materials

Article
How the Duration and Mode of Photopolymerization Affect the
Mechanical Properties of a Dental Composite Resin
Leszek Szalewski 1, * , Dorota Wójcik 2 , Weronika Sofińska-Chmiel 3 , Marcin Kuśmierz 3
and Ingrid Różyło-Kalinowska 4

1 Digital Dentistry Lab., Department of Dental and Maxillofacial Radiodiagnostics,

Medical University of Lublin, 20-093 Lublin, Poland
2 Department of Dental Prosthetics, Medical University of Lublin, 20-093 Lublin, Poland
3 Analytical Laboratory, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie
Skłodowska University, Maria Curie Skłodowska Sq. 3, 20-031 Lublin, Poland
4 Department of Dental and Maxillofacial Radiodiagnostics with Digital Dentistry Lab.,
Medical University of Lublin, 20-093 Lublin, Poland
* Correspondence: [email protected]; Tel.: +48-508-216-949

Abstract: Composite materials are the most common materials in use in modern dentistry. Over the
years, the methods of photopolymerization of composite materials have been improved with the use
of various devices, such as quartz tungsten halogen lamps (QTHs), light-emitting diode units (LEDs),
plasma-arc lamps and argon-ion lasers. This study aimed to compare the mechanical properties of a
composite material, depending on the time and mode of photopolymerization. One hundred and
forty rectangular specimens (25 × 2 × 2 mm) and forty-two disc-shaped samples (5 mm diameter
and 2 mm thickness) were prepared from shade A2 Boston composite resin. Samples were cured
using the following seven photopolymerization protocols: four fast-cure modes (full power for 3, 5,
10, and 20 s), two pulse-cure modes (5 and 10 shots of 1 s exposures at full power), and one step-cure
mode (soft start with a progressive cycle lasting 9 s). Specimens were subjected to a flexural strength
test, Vickers microhardness test, and FTIR spectroscopy test. A 2-factor ANOVA and post-hoc tests
were carried out to assess the differences in the flexural strength parameter between the tested groups
Citation: Szalewski, L.; Wójcik, D.; of samples before and after aging. A mixed-model ANOVA was carried out to assess the differences
Sofińska-Chmiel, W.; Kuśmierz, M.; in the Vickers microhardness parameter between the tested groups of samples before and after aging.
Różyło-Kalinowska, I. How the
The lowest values of flexural strength (p < 0.001) and Vickers microhardness (p < 0.001) were obtained
Duration and Mode of
for the 3 s mode for the pre- and post-aging groups. The FTIR mapping tests showed a much more
Photopolymerization Affect the
homogeneous chemical structure of the composite after 20 s of continuous irradiation, compared to
Mechanical Properties of a Dental
the sample irradiated for 5 s in the continuous mode. The mode and cure time affects the mechanical
Composite Resin. Materials 2023, 16,
113. https://doi.org/10.3390/
properties of the composite resin. Appropriate selection of the cure mode and time ensures better
ma16010113 mechanical properties of composite resin. This suggests that the survival of dental restorations within
the oral cavity could be extended by using longer photopolymerization durations.
Academic Editor: Ana Arenillas

Received: 24 November 2022 Keywords: restorative dentistry; aesthetic dentistry; biomechanics; composites; photopolymerization;
Revised: 18 December 2022 flexural strength
Accepted: 19 December 2022
Published: 22 December 2022

1. Introduction
Copyright: © 2022 by the authors.
Composite materials are the most common materials in use in modern-day dentistry
Licensee MDPI, Basel, Switzerland. and were introduced in the 1960s. Since that time, their composition has been modified to
This article is an open access article achieve the best mechanical, biological, and aesthetic properties [1,2]. At present, composite
distributed under the terms and materials are used not only in conservative dentistry, but also in other areas of dentistry,
conditions of the Creative Commons such as prosthetics, periodontology, and dental surgery [1,3].
Attribution (CC BY) license (https:// Dental composite resins are mixtures of inorganic fillers, organic matrices, coupling
creativecommons.org/licenses/by/ agents, and some additives (photoinitiators, stabilizers and inhibitors). The most frequently
4.0/). used filler is silicon dioxide (SiO2 ), due to its matched refractive index with a resin matrix,

Materials 2023, 16, 113. https://doi.org/10.3390/ma16010113 https://www.mdpi.com/journal/materials

