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Available online at www.sciencedirect.com

ScienceDirect

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

Development of 3D printed resin reinforced with

modified ZrO2 nanoparticles for long-term
provisional dental restorations

Sultan Aati a,b , Zohaib Akram a , Hien Ngo a , Amr S. Fawzy a,∗
a UWA Dental School, University of Western Australia, 17 Monash Avenue, Nedlands WA 6009, Australia
b Dental Health Department, College of Applied Medical Sciences, King Saud University, Riyadh, 11433, Saudi Arabia

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

Article history: Objective. To characterize and investigate efficacy of loading functionalized ZrO2 nanoparti-
Accepted 12 February 2021 cles in 3-dimensional (3D) printed acrylate ester-based resin subjected to accelerated aging
Available online xxx in artificial saliva. As well as to evaluate the effect of ZrO2 nanoparticle volume fraction
addition on mechanical and physical properties of printed composite.
Keywords: Methods. Functionalized ZrO2 nanoparticles were characterized using TEM and Raman
3D printed resins spectroscopy. 3D printed dental resin was reinforced, with ZrO2 nanoparticles, in the
Zirconium oxide concentration range (0–5 wt.%). The resulted nanocomposites, in term of structure and phys-
Nanoparticles ical/mechanical properties were evaluated using different mechanical testing, microscopic
Nanocomposites and spectroscopic techniques.
Provisional restorations Results. ZrO2 based nanocomposite was successful and formed composites were more
ductile. Degree of conversion was significant at the highest level with blank resin and
1 wt.%. Sorption revealed reduction associated with volume fraction significant to neat resin,
however solubility indicated neat and 4 wt.% had the lowest significant dissolution. Vick-
ers represented critical positive correlation with filler content, while nanohardness and
elasticity behaved symmetrically and had the maximum strength at 3 wt.% addition. In addi-
tion, 3 wt.% showed the highest fracture toughness and modulus. Improvement of flexural
strength was significantly linked to filler concentration. Overall properties dramatically were
enhanced after 3 months aging in artificial saliva, especially degree of conversion, micro-
hardness, nanoindentation/elasticity, and flexural modulus. However, significant reduction
was observed with flexural modulus and fracture toughness.
Significance. The outcomes suggest that the newly developed 3D printed nanocomposites
modified with ZrO2 nanoparticle have the superior potential and efficacy as long-term
provisional dental restoration materials.
© 2021 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

∗
Corresponding author at: UWA Dental School, University of Western Australia, 17 Monash Avenue, Nedlands, WA 6009, Australia.
E-mail address: amr.fawzy@uwa.edu.au (A.S. Fawzy).
https://doi.org/10.1016/j.dental.2021.02.010
0109-5641/© 2021 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

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digital technique to produce surgical guides, custom tray, diag-

1. Introduction
In fixed prosthodontics, the performance of provisional
restorations is essential and integral to the success of the
final prostheses [1]. Provisional restorations are much more
than just temporary restorations as one can argue that
they contribute significantly to the overall wellbeing of the
patients. They restore function, improve aesthetics, keep ver-
tical distance, and maintain proper occlusion [2]. In addition,
provisional prostheses should protect the prepared teeth from
thermal and mechanical stresses. The requirements on provi-
sional materials become more complex in implant-supported
prosthesis, owing to complex osseointegration mechanisms
and recovery process [3]. Therefore, when designing pro-
visional restorations, it is essential to incorporate all the
other important requirements such as superior mechani-
cal/physical properties, adequate biocompatibility, ease of
handling, and cost effectiveness of the material [4,5].
Provisional restorations are commonly manufactured
using composite resin-based materials, which are homoge-
nized combination of filler particles, a coupling agent, resin
matrix, and catalyst [6]. However, the oral environment is
challenging to these materials. They are exposed to an exces-
sive water and functional stress, which causes degradation
and subsequently lead to clinical failure due to the brittle-
ness nature and low fracture toughness of these materials [7].
Accordingly, efforts have been made to improve longevity and
performance of provisional composite resins. Most of these
recent attempts have focused on modifying the resin matrix by
the incorporation of various organic and inorganic, nano fillers
that create nanocomposites with superior properties [8,9].
Previous studies have revealed that modifying dental
resins with different fillers, which typically have micro and
nanoscale sizes significantly enhanced mechanical, physical
and biological properties [10,11]. On the other hand, some of
these modifications showed adverse effects that lead to lower
material efficiency, such as generating voids/porosity, decreas-
ing biocompatibility, limiting depth of curing and degree of
polymerization especially overtime [12–15].
Ceramic fillers have become one of the most used reinforce-
ment filler materials in many resin-based dental composites.
Among these, zirconium oxide (ZrO2 ) nanoparticles are
excellent candidates, with promise as a filler additive for
clinical use. Studies showed that inconsequential addition of
ZrO2 nanoparticles (≤5 wt.%) enhanced mechanical, physical
and/or biological properties including flexural strength, frac-
ture toughness, hardness, wear resistance, thermal stability,
and biocompatibility of the nanocomposites [13,15–18].
Three-dimension (3D) technology has substantially influ-
enced materials production and consolidated different
application outcomes. This high-tech advancement has been
implemented in many medical and dental applications with
the potential of future wider usage owing to its relatively
high precision and economic advantages. For many years,
computer-aided design and manufacturing (CAD/CAM) has
been used in dentistry to produce ceramic restorations and
dental implants [19,20]. Additive manufacturing (Rapid Proto-
typing) has also had a remarkable impact on dental prosthesis
fabrication. 3D photo-curable resin printers have a superior
nostic models, prosthesis wax patterns, splints, and interim
restorations [21,22]. Certainly, this approach could be taken
up further to involve the fabrication of complete dentures;
however, such techniques are limited to short-term use [23].
Therefore, recent studies have emphasized developing print-
able resin that is modified with nanostructure to optimize
dental restoration mechanical properties and antimicrobial
behavior [24].
Taking an advantage of 3D printing technology, this
study aims to modify printable liquid resins, for provisional
dental restorations, with ZrO2 nanoparticles at different
loading contents. In addition, to characterize the resulted
nanocomposites in term of structure and physical/mechanical
properties using different microscopic and spectroscopic tech-
niques; and mechanical/physical assessment methods. The
null hypotheses are modifying 3D-printable resin materials
with silanized ZrO2 nanoparticles, at different contents, have
no effect on degree of conversion, surface roughness, flex-
ural properties, fracture toughness, surface microhardness
and nanoindentation properties of the printed resin-based
nanocomposites with aging in artificial saliva up to 3 months.
2. Materials and methods
All materials were used without further purification. 3-
(Trimethoxysilyl)propyl methacrylate with molecular weight
248.35 (␥-MPS), calcium chloride anhydrous purity ≥97%
(CaCl2 ), magnesium chloride hexahydrate (MgCl2 6H2 O)
purity ≥99%, potassium dihydrogen phosphate (KH2 PO4 )
purity ≥99%, potassium chloride (KCl) purity ≥99%,
sodium azide (NaN3 ) purity ≥99.5%, and hydroxyethyl-
piperazineethane-sulfonic acid (HEPES) buffer were purchased
from Sigma–Aldrich (Australia). Isopropyl and ethanol abso-
lute alcohol were purchased from ThermoFisher Scientific
(Australia). Zirconia nano-powder with purity of 99% and
particle size ranges from 20–40 nm was obtained from Jiangsu
XFNANO Materials (China). 3D printed crown and bridge
dental resin was purchased from NextDent (Netherlands).
2.1. Surface modification of ZrO2 nanoparticles
To expedite an ultimate interaction between ZrO2 nanoparti-
cles and resin mixture, nanoparticles were functionalized with
silane coupling agent ␥-MPS (Sigma–Aldrich, Australia) to form
a reactive group. The addition of the coupling agent was mea-
sured as the minimum required amount to coat ZrO2 surface
based on Arkle’s (Eq. (1)) as follows [25]:
Amount of silane (g)
Amount of nanoparticles (g) × Surface area (m2 /g)
= (1)
Minimum coating area of  MPS (m2 /g)
Where surface area for ZrO2 equals 12.31 m2 /g, and the mini-
mum coverage area of ␥-MPS is 314 m2 /g. Briefly, ZrO2 powder
was dried overnight in the oven at 110 ◦ C before coating. ␥-MPS
(400 mg) was dissolved in ethanol and gently stirred for 60 min,
using hydrochloric acid (HCl) to accelerate hydrolyzes process,
pH was adjusted between 4–5 and temperature was set at

