by the sol-gel method, using toxic and expensive precur-
sors and chemicals, like tetraethylorthosilicate and the high modulus
sodium silicate. The current study focused on obtaining silica from an
inexpensive source and without the use of toxic chemicals. Rice husk
was used as the source of silica which was modified to possess a spher-
ical shape with a low specific surface area. For this purpose, an edible or-
ganic acid was used as the precipitating acid to obtain spherical
nanohybrid silica from rice husk.
Silica has been extracted from rice husk in different forms using var-
ious methods [8,9]. Spherical nanosilica has been previously prepared
from rice husk using nitric, carboxylic and orthophosphoric acids as pre-
cipitating agents in conjunction with different solvents (ethanol and 2-
propanol) [10,11]. Using orthophosphoric acid as a precipitating agent,
Zulkifli et al. [12] studied the effect of sodium silicate precursor concen-
tration, pH and solvent on the obtained silica particles. Jullaphan et al.
[13] synthesized mixed-phase bimodal mesoporous silicas (BMS) by a
simple sol–gel technique using rice husk ash-derived sodium silicate
as a silica source. Rice husk ash was treated with acid leaching and
then boiled with base to leach silica [14]. Lu and Hsieh [15] successfully
extracted amorphous silica at a 90.8% yield through base dissolution–
acid precipitation of rice straw ash generated by a three-stage heating
process.
A review of literature showed that most of the studies focused on
obtaining silica with a high specific surface area. It was reported that ac-
tive silica with a high specific surface area (up to 81m2/g) could be pro-
duced from rice husk ash after heat-treating at 973 K in air [16]. Zhang
et al. [17] prepared D-xylose and superfine silica consecutively from
rice husk. The silica obtained was of high purity (99.87 wt.%) with a di-
ameter of 30–200 nm and a specific surface of 287.86 m2/g. Porous silica
with a high specific surface area of up to 1018 m2/g, from pyrolyzed rice

http://dx.doi.org/10.1016/j.powtec.2016.05.035
0032-5910/© 2016 Elsevier B.V. All rights reserved.
20 M. Noushad et al. / Powder Technology 299 (2016) 19–25
husk was prepared in less than 10 h by precipitation at pH 3.2 [18].
Using polyethylene glycol as a template, porous silica with high specific
surface area (936 m2/g) was also produced from rice husk ash, by pre-
cipitation with ortho-phosphoric acid [19]. Our study aimed at
obtaining silica with a low specific surface area in order to assess its fea-
sibility for use as fillers in dental composites. The silica was modified to
attain a morphology ideal for use as fillers in dental nanocomposites, i.e.,
nanohybrid silica particles that are spherical in shape with a low specific
surface area. It has been shown that filler loading increases as a conse-
quence of a lower surface area to volume ratio, thereby improving me-
chanical properties [2]. The lower surface area to volume ratio has also
been shown to decrease water uptake [5]. In the current study, silica
fillers with a low surface were used so as to improve the mechanical
properties of the experimental dental composites. The dental compos-
ites prepared using this silica were tested for mechanical properties
and surface roughness. The effect of filler loading was also explored
using two different filler loads.
In our study, we chose Filtek™ Z250 as the comparative commercial
dental composite due to the hybrid nature of its filler particles and due
to the inclusion of nanoparticles in its filler system. To the best of knowl-
edge of the authors, there has not been any study on dental composites
prepared using silica from rice husk as fillers.
2. Materials and methods
2.1. Materials
Rice husk was obtained from a local rice mill in Pak Badol, Kelantan,
Malaysia. Anaylytical grade hydrochloric acid (HCl), sodium hydroxide
(NaOH), and alcohol were obtained from Merck KGaA, Germany. HCl
was used in diluted form to remove the metallic impurities from the
rice husk. Camphorquinone (CQ), N-N-dimethyl aminoethyl methacry-
late (DMAEMA) and 3-(Trimethoxysilyl) Propyl Methacrylate (γ-MPS)
were purchased from Merck, Germany, and bisphenol A glycidyl meth-
acrylate (BisGMA) and triethyleneglycol dimethacrylate (TEGDMA)
were purchased from ESSTECH, USA. All other chemicals were used
without further purification. Deionized water was used wherever
applicable.