Materials 2023, 16, 113 2 of 18

good stability and mechanical properties, and easy production [4]. Organic matrices are
composed of different monomers, such as BisGMA, UDMA, TEGDMA, and DMAEMA [1].
Since the tensile strength of the composites is much lower than their compressive
strength and typically much more sensitive to internal flaws, it is probably the most appro-
priate property to be assessed in strength testing [5]. However, flexure testing, a potentially
simpler method that is highly related to tensile failure, is usually substituted in its place.
Flexure testing is the standard means for the strength testing of dental composites (ISO
4049) and has been shown to correlate with material wear in some studies [5]. Manufactur-
ers continue upgrading their composite materials using different resins or fillers. Sideridou
et al. confirmed that the higher the percentage content of filler, the higher the flexural
strength [6]. The final properties of composites may be affected by the material composition,
as well as by the photopolymerization mode [7,8]. The origins of light-polymerization
date back to the 1970s, when UV light (with a wavelength of approx. 365 nm) was used to
polymerize composite resins [7]. Over the years, the methods of photopolymerization of
composite materials have been improved with the use of various devices, such as quartz
tungsten halogen lamps (QTHs), light-emitting diode units (LEDs), plasma-arc lamps, and
argon ion lasers (with wavelengths from 360 to 560 nm) [9]. Numerous manufacturers
continued to introduce increasingly advanced lamps to the market, modifying photopoly-
merization programs and the power of devices to ensure the best mechanical parameters
of composite materials. However, many dentists fail to use their photopolymerization
lamps properly by focusing mainly on the anatomical shape and the aesthetics of fillings [9].
In a survey study by Kopperud et al., nearly one-third of the dentists did not properly
protect their eyes against the blue light, while 78.3% of the responders were unaware
of the irradiance values of their photopolymerization lamps [9]. Numerous responders
never verified the quality of the light emitted by their photopolymerization lamps. An
incorrect angle of the lamp tip during polymerization or a malfunctioning lamp can cause a
significant reduction in the energy that reaches the composite material, and thus disturb the
polymerization process. This may result in poorer mechanical properties of the material.
Other studies showed that pre-clinical dental students and dentists in their internship
year improperly use photopolymerization lamps, not delivering the required energy to the
composite layer [10].
With the development of equipment, the duration of photopolymerization has also
changed. For years, 20 s of irradiation was the gold standard, whereas new photopolymer-
ization lamps offer photopolymerization times reduced to 3 s [3]. The mechanical properties
of composite resins must improve or remain at the same level after technological changes.
New solutions that could deteriorate the mechanical properties of materials should not be
introduced. A shortened duration is not a sufficient reason to use such solutions.
This study aimed to compare the mechanical properties of a composite material
depending on the duration and mode of photopolymerization before and after artificial
aging. The null hypothesis was as follows: (1) the different modes and durations of
photopolymerization would not affect the flexural strength, Vickers microhardness, degree
of conversion, or chemical structure of the composite resin; (2) there is no difference “before
and after artificial aging” in flexural strength, Vickers microhardness, degree of conversion
or chemical structure of the composite resin.

2. Materials and Methods

One hundred and forty specimens have been prepared for flexural strength tests
and forty-two specimens were prepared for Vickers microhardness tests, as per the ISO
4049:2010-12 standard, from shade A2 Boston composite resin (Arkona LFS, Nasutów,
Poland). The resin is a nano-hybrid composite with a 78% filler content (barium–aluminium–
silicon glass, fumed silica; titanium dioxide) with a particle size of 15–2000 nm. The matrix
comprises Bis-GMA, UDMA, Bis-EMA, and TEGDMA resins. Rectangular specimens
(25 × 2 × 2 mm) and disc-shaped samples (5 mm diameter and 2 mm thickness) were
produced using a steel mold placed on a microscope slide to achieve a flat surface (Figure 1).
 One hundred and forty specimens have been prepared for flexural strength tests and
forty-two specimens were prepared for Vickers microhardness tests, as per the ISO
4049:2010-12 standard, from shade A2 Boston composite resin (Arkona LFS, Nasutów,
Poland). The resin is a nano-hybrid composite with a 78% filler content (barium–
aluminium–silicon glass, fumed silica; titanium dioxide) with a particle size of 15–2000
Materials 2023, 16, 113 nm. The matrix comprises Bis-GMA, UDMA, Bis-EMA, and TEGDMA resins. Rectangular 3 of 18

specimens (25 × 2 × 2 mm) and disc-shaped samples (5 mm diameter and 2 mm thickness)

were produced using a steel mold placed on a microscope slide to achieve a flat surface
(Figure 1). Subsequently,
Subsequently, one portion one portion ofresin
of composite composite resin waswith
was condensed condensed
a dentalwith a dental
plugger and
plugger and
flattened flattened
by being by being
pressed by thepressed by the
slide. The slide. The
composite composite
material material
was then was then
polymerized
through
polymerizeda layer of polyethylene
through a layer offilm (40 µm) tofilm
polyethylene eliminate
(40 μm) oxygen inhibition
to eliminate on the
oxygen surface.
inhibition
Samples were polymerized
on the surface. Samples were using a high-powered
polymerized using aLED LCU (MiniLED
high-powered LEDLCUIII Supercharged,
(Mini LED III
Acteon Group, Acteon
Supercharged, Merignac, France).
Group, Samples
Merignac, were Samples
France). cured usingwere the following
cured using the7 photopoly-
following
merization
7 photopolymerization protocols: 4 fast-cure modes (full power for 3, 5, 10,2and
protocols: 4 fast-cure modes (full power for 3, 5, 10, and 20 s), pulse-cure
20 s), 2
modes (5 and
pulse-cure 10 shots
modes (5 andof 10
1 sshots
exposures
of 1 s at full power),
exposures and
at full 1 step-cure
power), and 1mode (softmode
step-cure start
with
(soft astart
progressive cycle lastingcycle
with a progressive 9 s) (Table
lasting1).
9 s)A (Table
total of1).
20Arectangular
total of 20and 6 disc-shaped
rectangular and 6
samples
disc-shapedweresamples
made forwereeach made
mode and time of
for each photopolymerization.
mode According to the
and time of photopolymerization.
manufacturer’s information, the photopolymerization power was 2000 mW/cm 2 when a
According to the manufacturer’s information, the photopolymerization power was 2000
7.5 mm diameter
mW/cm tipmm
2 when a 7.5 wasdiameter
used. Eachtip rectangular
was used. Eachsample was polymerized
rectangular sample wasat 4polymerized
points (in a
longitudinal
at 4 points (indirection every 6direction
a longitudinal mm), and the disc-shaped
every 6 mm), and the specimens were specimens
disc-shaped polymerized wereat
1polymerized
point. at 1 point.