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60 ◦ C. After that, nanoparticles were dispersed in ethanol and
mixed for 2 h at 600 rpm. ␥-MPS solution was dropped wisely,
and magnetic stirring continued for another 4 h. The mixture
was centrifuged for 1 h at 4500 rpm, then washed twice with
80% ethanol to remove any unreacted traces, and the slurry
was collected and dried overnight at 80 ◦ C [16].
2.2. Nanocomposite formation and 3D printing
The newly formed nanocomposites were obtained from subse-
quent incorporation of ZrO2 nanoparticles at various contents
of 1%, 2%, 3%, 4%, and 5% (w/w). Preparation procedures
involved the gradual addition of nanoparticles proportions
into the printable resin solutions under continuous mag-
netic stirring (Thermo Fisher Scientific, Ceramic) for 24 h,
followed by sonication for 30 min in distal water bath. For 3D
printing, a digital light processing printer (Kulzer 3D Printer
System, Australia) was used. Different sizes and geometries
of specimens were designed by CAD software. The generated
stereolithography (STL) files were sliced using Cara Print 4.0
software and then sent to the 3D printer. The modified resin
mixtures were poured in the tray carefully to avoid air bubbles.
The job resolution was set at 50 ␮m thickness for each layer.
The printed specimens were scrapped off from the printing
stage, cleaned, and sonicated twice with isopropanol for 5 min
to remove any excess uncured resin, then rinsed twice with
distal water. To reach maximum strength, they exposed to a
post-curing step. The printed specimens were placed in a high-
performance light curing unit at 200 W for 20 min (HiLite Power
3D; Kulzer). Finally, specimens were finished using silicon car-
bide grinding paper with ascending grid size 600, 800, and
1200 for 30 seconds with 300 RPM under water coolant. Polish-
ing was performed using TriDentTM cloth with 1 ␮m diamond
paste followed by fine MicroClothTM with 0.25 and 0.05 ␮m,
respectively, and a sonication step in between to avoid surface
contamination.
2.3. Preparation of the artificial saliva solution
To mimic the environment of the oral physiological condi-
tions, specimens were stored in artificial saliva for 3 months
at 37 ◦ C. The artificial saliva solutions were replenished every
fortnight to ensure consistency and freshness throughout the
storage time periods. The artificial saliva solution was pre-
pared according to previously published protocol: 0.7 mM of
CaCl2 , 0.1 mM of MgCl2 6H2 O, 4.0 mM of KH2 PO4 , 30 mM of KCl,
30.8 mM of NaN3 , and 20.0 mM of HEPES were added to 1000 mL
distal water, and pH was adjusted to 7.0 [26].
2.4. Microscopic characterization
Coated and uncoated ZrO2 nanoparticles were viewed using
transmission electron microscope (TEM: FEI Titan G2 80–200
TEM/STEM; Thermo Fisher Scientific). An amount of 1 mg of
powder was dispersed in dry ethanol, gently shacked, and
then pipetted on copper grid coated with carbon. After drying,
specimens were placed in a holder that had an accelerating
voltage of 200 kV.
For studying the surface morphological of the fractured
3D printed resins/nanocomposites, specimen from each group
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provisional dental restorations. Dent Mater (2021), https://doi.org/10.1016/j.dental.2021.02.010
xxx.e3
was mounted on aluminum stubs and sputtered with a 4.0 nm
thick layer of platinum. To improve imaging quality, outer
edges of all specimens were isolated with copper film for
increasing electron beam reflectance, and specimens were
imaged with scanning electron microscope operated with
accelerating voltage of 5.0 kV (Verios XHR SEM; Thermo Fisher
Scientific, USA).
Atomic force microscope (AFM) characterization was per-
formed to investigate the effect of nanoparticles incorporation
on the 3D printed resin surface micro-topography. Unmodi-
fied and modified, with ZrO2 nanoparticles, specimens were
investigated under AFM (Keysight 5500 SPM, USA) for surface
micro-topography and roughness. AFM was operated at high
resolution under the acoustic AC mode. All measurements
of 512 lines × 512 lines were taken at a scan rate of 1.5–2.2
lines per second at room temperature. The 3D morphologi-
cal reconstructions were obtained by Gwyddion software 2.55.
The average roughness of the surface (Ra ) was measured based
on different random sites within a 1 ␮m × 1 ␮m area size.
2.5. Raman spectroscopy analysis
A Raman microscope (WITec alpha 300RA; Germany) equipped
with a laser having an excitation wavelength of 532 nm was
used to estimate degree of conversion (DC). First, the sys-
tem was calibrated using silicon wafer film, and a standard
reference peak was recorded at 520 cm−1 . Printed resin speci-
mens 2 × 5 mm size were placed on a glass slide, then random
multiple sites were selected with a 20× objective lens. The
spectrums were collected with an integration time of 0.5 sec-
onds and 200 accumulations. To determine DC, aromatic peak
intensity of control uncured resin at 1610 cm−1 was taken
as an internal reference for calculation. The ratio between
aliphatic (C C) at 1640 cm−1 and the aromatic (C C) at
1610 cm−1 peaks was used to calculate percent DC for each
specimen using a baseline method to calculate area under
curve using Project Five & Origin lab Pro software.
 