2.2. Extraction of silica from rice husk
Rice husk was washed thoroughly with water to remove the soluble
particles and dried overnight in an oven at 110 °C. The dried rice husk
was heated in an acidic solution (1 M solution of HCl in a hot water
bath) at 75 °C for 90 min to remove metallic impurities and thoroughly
washed several times with deionized water. The wet solid was subse-
quently dried overnight in an oven at 110 °C. The rice husk was further
treated in a 10% solution of NaOH at 90 °C for 1 h and filtered to obtain
sodium silicate solution (SSS). The filtrate was used as the source for the
nanohybrid silica. The nanohybrid silica was obtained by precipitating
SSS with an edible organic acid solution with constant stirring until
the pH dropped to 8. Prior to precipitation, 40 ml of alcohol was
added to the SSS. As the pH dropped to 8, the precipitation was stopped
and the gel further stirred for another 45 min. The gel was washed sev-
eral times and centrifuged at 4000 rpm for 5 min with each wash in
order to obtain an acid free white precipitate. The white precipitate
was calcined at 500 °C for 30 min in a muffle furnace to obtain pure
white silica powder.
2.3. Surface modification of silica particles
The surface treatment solution was prepared by adding 6 wt.% γ-
MPS relative to silica to a 70/30 ethanol/water solution. The silica parti-
cles were added to the treatment solution and stirred for approximately
1 h using an overhead stirrer (model ST0707V2 Germany). The mixture
was filtered and washed with ethanol to remove excess γ-MPS. The
treated silica particles were dried in a hot air oven at 80 °C for 24 h
and characterized using FTIR and NMR spectroscopy.
2.4. Preparation of dental composite
The surface treated silica particles were used as fillers for the prepa-
ration of the experimental dental composites. Camphorquinone and
DMAEMA used as the photo-initiator system, were dissolved in the ma-
trix resin (Bis-GMA/TEGDMA, 60/40 wt.%.) under sub-ambient light.
The silanized fillers were then incorporated incrementally into the ma-
trix and thoroughly mixed to obtain a homogenous paste. A filler to ma-
trix ratio of 40/60 (Composite A) and 50:50 (Composite B) was used in
the current study. Silica was the only filler used. Z250 was used as the
comparative commercial dental composite.
2.5. Characterization of the silica from rice husk
The silica particle morphology was characterized using a transmis-
sion electron microscope (Philips Electron Optics, Eindhoven, Nether-
lands). Image analysis was done using Olympus ‘Cellsens’ software
(Soft Imaging Solution GmbH, Munster, Germany). Fourier transform
infrared spectroscopy (FTIR) analyses were carried out using a Perkin
Elmer (Spectrum 100 Optica) FTIR spectrometer (USA) by employing
the KBr pellet method. The specific surface area of the silica samples
was measured by N2 adsorption at 77 K using the Brunauer Emmett
Teller (BET) method (Quantachrome Instruments v2.02, USA).
2.6. Flexural strength and flexural modulus testing
Ten specimens with a size of (25 ± 2) × (2 ± 0.1) × (2 ± 0.1) mm
were made from each formulation of the experimental dental compos-
ites and Z250, according to ISO 4049 [20]. The dental composites were
inserted in a split stainless steel mould (25 × 2 × 2 mm), covered
with a Mylar strip and a glass microscope slide, then light-cured using
the light curing unit (Elipar™ Freelight 2 LED, 3 M ESPE). The curing
was done for 30 s in increments from each side of the mould. After
24 h storage in deionized water at 37 °C in the dark, the specimens
were removed and the dimensions measured using a digital micrometer
to correspond to ISO standards. For flexural strength and flexural mod-
ulus testing, a three-point bending test with a span of 20 mm was used
to fracture the specimens at a crosshead speed of 0.75 mm/min on a uni-
versal testing machine (UTM) (Model 3366, Instron). The flexural
strength and flexural modulus were calculated based on the following
equation:
2
Flexural strength ¼ 3PL=2bt ð1Þ
3
Flexural modulus ¼ L3 m=4bt ð2Þ
where P is the maximum force applied, L is the span length, b the
width, t is the thickness and m is the slope of initial straight line deflec-
tion curve.