Figure 1.
Figure 1. Pictures
Pictures of
of samples:
samples: (A)
(A) rectangular
rectangular specimen
specimen for
for flexural
flexural strength
strength test;
test; (B)
(B) disc-shaped
disc-shaped
specimen for Vickers microhardness test.
specimen for Vickers microhardness test.

Table1.1.Characteristics
Table Characteristicsof
ofthe
thephotopolymerization
photopolymerizationmodes.
modes.

Mode Mode Description Description Total

Total Energy
Energy (J/cm
(J/cm 2 ) 2)

Fast-Cure 3s Full power for 3 s 6

Fast-Cure 3s Full power for 3 s 6
Fast-Cure 5s Fast-Cure 5s Full power for 5 s
Full power for 5 s 10 10
Fast-Cure 10s Fast-Cure 10s Full power for 10Full s power for 10 s 20 20
Fast-Cure 20s Fast-Cure 20s Full power for 20Full s power for 20 s 40 40
5 shots of 1 s (full power with emission of 5/10 successive one-second
5 shots of 1 s (full power withflashes with a
Pulse-Cure 5s 10
rest of period of 250 ms between
emissioneach flash)
of 5/10 successive
Pulse-Cure 5s
10 shots of 1 s (full power with emission of one-second
5/10 successive one-second flashes 10
Pulse-Cure 10s flashes with a rest of with a 20
rest of period of 250 period
ms between
of 250each flash) each flash)
ms between
Step-Cure 9s 6 s progressively and103 shots
s at full
of power
1 s (full power with 12
emission of 5/10 successive
Pulse-Cure 10s 20
one-second flashes with a rest of
period of 250 ms between each flash)
Step-Cure 9s 6 s progressively and 3 s at full power 12
MINI LED III Supercharged, Acteon Group, France; wavelength range: 420–480 nm; central wavelength:
455–465 nm; intensity: 2000 mW/cm2 ± 10% for an active fiber diameter of 7.5 mm.

After photopolymerization, the specimens were released from the mold. The steel
mold blocked the light from the side of the samples, which made it possible to obtain
reproducible results. There was no risk of false results due to lateral polymerization of the
 MINI LED III Supercharged, Acteon Group, France; wavelength range: 420–480 nm; central wave-
length: 455–465 nm; intensity: 2000 mW/cm2 ± 10% for an active fiber diameter of 7.5 mm.

After photopolymerization, the specimens were released from the mold. The steel
mold blocked the light from the side of the samples, which made it possible to obtain
Materials 2023, 16, 113 4 of 18
reproducible results. There was no risk of false results due to lateral polymerization of the
sample. Next, the specimens were examined for the presence of air bubbles and defective
specimens were excluded from the study. The specimens were immersed in distilled wa-
sample. Next, the specimens were examined for the presence of air bubbles and defective
ter at the temperature of 37 °C for 24 h. One-half of the rectangular specimens were im-
specimens were excluded from the study. The specimens were immersed in distilled
mediately subjected to flexural strength tests, while the rest of the specimens were artifi-
water at the temperature of 37 ◦ C for 24 h. One-half of the rectangular specimens were
cially
immediatelyArtificial
aged. subjectedaging included
to flexural the immersion
strength tests, while of
thethe
restspecimens for 90 days
of the specimens were in dis-
tilled wateraged.
artificially at 37Artificial
°C. After thisincluded
aging time, thethe specimens
immersion of were dried andfor
the specimens tested forinflexural
90 days
strength.
distilled water at 37 ◦ C. After
All disc-shaped specimens
this time,were subjectedwere
the specimens to Vickers microhardness
dried and testing, and
tested for flexural
subsequently immersed specimens
strength. All disc-shaped in distilledwere
water at 37 °C
subjected for 90 days.
to Vickers After thistesting,
microhardness time, and
specimens
subsequently
were once againimmersed in distilled
tested for Vickerswater at 37 ◦ C for 90
microhardness days. 2).
(Figure After this time, specimens
were once again tested for Vickers microhardness (Figure 2).

Figure 2. Flow chart of the research process.