AliphaticCured / Aromatic Cured
% DC = 1 − *100
Aliphatic Uncured / Aromatic Uncured
where Aliphaticcured is the peak absorption of polymerized
resin at 1640 cm−1 , Aromaticcured is the peak absorption of
polymerized resin peak at 1610 cm−1 , Aliphaticuncured is the
peak absorption of unpolymerized resin at 1640 cm−1 , and
Aromaticuncured is the peak absorption of the unpolymerized
resin peak at 1610 cm−1 [27].
2.6. 3-points bending test
The variations in the flexural strength and modulus of the
3D printed specimens were characterized through a 3-point
bend test using a universal testing machine (ElectroPulsTM
E3000; Instron USA), according to the International Stan-
dards Organization (ISO) 10477, after 24 h and 3 months
storage in the artificial saliva solution at 37 ◦ C [28]. Fif-
teen specimens were assigned per group with dimensions
of (25 mm × 2 mm × 2 mm), and specimens were inspected for
any deformity, these specimens were excluded before storage
and testing. For testing, each specimen was mounted on a 3-
points fixture with 20 mm support distance; and a load was
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applied until fracture at a cross-head speed of 1 mm/min. The
flexural strength (␴) and flexural modulus (E) were calculated
in MPa according to the following formula [29]:
3Fl
 =
2bh2
F1 l3
E=
4bh3 d
Where F is the maximum applied load (N); l is the distance
(mm) between the supports; b is the width of the test specimen
(mm); h is the height of the specimen (mm); F1 is the load (N)
at a point in the straight-line portion of the load/deflection
curve; and d is the deflection (mm) at load F1 .
2.7. Fracture toughness testing
To assess fracture toughness, the modified/unmodified 3D
printed resin specimens stored in the artificial saliva solution
for 7 days and 3 months respectively, were character-
ized using the same 3-points bending fixture as described
above, according to the ISO 20795 standard [29]. All spec-
imens were designed and printed with dimensions of
39 mm × 8 mm × 4 mm, with a predefined notch made in
the center of 3.2 mm length. Subsequently, specimens were
inspected visually to exclude damaged specimens before stor-
age process. For testing, each specimen was loaded on a
fixture with 32 mm support span with a displacement rate of
1 mm/min. The recorded maximum force was used to deter-
mine the fracture toughness (KIc ) according to the following
formula [29]:
f Fmax l
 grams per cubic millimeter according to the following formula
KIc = ∗ 10−3
bh3/2
3x1/2 [1.99−x(1−x)(2.15−3.93x+2.7x2 ]
Where f =   , x = a/h, Fmax is the
2(1+2x)(1−x)3/2
maximum recorded load (N) at fracture; l is the support span
distance (mm); b is the width of the specimen (mm); h is the
height of the specimen (mm); and a is the crack length (mm).
2.8. Vickers microhardness test (VHN)
The surface microhardness of the 3D-printed resin specimens
was measured and reported as Vickers hardness num-
ber (VHN) using microhardness tester (Duramin-40; Struers,
Australia). Specimens from each group (n = 6) were tested at
24 h and 3 months storage in the artificial saliva. A pyramid-
shaped diamond indenter with specified angle was forced into
the surface using a load force of 50 gf and dwell time of 30 s.
Each specimen had a line pattern with 10 indentation points
at 1 mm distance, and the result was reported as the average
of indented locations for each specimen.
2.9. Nanoindentation properties
Nanomechanical properties, in term of nanohardness and
elastic modulus, were measured (n = 5) with a Hysitron
Triboindenter TI 950 machine, equipped with a Berkovich dia-
mond indenter, at 24 h and 3 months storage in the artificial
Please cite this article in press as: Aati S, et al. Development of 3D printed resin reinforced with modified ZrO2 nanoparticles for long-term
provisional dental restorations. Dent Mater (2021), https://doi.org/10.1016/j.dental.2021.02.010
saliva, the result was reported as an average of 12 indents
for each specimen. A double calibration technique was used
to minimize any error during measurement, first with alu-
minum to clean any traces attached to the indenter, and
then using a fused quartz reference specimen. A grid pattern
(2)
of 3 × 4 indents at separations of 50 ␮m was used for each
specimen before and after aging in the artificial saliva for 3
months. Nanohardness (H) and reduce elastic modulus (Er)
(3)
were calculated based on load function profile for 5 s of load-
ing/unloading at maximum load force of 5000 ␮N and holding
time for 10 s.
2.10. Water sorption and solubility evaluation
To evaluate the water sorption and solubility of the printed
resin nanocomposites, disc shaped specimens (n = 7) with a
diameter of 15 mm and thickness of 1 mm were characterized
according to ISO 10477 [28]. Specimen volume was measured
using a digital caliper, then specimens were placed in a des-
iccator containing silica gel for 24 h at 37 ◦ C. After that they
were transferred into a second desiccator with similar condi-
tions for 2 h. specimens were taken out and weighed using an
analytical balance with an accuracy of 0.001 g (Ohaus PR224;
Germany), The drying procedure was repeated as mentioned
above until constant mass (m1 ) was reached. Subsequently,
specimens were immersed in distal water (15 mL) and kept at
37 ◦ C for 7 days. After that, specimens were removed, wiped
with absorbing paper, and weighed again (m2 ). To obtain (m3 ),
specimens were reconditioned in a desiccator following the
previous method until they achieved constant mass. Water
sorption (ws ) and solubility ( sl ) were calculated in micro-
(4) [28]:
ws =
m2 − m3
(5)
V
m1 − m3
sl = (6)
V
where m1 is the mass of the conditioned specimen, in micro-
grams; m2 is the mass of the specimen, in micrograms, after
immersion in water for 7 days; m3 is the mass of the recondi-
tioned specimen, in micrograms; and V is the volume of the
specimen, in cubic millimeters. This was done to analyze the
effect of artificial aging on sorption and solubility.
2.11. Statistical analysis
Data were presented as means ± standard deviations and
analysed using ANOVA followed by Tukey’s post hoc test
for pair-wise comparison at statistical significance of P-
value < 0.05. A repeated measures ANOVA testing was
performed to generate the statistical significance for flexural
strength, flexural modulus, fracture toughness, DC, micro-
hardness, and nanomodulus for two time points (before and
after aging).
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the groups. In addition to ductile failures and roughness, sec-