2.7. Compressive strength testing
Compressive strength tests were carried out according to ISO 9917
[21] on nine cylindrical specimens, 4 mm in diameter and 6 mm in
height prepared in a split stainless steel mould. The specimens were
light cured from each side for 30 s and stored in deionized water for
24 h. Compressive strength was tested on the universal testing machine
at a crosshead speed of 0.75 mm/min. The compressive strength was
calculated based on the following equation.
2
Compressive strength ¼ 4P=πd ð3Þ
where P is the maximum force applied and d is the sample diameter.
 M. Noushad et al. / Powder Technology 299 (2016) 19–25
2.8. Vickers' hardness
Nine specimens were prepared in acrylic molds of 5 mm diameter
and 2 mm thickness, and stored in distilled water for 24 h at 37 °C.
The hardness was tested using a Vickers' hardness tester (Model VM
50, FIE) under 1 kg load for 15 min dwell time. The indentations were
made in each specimen and the mean length of the indentation was
calculated.
2.9. Surface roughness
Five specimens were prepared in acrylic molds (5 mm in diameter
and 2 mm thickness). Surface roughness was estimated using a
profilometer.
2.10. Statistical analysis
For all the tests, data obtained were statistically analyzed using One-
Way ANOVA. Post hoc Scheffe tests were performed with the level of
significance at 0.05.
3. Results
3.1. Characteristics of silica nanoparticles
TEM images of the silica (Fig. 1) shows the spherical shape of the
particles. The particle size distribution of the silica particles was calcu-
lated from the TEM images using the imaging software CellSens (Olym-
pus, USA). The particles ranged from 48 to 534 nm in diameter, with a
mean diameter of 261 nm. TEM images confirm the presence of clearly
spherical silica nanohybrid particles of varying sizes.
The FTIR result confirms that the nanohybrid particles extracted
from rice husk are indeed silica particles [22]. The BET surface area of
the silica particles was found to be 30 m2/g, whereas the average pore
diameter was found to be 5.6 nm. Fig. 2 shows the isotherm curves of
the silica sample obtained from rice husk. Based on the IUPAC classifica-
tion, the BET graphs suggest that it belongs to the type II category, with
H3 hysteresis loop. Type II isotherm represents unrestricted monolay-
er–multilayer adsorption.
3.2. Surface modification of silica particles
Silane coupling agents provide a crucial link between the filler and
the matrix that significantly enhances the mechanical properties of den-
tal composites by two possible mechanisms, namely, by enhancing dis-
persion of the filler in the matrix and by promoting a chemical bond
Fig. 1. TEM image of the spherical silica particles of varying sizes.
21
Fig. 2. The N2 adsorption/desorption isotherms of silica particles obtained from rice husk
using the precipitation technique.
between the two phases [23,24]. The intense peak at 1721 cm−1 is sug-
gestive of the hydrogen bonding between silanol groups of γ-MPS (Fig.
3). The band at 2947 cm−1 can be assigned to the symmetric and asym-
metric stretching vibrations −CH3 and −CH2 groups of γ-MPS [25]. In
the NMR analysis, chemisorptions of silane and effectiveness of modifi-
cation have been confirmed by the detection of the T1, T2 and T3 struc-
tures characteristic of the condensation of one, two and three alkoxy
groups, respectively of γ-MPS with the silica matrix (T1, − 50 ppm,
T2, −59 ppm and T3, −64 ppm) as shown in Fig. 4 [26,27].
3.3. Mechanical properties of the composites
The mechanical tests conducted were flexural strength, flexural
modulus, compressive strength, hardness and surface roughness tests.