Figure 2. Flow chart of the research process.
2.1. Flexural Strength Test
FlexuralStrength
2.1. Flexural strengthTest
was tested by three-point bending tests using the Cometech QC-
508M2 (Cometech Testing Machine, Taichung, Taiwan) testing machine with an opening
widthFlexural
of 20 mm, strength was tested
initial gripping forceby
of 1three-point bending
N, and a crosshead testsof using
speed the Cometech
0.75 mm/min. Each QC-
508M2
sample(Cometech
was measured Testing
beforeMachine, Taichung,
the test. Only samplesTaiwan) testing machine
with dimensions with
that met the an opening
criteria
width
of 2 mmof 20
± mm,
0.01 mminitial gripping
were tested (6force of 1 N, were
specimens and arejected).
crosshead speed
The exactofmeasurements
0.75 mm/min. Each
of each was
sample specimen were entered
measured intotest.
before the the equation to calculate
Only samples the flexural strength
with dimensions that metvalue.
the criteria
ofThe test end
2 mm wasmm
± 0.01 marked
werebytested
the specimen being crushed.
(6 specimens Flexural strength
were rejected). The exactwasmeasurements
calculated of
using the following equation:
each specimen were entered into the equation to calculate the flexural strength value. The
S = 3Fl/2bh2
test end was marked by the specimen being crushed. Flexural strength was calculated
wherethe
using F isfollowing
the maximum load exerted on the specimens in Newton;
equation:
l is the distance (20 mm) between the supports, with an accuracy of ±0.01 mm;
S = 3Fl/2bh
b is the width (2 mm ± 0.01 mm) of the specimens
2
measured before testing;
h is the height (2 mm ± 0.01 mm) of the specimens measured before testing.
where F is the maximum load exerted on the specimens in Newton;
l is theMicrohardness
2.2. Vickers distance (20 Test
mm) between the supports, with an accuracy of ±0.01 mm;
The microhardness of the tested samples was evaluated on the Vickers scale using a
Pruftechnik KB-10 durometer (KB Pruftechnik GmbH, Hochdorf-Assenheim, Germany)
Materials 2023, 16, 113 5 of 18

with a load force of 200 g (1.962 N), which operated for 15 s. In cases of an uneven or illegible
probe footprint, the measurement was repeated. The diagonal length was measured using
the light microscope Matrix Vision 5MP (Matrix Vision GmbH, Oppenweiler, Germany).

2.3. Fourier Transform Infrared (FTIR) Spectroscopy

To observe the process of photopolymerization of dental resin composites as a result
of irradiation with a high-powered LED LCU photopolymerization lamp (Mini LED III
supercharged, Acteon Group, Merignac, France), Fourier transform infrared spectroscopy–
attenuated total reflectance (FTIR–ATR) spectroscopic tests were carried out. The prepared
composite samples (disc-shaped, 5 × 2 mm) with the following durations and modes
were tested using the FTIR Thermo Nicolet 8700 (Thermo Scientific, Waltham, MA, USA)
spectrometer with the Smart Orbit™ attachment diamond ATR and a DTGS (deuterated
triglycine sulfate) detector: uncured, 3, 5, 10 and 20 s continuous mode, 5 and 10 s pulsed
mode, and 9 s slow-start mode. The tests were carried out directly from the surface of the
composites at room temperature. FTIR spectra were obtained using the ATR technique with
a diamond crystal in the wavenumber range of 4000–400 cm−1 , with a spectral resolution
of 4 cm−1 . A total of 64 scans were obtained for each spectrum. The obtained spectra were
subjected to ATR correction, automatic baseline correction, and normalization using the
Omnic SpectaTM software 833-036200.

2.4. FTIR Microscopy

Chemical maps of the composites were made for the samples irradiated for 3 and 20 s
in the continuous mode. The tests were carried out using the FTIR iN10 MX microscope
(Thermo Scientific) with the specular reflection method at room temperature, using the
MCT-A detector cooled with liquid nitrogen. A total of 16 scans were obtained for each
spectrum. For the sample irradiated for 3 s in the continuous mode, the spectra were
collected from the area of 10,000 × 9000 µm. The map was created using the correlation
method with the peak at the position 2956 cm−1 . For the composite sample irradiated for
20 s in the continuous mode, the spectra were collected from the area of 10,000 × 7000 µm.
The map was created using the correlation method with the peak at the position 2951 cm−1 .

2.5. XPS Spectroscopy

X-ray photoelectron spectroscopy (XPS) studies were performed using a multi-chamber
UHV system (PREVAC, Rogów, Poland). Spectra were collected using a hemispherical
Scienta R4000 electron analyzer (Scienta Omicron, Uppsala, Sweden). A Scienta SAX-100 X-
ray source (Al Kα, 1486.6 eV; 0.8 eV band) equipped with an XM 650 X-ray Monochromator
(PREVAC, Rogów, Poland) (0.2 eV band) was used as complementary equipment.
The pass energy of the analyzer was set to 200 eV for survey spectra (with a 500 meV
step), and 50 eV for the C1s region (high-resolution spectra with a 50 meV step). The base
pressure in the analysis chamber was 5·10−9 mbar. During the spectra collection, it was not
higher than 3·10−8 mbar.