3. Results ondary cracks were clearly noticeable on the site with slight
agglomeration of nanoparticles due to inappropriate distribu-
3.1. Microscopic characterization tion (Fig. 1e and f). Overall, bulk voids due to improper adhe-
sion of ZrO2 nanoparticles were not detected (Fig. 2g), due to
The particle size and morphology of ZrO2 nanoparticles were
the influence of coupling agents and an even, uniform coating
analyzed using TEM (Fig. 1). Acquired images from TEM
layer. AFM rendered 3D images show the morphological topog-
showed that uncoated ZrO2 has a uniform shape with par-
raphy of unmodified resin as well as progression of incorpora-
ticle size range between 20–40 nm (Fig. 1a and b). Silanization
tions with various concentration of ZrO2 (Fig. 3A a–f). Flat and
with ␥-MPS did not affect the basic structure of nanoparticles,
smooth surface structures obviously can be seen over blank
other than forming a thin coating that ranged between 2–4 nm
resin. Minor channels and tracks are also found, due to the fin-
(Fig. 1c and d).
ishing and polishing step (Fig. 3a). Different peaks emerge with
The fractured end of the representative specimens of den-
the 1% and 2% additions; however, the concentrations were
tal resin and loaded resin with ZrO2 was evaluated using SEM
not sufficient to cover the surface completely (Fig. 3b and c).
micrographs (Fig. 2a–g). Brittle failure with smooth surfaces
A homogenous distribution of nanoparticles with 3% and 4%
and plane feature were associated with control dental resin
appears within 3D images (Fig. 3d and e), as well as negligible
(unmodified) specimens (Fig. 2a). The addition of 1% ZrO2
cluster formation, which is a beginning sign of agglomera-
nanoparticles showed a comparable pattern of fracture, which
tion developing with the 4% addition. With 5% incorporation
was mostly flat and identical to unmodified resin. With 2%
(Fig. 3f), the surface becomes more congested and has the
and 3% added, both ductile and brittle modes of failure were
most texture among the groups. Although there were different
exhibited with variable morphological features and a gradual
concentrations used, all specimens showed similar average
grade of surface roughness increase of 2% and 3%, respec-
surface roughness after the finishing and polishing procedure
tively (Fig. 2c and d). After increasing the proportion fraction
(Fig. 3B). The pattern was unpredictable, and the evidence
of ZrO2 nanoparticles up to 4% and 5%, a rougher structure
of correlation between concentration amount and roughness
was observed compared to any lower concentration among
was missing because of the polishing procedure.

Fig. 1 – Transmission electron microscopy (TEM) images illustrate basic zirconium oxide (ZrO2 ) nanoparticles (a and b) and
those modified with silane coupling agent (c and d). Arrows show the thin film coating of 3-(trimethoxysilyl)propyl
methacrylate (␥-MPS).

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Fig. 2 – Scanning electron microscopy (SEM) images show variable morphological structure of nanocomposites after
fracture. (a) Unmodified resin, (b) resin with 1% addition of zirconium oxide (ZrO2 ), (c) with 2%, (d) with 3%, (e) with 4%, and
(f) with 5% nanoparticles incorporated with experimental resin. (g) Highly magnified image presents ZrO2 nanoparticles
homogenously embedded with resin matrices.

3.2. Raman spectroscopy
Fig. 4(A) illustrates Raman spectrums for unmodified/modified
ZrO2 nanoparticles. It is clear that the hydrolyzed ␥-MPS
has attached to the hydroxyl group of zirconia (Zr–OH),
which leads to a dehydrated reaction followed by forma-
tion of chemical bonds between nano-ZrO2 and the coupling
agent [30,31]. Therefore, peaks appeared at 1639 cm−1 and
1716 cm−1 , assigned to the vibration of the aliphatic carbon
double bond to carbon (C C) and oxygen (C O), respectively.
The emerging peaks at 1554 cm−1 and 1457 cm−1 referred to
the skeletal vibrations of the aromatic benzene ring. Peak
intensity at 1100 cm−1 increased, which perhaps refers to Si-O
as one of the four shoulders associated with this peak [32].
Fig. 4(B) shows the presence of ZrO2 nanoparticles in addi-
tion to dental resin. Thus, the peak at 639 cm−1 is assigned
to the tetragonal phase of ZrO2 , which confirms formation
of nanocomposite [33]. An insufficient degree of polymer-

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Fig. 3 – (A) Atomic force microscopy (AFM) images represent different concentrations of zirconium oxide (ZrO2 )
nanoparticles. (a) Blank resin, (b) 1%, (c) 2%, (d) 3%, (e) 4%, and (f) 5% ZrO2 . (B) Graph shows fractional proportion of ZrO2
effect on modified resin surface roughness. Statistical analysis showed no significant difference among groups (p > 0.05).