The tests were carried out according to ISO standards. One-way
ANOVA (Fig. 5) revealed that there was no significant difference be-
tween the flexural and compressive strengths of Composites A and B,
but, there was significant difference between both Composites A and
B, and Z250. The statistical analysis results for flexural modulus showed
that there was significant different between all the composites tested
(Fig. 6). The results of all the three tests (Figs. 5, 6) revealed that an in-
crease in the filler loading resulted in an increase in the flexural
strength, flexural modulus as well as compressive strength values. Al-
though composite B contains only 50 wt.% of fillers as compared to
Z250 which contains 82 wt.% fillers [28], composite B exhibited a flexur-
al strength of more than 100 MPa. In the compressive strength and flex-
ural modulus tests also, composite B showed promising results (Figs. 5,
6).
The Vickers' hardness was also shown to be proportional to the
amount of filler loading, with the hardness increasing with an increase
in filler loading. One way ANOVA revealed that the Vickers' Hardness
and surface roughness were significantly different between all the den-
tal composites tested (Fig. 7). Z250 exhibited the highest hardness
values, followed by composite A and then composite B. In the surface
roughness testing, the roughness was found to be inversely proportion-
al to the filler loading. Z250 exhibited the lowest surface roughness
value, followed by composite A and then composite B (Fig. 8).
4. Discussion
Several researchers have concluded that rice husk is an excellent
source of high grade amorphous silica [29–31]. Amorphous silica pow-
der has been used in several applications. One application where the sil-
ica obtained from rice husk could be incorporated is as fillers in dental
composites and this has not been studied widely. In this study, silica
was extracted from rice husk and its morphology modified to make it
suitable for use as fillers in dental composites.
22 M. Noushad et al. / Powder Technology 299 (2016) 19–25

Fig. 3. FTIR spectra of pure silica and modified silica (a) γ-MPS (b) pure silica and (c) modified silica using ethanol as solvent.

Fig. 4. 29Si CP/MAS solid NMR of surface modified silica particles. (A) plain silica and (B) using using ethanol as the solvent.
 M. Noushad et al. / Powder Technology 299 (2016) 19–25
Fig. 5. Flexural and compressive strengths of the two experimental dental composites and
Z250.
The most favorable characteristics of silica particles as fillers in den-
tal composites are their nanosize and spherical shape. The spherical
shape of the fillers allow increased filler loading and also enhances the
fracture strength of the composites [6,32]. Moreover, a combination of
relatively small and varying size (hybrid) fillers allow a more dense
packing, which in turn increases the filler volume-fraction of the
resin-composites [33]. TEM images of silica prepared in this study re-
vealed that the silica particles are nanohybrid and spherical in shape.
From the evaluation of the particle size distribution, it was revealed
that the silica particles are of varying sizes, with a mean diameter of
261 nm, the size range varying from 48 to 534 nm in diameter. From
the morphology, it was therefore expected that it could be ideal for
use as fillers in dental composites.
To study the effect of filler content on the mechanical properties,
composites with varying filler, matrix ratios (Composite A: 40/60 and
Composite B: 50/50) were prepared. Mechanical testing was carried
out according to ISO standards. According to ISO [20], any dental
Fig. 6. Flexural modulus of the two experimental dental composites and Z250.
23
Fig. 7. Hardness values of the two experimental dental composites and Z250.
composite with a flexural strength equal to or greater than 50 MPa is
suitable for use in anterior restorations, whereas those with a flexural
strength equal to or above 80 MPa are suitable for use as posterior res-
torations. Both composites, A and B showed good mechanical properties
(Table 1), with both exhibiting flexural strength values well above the
minimum requirement for posterior restorations. The results in Figs. 5
and 6 revealed that an increase in the filler loading resulted in an in-
crease in the flexural strength, flexural modulus and compressive
strength values. Although composite B contains only 50 wt.% of fillers
as compared to 82 wt.% in Z250, its flexural strength was 100 MPa.
An increase in filler loading showed an increase in compressive
strength and flexural modulus values as exhibited by composite B. Mod-
ulus and hardness are known to improve as the filler content increases
[33]. This is true only up to a certain threshold level, beyond which, the
properties diminish with increasing volume-fraction [34]. In this study,
an increase in filler content was shown to improve the mechanical
properties. Zirconia is a major contributing factor in increasing the com-
pressive strength of dental composites as revealed in a study on zirconia
nanoclusters based dental composites [35]. In this study, good compres-
sive strength was attained even without the addition of zirconia or
other fillers.