2.6. Statistical Methods

To assess flexural strength, a comparative analysis of the mean values of flexural
strength (MPa) was carried out. The groups were compared regarding two different factors,
namely the mode of photopolymerization (7 different modes) and the aging process (before
and after). A 2-factor ANOVA and post-hoc tests (Bonferroni test) were performed. The use
of 2-ANOVA is acceptable due to the fulfillment of the normality condition and very high
partial eta2 values. We conducted a post-hoc power analysis and for the effects of aging in
this analysis, due to the compared parameters and interactions, the obtained power (1 − β)
ranged from 0.87 to 0.99. The effect of interactions between individual factors was also
considered. Due to the small number of observations, great care was when interpreting
the discovered associations. The hypotheses were assessed using the significance level of
p = 0.05. Mean values and standard deviations were calculated. The data were analyzed for
Materials 2023, 16, 113 6 of 18

normal distribution (Shapiro–Wilk’s test) with the determination of skewness and kurtosis
parameters. In addition, the homogeneity of variance was also investigated.
In the analysis of the Vickers microhardness test results, hypotheses related to the
differences between the mean values obtained for individual photopolymerization modes
and the aging effect were verified by mixed-model ANOVA assumptions analysis, followed
by mixed-model ANOVA and post-hoc tests. The hypotheses were verified using the
significance level of p = 0.05. Mean values and standard deviations were calculated. In
the first step, the normality of the distribution was analyzed using the Shapiro–Wilk’s
test, along with the analysis of skewness and kurtosis. Skewness and kurtosis are two
parameters that should be considered for samples with a small number of observations.
In addition, Levene’s test was included in the analyses to assess the homogeneity of the
variance. The analyses were conducted using IBM SPSS Statistics 27 software (International
Business Machines Corporation, New York, NY, USA).

3. Results
The measurements identified as outliers were removed. For pre-aging observations, a
total of three cases were removed from the results pool, including one for the 3 s fast-cure
mode, 5 s fast-cure mode, and 5 s pulse-cure mode. The results of the normality test did
not allow us to reject the null hypothesis about the normality of the distribution. For the
post-aging measurement, one finding was identified as an outlier for the 3 s fast-cure mode.
For the post-aging measurement, the distribution normality test results were statistically
significant at p < 0.05 for the 5 s fast-cure and 10 s fast-cure modes, although the significance
was not lower than p = 0.01. Taking this into account, and as part of exercising caution
when interpreting the obtained results, a 2-factor ANOVA was performed.
The results for the flexural strength variable were indicative of statistically significant
differences due to the aging process (F (1, 122) = 660.4; p < 0.001; η2 = 0.84). Greater strengths
were measured in the pre-aging tests. In addition, the photopolymerization modes were
also indicative of the significant difference in the strength level (F (6, 122) = 7.47, p < 0.001;
η2 = 0.27). A post-hoc analysis using the Bonferroni test was performed to compare the
flexural strengths for different photopolymerization modes. The lowest flexural strength
value was measured for the 3 s fast-cure mode (M = 84.17; SD = 3.18). The flexural strength
measured for this mode was significantly different from those measured for other modes,
except for the 5 s fast-cure mode (M = 94.62; SD = 3.1). The highest value of flexural strength
was measured for the 20 s fast-cure mode (M = 110.2; SD = 3.01). However, the difference
was statistically significant only when compared to the 3 s fast-cure and 5 s fast-cure modes.
Other differences in the comparisons between individual modes were found not to be
statistically significant.
The interaction effect (aging × photopolymerization mode) was observed to be of
statistical significance (F (6, 122) = 2.62, p = 0.02; η2 = 0.11). The differences were calcu-
lated using the post-hoc Bonferroni test. Significant differences in flexural strengths were
observed for each of the seven photopolymerization modes (Figure 3).
Before calculating the Vickers microhardness test results, an analysis of the measure-
ments in terms of the occurrence of outliers, normality of distribution and skewness was
performed to characterize the samples under individual conditions. One finding identi-
fied as an outlier was removed from the pool. In each group, the distribution of results
did not deviate from the normal distribution and the values of skewness and kurtosis
were considered to be acceptable. A mixed-model analysis of variance was carried out to
verify the hypothesis that the photopolymerization method has an impact on the Vickers
microhardness measurements. The result of Levene’s test suggested that the assumption
of the homogeneity of variance was not met for the post-aging mean values. The results
were statistically significant for both the pre-aging and post-aging photopolymerization
processes (F (6, 524.75) = 58.27; p < 0.001; η2 = 0.82; and FWelch (6, 14.6) = 30.54; p < 0.001;
η2 = 0.85, respectively). There was also a significant change in the Vickers microhardness
parameters as a result of aging (λ = 0.86, F (1, 34) = 215.27; p < 0.001; η2 = 0.86). However,
Materials 2023, 16, 113 7 of 18

the
Materials 2023, 16, x FOR PEER REVIEW effect of the interaction (ageing × polymerization mode) was statistically insignificant
7 of 18
(p > 0.05), indicating that the pattern of differences before aging corresponds to that after
aging. The differences in the mean pre-aging Vickers microhardness values are shown in
Figure 4. The differences in the mean post-aging Vickers microhardness values are shown
using the 5.
in Figure post-hoc Bonferroni
The change in meantest. Significant
values differences
as the result of thein flexural
aging strengths
process were ob-
is presented in
served for each of the seven photopolymerization modes (Figure 3).
Figure 6.