ization might significantly reduce the performance of resin
in terms of mechanical properties and biocompatibility [34].
Fig. 4(C) shows that the addition of ZrO2 has considerable
impact on the nanocomposite degree of conversion compared
to unmodified resin, especially after 1% addition of nanopar-
ticles. However, after storage in artificial saliva, the ratio of
DC remarkably increased equally among all groups, and the
difference became unnoticeable. This improvement ranged
between 11.8%–15.3% in comparison to specimens that were
measured after exposure to printer UV light only, where the
statistical analysis showed strong interaction between two dif-
ferent time points. This enhancement in DC proportion might
be related to the process associated with wash out of free
unpolymerized monomer molecules.
3.3. Water sorption and solubility
The results of the water sorption and solubility tests are
shown in Table 1. It is noted that the water sorption was
decreased as the filler content was increased. The high-
est sorption was observed with unmodified printed resin
(47.78 ± 1.34), while the lowest value was 40.07 ± 1.03 for 5 wt.%
ZrO2 . The blank resin showed significant sorption increments
among all other groups (p < 0.01), as the mean difference
from 1–5 wt.% ZrO2 additions was insignificant. Similar sig-
nificance was detected among all the storage specimens of 90
days compared to unmodified resin. Moreover, all specimens
demonstrated a slightly higher rate of sorption after aging,
except 2 wt.%, which decreased, whereas a critical change
in weight deference was noticed with 3, 4, and 5 wt.% ZrO2
(p < 0.01). Inconsistent trends of solubility were noticed among
the tested groups. The lowest value belonged to neat resin
(1.54 ± 0.63), while the highest attributes were found with
2 wt.% ZrO2 (5.66 ± 0.65). Regardless of the variations, con-
trol and 4 wt.% ZrO2 had significantly lower solubility among
groups. This scenario completely changed with aged speci-
mens, where the lowest value was recorded for 3 wt.% ZrO2
(−2.51 ± 0.64) and the highest for 2 wt.% ZrO2 (−0.40 ± 0.43).
Above all, the statistical analysis showed significant interac-
tion between incubation time versus composition content in
terms of sorption and solubility.

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Fig. 4 – Raman spectrums demonstrate (A) Formation of covalent bond between ZrO2 and silane coupling agent and (B)
increasing proportion percentage of nanoparticles within resin. (a) Control unmodified, (b) 1% ZrO2 , (c) 2% ZrO2 , (d) 3% ZrO2 ,
(e) 4% ZrO2 , and (f) 5% ZrO2 . The peak at 639 cm−1 refers to Zr–O. (C) The degree of conversion deference for 3-dimensional
(3D) printed nanocomposite immediately after printing and after storage in artificial saliva. (*p < 0.05, **p < 0.01, and
***p < 0.001).

Table 1 – Outlines mean and standard deviation of physical properties among groups.
Roughness (nm) % DC Water sorption (␮g/mm3 ) Solubility (␮g/mm3 )

Before After Before After Before After

Unmodified 1.22 (0.15) 72.50 (0.66) 76.05 (6.55) 47.21 (0.92) 47.78 (1.34) 1.54 (0.63) −2.02 (0.92)
1% ZrO2 1.27 (0.11) 70.11 (3.46) 78.78 (4.80) 42.28 (1.92) 42.68 (0.86) 4.28 (0.64) −0.97 (0.54)
2% ZrO2 1.40 (0.18) 51.60 (2.90) 81.43 (2.11) 42.20 (1.42) 41.96 (1.86) 5.66 (0.65) −0.40 (0.43)
3% ZrO2 1.24 (0.08) 61.57 (2.10) 80.95 (2.77) 41.23 (1.28) 43.98 (0.91) 5.09 (0.46) −2.51 (0.64)
4% ZrO2 1.40 (0.10) 56.16 (6.90) 79.95 (1.37) 40.82 (1.24) 42.60 (0.91) 1.86 (0.28) −1.54 (0.85)
5% ZrO2 1.30 (0.18) 55.71 (1.56) 80.44 (1.34) 40.07 (1.03) 43.17 (0.96) 3.15 (0.55) −1.37 (0.72)

3.4. Flexural strength and modulus of elasticity
Six study groups with 15 specimens each with different con-
centrations of ZrO2 nanoparticles in the specimens were
tested before and after aging. The flexural strength, flexu-
ral modulus, and standard deviations of each group in MPs
are illustrated in Table 2. The results revealed that all study
groups efficiently exceeded the minimum required level of
crown and bridge material ISO standard 10477 for flexural
strength (≥50 MPa). The addition of 3%, 4%, and 5% ZrO2
nanoparticles significantly improved flexural strength of the
dental resin compared to unmodified printed resin, whereas
1% and 2% showed a negligible increasing trend. As can
be clearly seen in Fig. 5(A), the maximum mean flexural
strength around 111.59 MPa belongs to 5% ZrO2 filling and
then starts to decrease until the minimum value with unmod-
ified resin (98.32 MPa). Prolonged storage affected all tested
groups, where the reduction of strength for all tested groups
ranged between 0.8% up to 11% compare to unaged speci-
mens. Although 3%, 4%, and 5% of incorporation presented

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Fig. 5 – Bar graphs demonstrate (A) flexural strength, (B) flexural modulus, and (C) fracture toughness of unmodified printed
resin and resin modified with 1% ZrO2 nanoparticles up to 5% before aging (stripped bars) and after storage aging with
artificial saliva for 3 months (gray bars). (*p < 0.05, **p < 0.01, and ***p < 0.001).

the highest level of loss (103.07, 97.96, and 103.24, respec-
tively), they stayed with a higher value compared to control
group after aging. A comparison of the flexural modulus of
the materials (Table 2) indicates that 3%, 4%, and 5% were sig-
nificantly stiffer than control and 1% of ZrO2 . After 3 months of
storage, unmodified, 1%, 2%, and 5% groups showed an unpre-
dicted significant increase of flexural modulus that ranged
from 11%–26%. However, the embedded resin with 3% had no
difference (Fig. 5B), and the flexural modulus decreased when
the 4% fraction of ZrO2 was used. These results revealed that
rigidity of dental resins does not rely on the amount of filler
content or flexural strength. The statistical analysis showed
storage aging condition and amount of nanoparticles concen-
tration significantly affected flexural strength (p < 0.01) and
flexural modulus (p < 0.001) of provisional dental resin.
3.5. Fracture toughness
Load capacity at fracture was increased among all the rein-
forced specimens compared to unmodified control (Fig. 5C).
There was a positive correlation with filler concentration up
to 3% of ZrO2 addition, and then the toughness decreased
gradually with 4% and 5%. Significantly, specimens that con-
tained 3% filler had a higher fracture toughness compared to
blank resin, 1%, and 2% of ZrO2 addition. Aging for 3 months in
artificial saliva initially revealed unfavorable effects on resin
nanocomposites, causing a significant reduction in fracture
toughness of all groups. A similar pattern to no-aging groups
was observed: the KCl increased until 3% addition, then peaked
started to decrease with 4% and 5% incorporation. Repeatedly,
3% presented significant fracture toughness compared to con-
trol and 1% of ZrO2 . Water taken up during storage aging may
cause hydrolysis between the filler and resin matrix, which
relatively softens material. The concentration of the filler dra-
matically shows a major role in the resulting nanocomposites,
whereas the reinforcement of the filler is not as concentration
dependent.
3.6. Vickers microhardness and Nanoindentation
properties
The surface hardness for all the groups was recorded directly
before storage in saliva and after 3 months of incubation
to simulate oral physiological condition. The results for
surface microhardness, nanoindentation, and nanomodulus
are depicted in Table 2 as mean and standard deviation,
as well displayed graphically in Fig. 6. The ANOVA with
repeated measures revealed significant differences between
aging condition and VH (p < 0.0001). However, there was a dif-
ferent trend observed in case of nanofiller concentration and
nanohardness, and modulus. After the addition of ≥3% ZrO2
nanoparticles within PMMA resin, there was a reduction in
nanohardness and modulus, respectively. After aging, both
nanohardness and modulus significantly improved among all
groups (p < 0.0001).