The hardness of a dental composite has been shown to be dependent
on the filler content [36]. Labella et al. [24] suggested an increase in the
Fig. 8. Surface roughness values of the two experimental dental composites and Z250.
24 M. Noushad et al. / Powder Technology 299 (2016) 19–25
Table 1
Flexural strength, flexural modulus, compressive strength, Vickers' hardness and surface roughness results of the experimental dental composites and Z250.
Experimental dental composite [filler/matrix ratio (wt.%)] Flexural strength
(MPa)
40/60 92.4 ± 10.8
50/50 106.6 ± 15.2
Z250 131.5 ± 19.1
Vickers' hardness with an increase in the filler content, which is in
agreement with this study. Incorporation of other fillers like zirconia,
aluminum oxide, etc., increases the hardness of dental composites
[37]. Unlike Z250 which contains zirconia [38], the experimental dental
composites contained only silica as the filler. Nonetheless, the experi-
mental composites exhibited reasonable hardness values.
Incorporation of nano size fillers has been shown to reduce surface
roughness as the nanoparticles can disperse homogenously in the poly-
mer matrix. In this study, both the experimental composites exhibited
positive surface roughness values with composite B exhibiting lesser
values. The comparatively higher surface roughness in composite A
could be a result of voids in the resin matrix, due to the lower filler load-
ing. According to Willems et al. [39], the enamel surface roughness
value at enamel-to enamel occlusal contact areas of 0.64–0.25 μm is
considered to be the standard with which to compare the roughness
values of composites. In this study, however, the surface roughness for
both experimental composites were even less than the threshold level
of 0.2 μm suggested by Bollenl et al. [40], below which, no bacterial ac-
cumulation could be expected.
Several commercial dental composites use two or more fillers in
order to improve the properties. For example Filtek Silorane from 3 M
ESPE uses silanized quartz and yttrium fluoride as fillers. Several com-
mercial dental composites use other fillers in conjunction with silica.
For example Filtek Supreme XT, which is a nanohybrid filler, uses silica
nanofiller and zirconia/silica nanocluster as fillers [4]. Grandio and
Grandio Flow uses silica and barium-alumia borosilicate as fillers [2]. It
should be noted that in this study, only silica obtained from rice husk
was used as the filler.
The use of small, spherical, varying size fillers have several positive
effects on the dental composites. It allows a more dense packing,
which eventually increases the filler volume-fraction of the dental com-
posites. The spherical shape of the fillers, especially in a mixture of dif-
ferent sizes, favors geometrically the incorporation of more inorganic
fillers in the resin matrix [41]. The spherical shape also improves the
fracture strength of the materials as stresses tend to develop preferably
at sharp edges of the fillers [32]. The silica obtained from rice husk pos-
sesses all the above-mentioned characteristics, which could be respon-
sible for acquiring good mechanical properties when used as fillers in
dental composites.
5. Conclusions
It was possible to prepare nanohybrid silica particles from rice husk,
with characteristics ideal for use as fillers in dental composites. The
preparation procedure was simple and cost effective. From the data it
can be concluded that the mechanical properties of dental composites
using silica obtained from rice husk as fillers showed promising results.
Therefore, it can be inferred that silica from rice husk is ideal for use as
fillers in dental composites.
Acknowledgement
The authors would like to express their gratefulness to Universiti
Sains Malaysia for the Research University Grant (RU-1001/PPSG/
814110) which supported the current research. Mohammed Noushad
would also like to thank USM for providing the USM fellowship.
Flexural modulus Compressive strength Vickers' hardness Surface roughness
(GPa) (MPa) (HV1) [Ra(μm)]
4.5 ± 0.44 181.4 ± 12.9 33.44 ± 1.26 0.07 ± 0.00
6.2 ± 0.82 190.6 ± 21.7 38.66 ± 0.70 0.057 ± 0.00
10.1 ± 0.93 269.6 ± 22.9 78.46 ± 0.93 0.031 ± 0.00
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