Mean flexural
Figure 3. Mean flexuralstrength
strengthvalues
values(MPa)
(MPa)andandstandard
standarddeviation
deviation (error
(error bars)
bars) (MPa)
(MPa) forfor pho-
photo-
polymerization mode
topolymerization modeand
andpre-/post-aging status.
pre-/post-aging status.

Before calculating the Vickers microhardness test results, an analysis of the measure-
ments in terms of the occurrence of outliers, normality of distribution and skewness was
performed to characterize the samples under individual conditions. One finding identi-
fied as an outlier was removed from the pool. In each group, the distribution of results
did not deviate from the normal distribution and the values of skewness and kurtosis
were considered to be acceptable. A mixed-model analysis of variance was carried out to
verify the hypothesis that the photopolymerization method has an impact on the Vickers
microhardness measurements. The result of Levene’s test suggested that the assumption
of the homogeneity of variance was not met for the post-aging mean values. The results
were statistically significant for both the pre-aging and post-aging photopolymerization
processes (F (6, 524.75) = 58.27; p < 0.001; η2 = 0.82; and FWelch (6, 14.6) = 30.54; p < 0.001;
η2 = 0.85, respectively). There was also a significant change in the Vickers microhardness
parameters as a result of aging (λ = 0.86, F (1, 34) = 215.27; p < 0.001; η2 = 0.86). However,
the effect of the interaction (ageing × polymerization mode) was statistically insignificant
(p > 0.05), indicating that the pattern of differences before aging corresponds to that after
aging. The differences in the mean pre-aging Vickers microhardness values are shown in
Figure 4. The differences in the mean post-aging Vickers microhardness values are shown in
Figure 5. The change in mean values as the result of the aging process is presented in Fig-
ure 6.
Materials 2023, 16, x FOR PEER REVIEW 8 of 18
Materials
Materials2023,
2023,16,
16,x113
FOR PEER REVIEW 8 of
8 of1818

Figure
Figure4.4.Mean
MeanVickers
Vickersmicrohardness
microhardnessvalues
valuesfor
fordifferent
differentphotopolymerization
photopolymerizationmodes
modes(pre-aging).
(pre-aging).
Figure 4. Mean Vickers microhardness values for different photopolymerization modes (pre-aging).

Figure 5. Mean Vickers microhardness values for different photopolymerization modes (post-aging).
Figure 5. Mean Vickers microhardness values for different photopolymerization modes (post-ag-
Figure 5. Mean Vickers microhardness values for different photopolymerization modes (post-ag-
ing).
ing).
ls 2023, 16, Materials
x FOR PEER 16, 113
2023,REVIEW 9 of 18 9 of 18

Figure 6. Change in mean

Figure 6. Vickers
Changemicrohardness values
in mean Vickers as the result values
microhardness of agingasinthe
groups
resultthat
of corre-
aging in groups that
sponded to different photopolymerization
corresponded modes (p < 0.001). modes (p < 0.001).
to different photopolymerization