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Fig. 6 – Bar graphs demonstrate (A) Vickers microhardness, (B) nanoindentation strength, and (C) modulus of elasticity of
unmodified printed resin and resin modified with 1% zirconium oxide (ZrO2 ) nanoparticles up to 5% before aging (stripped
bars) and after storage aging with artificial saliva for 3 months (left gray bars). (*p < 0.05, **p < 0.01, and ***p < 0.001).

For VH, the one-factor ANOVA demonstrated significant

differences between unmodified resins and those loaded
4. Discussion
with discrete concentrations of ZrO2 nanoparticles, with
The use of resin composites is still growing in the field of
some exceptions. For instance, no significant differences were
dentistry, as this material possesses reliable physical and
detected in microhardness between unmodified and 1%, 2%,
mechanical properties. However, the aforementioned charac-
and 3% or 3% and 4% addition of ZrO2 . The highest hardness
teristics are likely to be affected by the physiological processes
was recorded for the 5% and the lowest value for the unmod-
that take place during aging, which definitely have a correla-
ified. After aging in artificial saliva, all specimens showed
tive impact on composite degradation in the oral cavity, which
slightly significant increases in hardness ranges between
leads to reduced longevity and inferior mechanical properties
0.007% up to 0.062% compared to initial groups, except the
of those materials [35]. Clinically, the mechanical properties
3% addition showed a negligible decrease (Fig. 6A).
of regular provisional restorations have been addressed and
The impact of the weight percentages of the filler on
are reported to be achievable when using resin-based mate-
the nanohardness and modulus was even more pronounced
rial for a short time, between 1 to 2 weeks. On the contrary,
(Fig. 6B and C). Nanohardness and modulus before aging of
restoration stability could be somewhat hard to manage with
all specimens followed a positive pattern of enhancement
an extended wear time, such as dental implant replacements,
linked to weight percentage increment until 3% addition, after
where the recovery is estimated to be around 6 months [36].
which the strength began gradually decreasing with 4% and
In addition, patients who develop cancer have a more sophis-
5%. Likewise, microhardness and nanomechanical character-
ticated recuperation mechanism than typical individuals, so
istics showed progressive strength growth limited to 3%, and
they need about 1 year or even longer for the osteointegra-
then it steeply dropped with concentration addition. Overall,
tion incubating period. Additionally, the level of complexity
3% revealed the highest mean value of both hardness and
increases in patients who demonstrate parafunctional habits
elasticity, converse to unmodified dental resin, which showed
such as bruxism. Therefore, the provisional restoration should
the lowest value among all groups (Table 2). Furthermore,
be fabricated of durable material that can withstand an
the statistic results endorse that uncertain interaction would
extreme applied force and ensure longevity, especially in long
affect material strength.
span restorations, which are usually susceptible to fractures

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[10]. Therefore, in this study, we introduced modified ZrO2

3.77 (1.01)
5.00 (0.67)
5.42 (1.03)
7.17 (1.50)
5.33 (0.81)
5.04 (0.75)
nanoparticles to enhance properties of 3D printed resin for

After
provisional dental restorations.

Nano modulus
We silanized ZrO2 nanoparticles in this study. These are
functionalized ceramic nanoparticles that are coated with

1.28 (0.38)
3.73 (1.25)
4.17 (1.13)
4.71 (1.53)
4.33 (1.85)
4.50 (1.76)
a silane coupling agent such as 3-(Trimethoxysilyl)propyl

Before
(GPa) methacrylate (␥-MPS). Silanization is an adaptive process that
reduces filler surface energy, protecting nanoparticles from
dissolution as well as enhancing interphases with resin and
dispersing evenly as phases continue. Typically, silane cou-
0.12 (0.06)
0.23 (0.07)
0.25 (0.07)
0.36 (0.10)
0.27 (0.07)
0.21 (0.04)
pling agents adsorb on nanoparticle surfaces, which creates
After

a chemisorbed silane layer and covalently will bind to par-

Nanohardness

ticle surfaces and then copolymerize with the methacrylic

polymer matrix [37]. Although this interphase is the least
0.03 (0.02)
0.13 (0.06)
0.20 (0.09)
0.26 (0.11)
0.20 (0.11)
0.16 (0.08) abundant structure in the composites, studies have shown
Before
(GPa)

its significant effects on the physicomechanical properties of

the composites [38]. The basic intermediate mechanism with
ZrO2 nanoparticles is the hydrolysis of ␥-MPS to form silanol
(Si–O–H) and an alkoxy functional group (CH3 O–), which is
17.39 (0.31)
17.75 (0.26)
17.80 (0.45)
18.33 (0.36)
19.05 (0.25)
20.02 (0.57)

eventually exchanged by the hydroxyl group to form Si–OH.

After

This activation leads to conjugation with the hydroxyl group

of zirconia (Zr–OH) followed by a condensation reaction to pro-
Microhardness

duce such chemical bonds between zirconium oxide particles

and ␥-MPS (Zr–O–Si). Further, the free radical organofunctional
16.71 (0.62)
16.72 (0.55)
17.92 (0.27)
18.05 (0.21)
18.54 (0.35)
19.14 (0.33)
(HV0.05)

groups bond acrylic ester-based monomers through photo-

Before

activation of initiator components in the resin matrix [39,40].