The lowest
The lowest Vickers Vickers microhardness
microhardness value was measured valuefor was
themeasured
3 s fast-cureformode
the 3 (M
s fast-cure mode
(M = it
= 44.59, SD = 2.65); 44.59,
was SD = 2.65); it was
significantly lower significantly lower than
than the values the values
measured measured
for all the otherfor all the other
modes. The second-lowest
modes. The second-lowest Vickers microhardness
Vickers microhardness value was
value was obtained forobtained for the 5 s pulse-cure
the 5 s pulse-
cure mode (M = 57.58, SD = 3.57). In this case, the Vickers microhardness value was statis-was statistically
mode (M = 57.58, SD = 3.57). In this case, the Vickers microhardness value
significantly
tically significantly different different fromobtained
from those those obtained
for thefor the modes,
other other modes,
exceptexcept
for thefor 5 the
s 5 s fast-cure
fast-cure mode.mode. The Vickers
The Vickers microhardness
microhardness value measured
value measured for the 5for thefast-cure
s the 5 s the fast-cure
mode mode was
also significantly
was also significantly differentthan
different (lower) (lower)
thosethan those obtained
obtained for the
for the other other photopolymerization
photopolymeri-
zation modes. modes.
In contrast,In contrast, no statistically
no statistically significant
significant differencesdifferences
in Vickersin Vickers microhardness values
microhardness
values were observed for the 10 s fast-cure mode, 20 s fast-cure mode, 10 s pulse-cure mode or 9 s
were observed for the 10 s fast-cure mode, 20 s fast-cure mode, 10 s pulse-cure
step-cure
mode or 9 s step-cure mode.
mode.
The analysis
The analysis of differences in ofVickers
differences in Vickers microhardness
microhardness values resulting values
fromresulting
the use offrom the use of
different modes different modesphotopolymerization
of post-aging of post-aging photopolymerization
was carried outwas carried
using out using
a post-hoc testa post-hoc test
with the Games–Howell correction. The correction
with the Games–Howell correction. The correction was applied due to the breach of the was applied due to the breach of the
homogeneity
homogeneity of variance. of variance.
In addition, inIn addition,
this in lowest
case, the this case, the lowest
Vickers Vickers microhardness
microhardness value wasfor
value was measured measured for the
3 s fast-cure mode (M = 38.73, SD = 5.8); it was significantly
the 3 s fast-cure mode (M = 38.73, SD = 5.8); it was significantly lower than the values lower than the values measured
measured for all the other modes. The second-lowest Vickers microhardness value was was obtained
for all the other modes. The second-lowest Vickers microhardness value
obtained for thefor5the 5 s pulse-cure
s pulse-cure mode mode
(M =(M = 49.85,
49.85, SD =SD = 1.88).
1.88). Significant
Significant differences
differences werewere observed
between this mode and the 3 s fast-cure mode, 20 s fast-cure mode, 10 s pulse-cure mode
observed between this mode and the 3 s fast-cure mode, 20 s fast-cure mode, 10 s pulse-
and 9 s step-cure mode. However, no difference was observed between the average Vickers
cure mode and 9 s step-cure mode. However, no difference was observed between the
microhardness value obtained by this photopolymerization mode and the 5 s fast-cure
average Vickers microhardness value obtained by this photopolymerization mode and
mode, or the 10 s fast-cure mode. The 5 s fast-cure mode (M = 53.69, SD = 1.56) differed
the 5 s fast-cure mode, or the 10 s fast-cure mode. The 5 s fast-cure mode (M = 53.69, SD =
significantly from the 3 s fast-cure mode, 20 s fast-cure mode, and 10 s pulse-cure mode.
1.56) differed significantly from the 3 s fast-cure mode, 20 s fast-cure mode, and 10 s pulse-
On the other hand, the 10 s fast-cure mode (M = 57.5, SD = 4.39) only differed significantly
cure mode. On the other hand, the 10 s fast-cure mode (M = 57.5, SD = 4.39) only differed
from the 3 s fast-cure mode. The highest Vickers microhardness values were obtained for
significantly from the 3 s fast-cure mode. The highest Vickers microhardness values were
the 10 s pulse-cure mode (M = 60.23, SD = 1.48) and the 20 s fast-cure mode (M = 60.78,
obtained for the 10 s pulse-cure mode (M = 60.23, SD = 1.48) and the 20 s fast-cure mode
SD = 1.52).
(M = 60.78, SD = 1.52).
The chemical formulae of the resins BisGMA, TEGDMA, UDMA, and BisEMA, which
were the main materials that underwent the photopolymerization process as a result of
 Materials 2023, 16, x FOR PEER REVIEW 10 of 18

Materials 2023, 16, 113 10 of 18

The chemical formulae of the resins BisGMA, TEGDMA, UDMA, and BisEMA,
which were the main materials that underwent the photopolymerization process as a re-
irradiation, are shown
sult of irradiation, in Figure
are shown 7. The 7.
in Figure figure
The shows the chemical
figure shows bondsbonds
the chemical involved in the
involved
photopolymerization process.
in the photopolymerization process.

Figure 7.
Figure 7. Chemical
Chemicalformulae
formulaeofofthe
theresins
resinsincluded in in
included thethe
composites with
composites the the
with denoted bonds
denoted in-
bonds
volved ininthe
involved thephotopolymerization
photopolymerization process.
process.

Toobserve
To observethe
the photopolymerization
photopolymerization process
process that occurs as a result
result of
of different
different modes
modes
of irradiation
of irradiationofofdental
dentalcomposite
compositeresin,
resin,FTIR
FTIRspectroscopic
spectroscopictests
testswere
werecarried
carriedout.
out.Figure
Figure8
8 presents
presents thethe FTIR
FTIR spectrum
spectrum obtained
obtained using
using thethe
ATRATR technique
technique for for
thethe composite
composite before
before the
the irradiation
irradiation process.
process.
The FTIR studies proved the presence of signals that were characteristic of the chemical
bonds present in the resins and the composite filler. Bands that were characteristic of the
stretching vibrations of OH groups in the wavenumber range of 3700–3200 cm−1 and
those characteristics of the stretching vibrations of -CH3 and -CH2 groups in the range of
3000–2700 cm−1 were observed. An intense peak that corresponded to the C=O stretching
vibrations in the range of 1900–1600 cm−1 was found. The FTIR spectra also showed the
presence of C=C stretching vibrations in the wavenumber range of 1690–1580 and the
presence of aromatic ring vibrations in the wavenumber range of 1550–1450 cm−1 . The
tests also exhibited the presence of signals that were characteristic of the CH3 groups in the
 Materials 2023, 16, 113 11 of 18

range of wave numbers 1470–1350 cm−1 . Signals that were characteristic of silicon present
in the composite filler were also observed in the form of an intense peak in the wavenumber
16, x FOR PEER REVIEW 11 of 18
range of 1100–900 cm−1 . Figure 9 presents the summary of FTIR-ATR spectra before and
after irradiation with the denoted bands involved in the photopolymerization process.