Consequently, based on this concept, our Raman and TEM
Table 2 – Demonstrates mean and standard deviation of mechanical properties among groups.

images (Fig. 1(d) and 4 (A)) indicated that nanoparticles were

1.68 (0.17)
1.71 (0.20)
1.75 (0.14)
1.84 (0.15)
1.74 (0.16)
1.68 (0.16)

successfully modified with an ␥-MPS coupling agent, as shown

with peaks emerging at 1639 cm−1 and 1716 cm−1 that assign
After

carbon to the carbon bond and to oxygen, respectively. In addi-

tion, the followed technique ensured that ZrO2 nanoparticles
(MPa.m1/2)
Toughness

had an elliptical shape and a size of 20–40 nm, similar to initial

1.93 (0.20)
1.98 (0.09)
2.04 (0.23)
2.16 (0.22)
2.03 (0.21)
2.06 (0.08)
Fracture

Before

unmodified particles with thin film that had 2–4 nm thick-

ness (Fig. 1c and d) and thus had enhanced ZrO2 adhesion
and distribution as shown with SEM (Fig. 2g).
Physical and chemical properties of dental resin are an
2.33 (0.24)
2.35 (0.17)
2.44 (0.22)
2.57 (0.21)
2.33 (0.24)
2.59 (0.18)

essential aspect that directly influence longevity of oral

After

restorations. For example, surface roughness is an impor-

Modulus (GPa)

tant characteristic that should be considered when fabricating

dental restorations. Indeed, a very rough surface is sig-
1.96 (0.17)
1.93 (0.15)
1.93 (0.18)
2.60 (0.23)
2.59 (0.26)
2.32 (0.20)

nificantly correlated with poor restoration aesthetics and

Flexural

Before

superficial staining that reduces gloss appearance and sur-

face hardness, and a smother surface has been reported to
be tougher than a rougher surface [41]. Moreover, there is a
clear evidence about the association between roughness and
103.10 (3.91)

103.25 (4.80)
94.14 (6.31)
95.90 (6.29)
98.40 (5.90)

97.70 (6.62)

other complications such as gingival inflammation, secondary

caries, and bacterial plaque accumulation [42]. Loading 3D
After

printed resin with ZrO2 does not affect the roughness when
this nano-size filler is dispersed homogeneously in a polymer
Strength (MPa)

matrix, and physical entanglement among resin matrices may

109.40 (7.03)
110.10 (5.24)
111.56 (5.74)
98.32 (3.94)
99.12 (6.50)
99.24 (5.30)

obstruct nanoparticle migration to the surface, which reduces

Flexural

Before

roughness.
On the other hand, monomer degree of conversion has a
critical impact on mechanical properties such as hardness,
while this feature would be enhanced in accordance with
Unmodified

the rate of converted monomer into a polymer network [43].

1% ZrO2
2% ZrO2
3% ZrO2
4% ZrO2
5% ZrO2

The degree of polymerization of composite resins is strongly

linked to the curing process, which might be influenced by
irradiation strength energy, the wavelength range, exposure

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time, translucency, and scattering of light by the filled sys-
tem [44,45]. Additive manufacturing technology is state of the
art with the recent dental restoration fabrication method. One
advantage is its thin single layer curing (50 ␮m), in compari-
son to the conventional curing method, where the inner layers
of resin are not similarly accessible. In addition, postcuring
steps after printing give extra strength to the entire struc-
ture. The modified dental resin with nano-ZrO2 in our study
(2%–5%) showed a significant reduction in DC compared to
unmodified and 1% filler. This phenomenon is explained by
the opacity of the ZrO2 filler, which may hinder proper even-
tual light scattering. Another prospect is using progressively
higher percentage fillers in the composites to increase resin
viscosity, which might limit mobility of unreacted monomer
molecules [41]. Surprisingly, after aging, all specimens had
recovered with a comparable value of DC, which conflicts with
previous assumptions and confirms that the double curing
methods of printing and post-UV curing unit eliminate the
ZrO2 filler interaction tendency. Therefore, the storage con-
dition might lead to the dissolution of the outer improperly
cured layer, after which the residual free unreacted monomer
leaches out.
In dental restorations, water sorption and solubility are
essential aspects to assess resistance of material to surround-
ing oral fluid, due to hydrolytic degradation and expansion,
which ensure its clinical longevity. Intrinsically, hydrophilicity
is an inherent feature of polymer materials due to weak bond-
ing that allows water molecules to penetrate and eventually
affect mechanical properties as a plasticizer. In addition, water
diffusion consequences might extend to dissolute interphase
bonds because of high filler surface energy and water perme-
ability, and thus lead to internal stress as well as loss of particle
adhesion, which generates voids and porosities within the
resin matrix [42]. Our investigation revealed that the addition
of ZrO2 in different concentrations enhanced resin sorption;
for example, 4 wt.% ZrO2 presented lower sorption (13.5%)
in unmodified resin. Even though the aging process slightly
increased the level of sorption, it was still acceptable, showing
the benefit of modifying nanofiller with ␥-MPS, which reason-
ably improves hydrophobicity and diminishes water uptake.
For restorative composites the upper limit of sorption was
suggested to be 50 ␮g/mm3 [46], which has been achieved in
this study (40.82–47.2150 ␮g/mm3 ). On the other hand, solu-
bility depends mainly on the amount of converted monomer
and reflects leaching of unreacted resin. This sensation hap-
pens because of monomer entrapment during polymerization
within polymer chains or micropores as a result of inadequate
handling techniques or agglomeration of filler [42,46]. There-
fore, after synthesis, the unmodified printed resin showed
the lowest solubility, which represented the highest degree
of conversion, as mentioned previously. Additionally, long-
term soaking in saliva was sufficient to release unpolymerized
monomer, and it had also recovered a degree of conversion in
the range of unmodified resin. Despite the fact that specimens
showed a negative solubility due to weight gaining of entangle
water molecules, the results were still in agreement with the
ISO standard of provisional restoration solubility and did not
exceed 7 ␮g/mm3 .
Several reasons could be attributed to the interaction of
water sorption and solubility with aged and non-aged PMMA
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resin. Firstly, sorption arising from the resins hydrolytically
degrades the network structure, detaches the silanized fillers,
and consequently affecting the solubility [47]. In addition,
Dogan et al. have hypothesized that the residual monomer
near the surface of the resin leaches into water, causing a
decrease in polymer mass. If the residual monomer is not close
to the surface of the specimen, but rather entrapped in the
inner layers of resin specimen, it cannot diuse into water after
a short time [48]. Furthermore, the reduction of solubility may
be hypothesized by the addition of ZrO2 nanoparticles which
may have reacted with the saturated remaining monomer [48].
ZrO2 is an oxidative metal that has superior mechanical
strength, fracture toughness, hardness, and wear resistance
[13,15,18]. It is expected that different fractional additions of
nanofiller would significantly enhance the mechanical prop-
erties of 3D printed resin composites, in contrast to the neat
resin, and the higher filler content, the higher microhardness.
In general, hardness evaluates a material’s capacity to resist
abrasion and permanent indentation marks. Hardness is an
indirect method to evaluate the depth of polymerization, and
this attribute is also regulated by the organic and inorganic
content ratio [43,49]. In this study, VHN increased proportion-
ately to the filler amount. Particles in nano-size can have an
enormous contact area with resin than larger filler; there-
fore, well dispersion of filler helped significantly to increase
material hardness. Even though the material went through
accelerated aging, the hardness remained steady. This could
be related to high interfacial shear strength between resin and
ZrO2 due to proper silanization, or perhaps the assigned aging
time was not long enough to disband the interphase interac-
tion. On the other hand, nanomechanical properties have a
narrow scope of nano-size to represent material strength, as
they correlate with resin nature (linear or cross-linked), filler
size, and distribution [50]. Nanoindentation results showed an
increased pattern linear to the amount of ZrO2 . However, after
3% addition, nanohardness and modulus decreased gradu-
ally. This corresponded to agglomeration of nanoparticles and
was concentrated in confined areas rather than uniformity
dispersion over the surface. In addition, the extremely high
standard deviation compared to microhardness expresses one
of the challenges of controlling nanocomposites fabrication,
which could be seen in high filler concentration materials
showing less capacity to tolerate deformity. Storage specimens
demonstrated an enhancement of nano-mechanics relative to
unaged specimen values, which may have occurred because
of dissolution of the superficial weak layer of resin as well as
relaxation phenomena improving the physical and mechani-
cal properties [50].
Clinically, internal microfractures, voids, porosity, and
crack propagation are the major causes behind composite
restoration failure [51]. Intraoral restorations frequently are
exposed to such repetitive sorption/desorption mechanisms
in addition to a dynamic environment, both of which apply
massive stress to strongly influence brittle materials. Flexural
strength and toughness are indispensable merits that describe
the capacity of composite restorations to absorb or withstand
load or initial crack, and then distribute this evenly through
the bulk structure. This concept accordingly promotes the
importance of manipulating filler composition [11,13,15,16].
Regardless of physiological factors that affect strength, flex-
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ural strength, flexural modulus, and fracture toughness are
subjected to type, size, shape, concentration, interactions, dis-
persion, and agglomeration of the filler inside the polymer
network [52]. The effect of ageing seems to have eliminated
any clinically important differences in the flexural strength
and flexural modulus among the low filler content groups.
The addition of ZrO2 has significantly improved the allo-
cated mechanical properties; this enhancement was parallel
to the amount of concentration. However, after composite
resins were stored in artificial saliva for 3 months, the reduc-
tion of strength was more pronounced after incorporating a
higher filler content compared to groups having lower filler
content. Similarly, toughness toward pre-crack, 5 wt.% ZrO2
decreased by 18% compared to lower fillers (1–4 wt.% ZrO2 ).
The possible explanation for this is the fillers at a high
loading tended to agglomerate and behaved as local stress-
concentration areas or crack-initiation sites that hindered
polymer chain mobility and then jeopardized mechanical
properties. SEM images of fractured specimens with higher
loading indicated the agglomeration regions, which intro-
duced such rough and ductile fractures.
On the other hand, increasing concentrations of ␥-MPS
had an adverse impact on resin modules due to physi-
cal adsorbed formation between filler and resin [38]. As a
result of increasing amounts of filler there was a chance to
include more physical adsorption on the ZrO2 particle sur-
faces, which causes dispersed silane molecules to work as
plasticizer. Because of this, the flexural modulus markedly
decreased after 4 wt.% incorporation. The physical adsorption
has been reported to be sensitive to fluid diffusion and suscep-
tible to degradation [42], therefore storage groups showed an
improvement with modulus. This may possibly be explained
as specimens being exposed for an indirect washing pro-
cess, which removed unattached layers as well as residual
monomer, which eliminated impurities and improved elastic-
ity of modified 3D printed resin.
The limitations of this study are associated with viscosity
of the current printed resin as well as nanoparticle agglomer-
ation. Those two factors were found to influence the physical
and mechanical properties significantly. Therefore, a further
optimization should be conducted to ensure efficient filler dis-
persion among resins. Moreover, this study found that residual
monomer is entrapped after printing and was released during
the aging process; hence, an in vitro study should be carried
out in the future to evaluate cytotoxicity and the other related
biological and microbiological properties.
5. Conclusion
This study introduced the feasibility of improving 3D-printed
resin using ZnO2 nanoparticles. Various fractional addi-
tions of ZrO2 nanoparticles significantly improved physical
and mechanical properties of 3D printed resin compared to
unmodified resin. Hardness showed improvement by increas-
ing the filler content. Degree of conversion, microhardness,
nanoindentation/elasticity, and flexural modulus enhanced
with aging. The newly developed 3D printed nanocomposites
may have the superior potential and efficacy for long-term
provisional dental restoration materials.
Please cite this article in press as: Aati S, et al. Development of 3D printed resin reinforced with modified ZrO2 nanoparticles for long-term
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xxx.e13
Funding source
This research was partially supported by the following
research grants from the Faculty of Health and Medical
Sciences, Dental School University of Western Australia,
Colgate Palmolive® (PG 008/10402012, 00800/70237003, and
00800/68001004) and Australian Dental Research Foundation
(PG 00800/51002200 and 00800/51001600).
Acknowledgment
We thank our colleague Associate Professor Martin Saunders,
CMCA University of Western Australia who provided insight
and expertise for TEM that greatly assisted the research. The
authors extend their appreciation to the Deanship of Scientific
Research at King Saud University.
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Please cite this article in press as: Aati S, et al. Development of 3D printed resin reinforced with modified ZrO2 nanoparticles for long-term
provisional dental restorations. Dent Mater (2021), https://doi.org/10.1016/j.dental.2021.02.010