Figure 8. FTIR-ATR spectrum of the composite before irradiation with the denoted spectral bands.

The FTIR studies proved the presence of signals that were characteristic of the chem-
ical bonds present in the resins and the composite filler. Bands that were characteristic of
the stretching vibrations of OH groups in the wavenumber range of 3700–3200 cm−1 and
those characteristics of the stretching vibrations of -CH3 and -CH2 groups in the range of
3000–2700 cm−1 were observed. An intense peak that corresponded to the C=O stretching
vibrations in the range of 1900–1600 cm−1 was found. The FTIR spectra also showed the
presence of C=C stretching vibrations in the wavenumber range of 1690–1580 and the
presence of aromatic ring vibrations in the wavenumber range of 1550–1450 cm−1. The tests
also exhibited the presence of signals that were characteristic of the CH3 groups in the
range of wave numbers 1470–1350 cm−1. Signals that were characteristic of silicon present
in the composite filler were also observed in the form of an intense peak in the wavenumber
range of 1100–900 cm−1. Figure 9 presents the summary of FTIR-ATR spectra before and
Figure 8. FTIR-ATR spectrum
after
Figure of the
irradiation
8. FTIR-ATR composite
with ofbefore
the denoted
spectrum irradiation
bands with
involved
the composite before inthe
thedenoted spectral bands.
photopolymerization
irradiation with the denoted process.
spectral bands.

The FTIR studies proved the presence of signals that were characteristic of the chem-
ical bonds present in the resins and the composite filler. Bands that were characteristic of
the stretching vibrations of OH groups in the wavenumber range of 3700–3200 cm−1 and
those characteristics of the stretching vibrations of -CH3 and -CH2 groups in the range of
3000–2700 cm−1 were observed. An intense peak that corresponded to the C=O stretching
vibrations in the range of 1900–1600 cm−1 was found. The FTIR spectra also showed the
presence of C=C stretching vibrations in the wavenumber range of 1690–1580 and the
presence of aromatic ring vibrations in the wavenumber range of 1550–1450 cm−1. The tests
also exhibited the presence of signals that were characteristic of the CH3 groups in the
range of wave numbers 1470–1350 cm−1. Signals that were characteristic of silicon present
in the composite filler were also observed in the form of an intense peak in the wavenumber
range of 1100–900 cm−1. Figure 9 presents the summary of FTIR-ATR spectra before and
after irradiation with the denoted bands involved in the photopolymerization process.

Figure
Figure9.9.Comparison
Comparisonof
of the
the FTIR-ATR spectraof
FTIR-ATR spectra ofcomposites
compositeswith
withthe
the denoted
denoted bands
bands involved
involved in
in the
the photopolymerization process.
photopolymerization process.

The FTIR-ATR tests showed an evident increase in the intensity of the peak that corre-
sponded to the stretching vibrations of the -CH2 groups after irradiation of the composites,
which indicates the photopolymerization process. As a result of the photopolymerization
process of the composite, the quantity of C=C double bonds decreases, and the quantity of
-CH2 bonds increases. The lowest peak intensity at the position of 2948 cm−1 was observed
for the unexposed composite. The highest peak intensity was found for the composite
irradiated for 10 s in the pulsed mode. With the increase in the irradiation duration of the
 The FTIR-ATR tests showed an evident increase in the intensity of the peak that cor-
responded to the stretching vibrations of the -CH2 groups after irradiation of the compo-
sites, which indicates the photopolymerization process. As a result of the photopolymer-
ization process of the composite, the quantity of C=C double bonds decreases, and the
quantity of -CH2 bonds increases. The lowest peak intensity at the position of 2948 cm−1
Materials 2023, 16, 113 was observed for the unexposed composite. The highest peak intensity was found12for the
of 18
composite irradiated for 10 s in the pulsed mode. With the increase in the irradiation du-
ration of the composite in the continuous mode, there was an increase in the intensity of
the peak in
composite at the
thecontinuous
position of mode,2948 cm −1. The tests proved the much higher degree of photo-
there was an increase in the intensity of the peak at the
polymerization of−
position of 2948 cm . The tests proved thethe
the
1 composite using pulsed
much anddegree
higher slow-start mode compared toof
of photopolymerization the
continuous
the compositemode. using the pulsed and slow-start mode compared to the continuous mode.
ToTo observe
observe thethe photopolymerization
photopolymerization process
process onon the
the entire
entire surface
surface ofofthethe composite,
composite,
tests
tests were
were carried
carried outout using
using the
the FTIR
FTIR Nicolet
Nicolet In10MX
In10MX microscope.
microscope. The
The tests
tests referred
referred toto
thethe
sample
sample irradiated
irradiated forfor5 s 5insthe
in the continuous
continuous mode mode ands in
and 20 20the
s incontinuous
the continuous
mode.mode. The
The test
test results
results are shownare shown
in Figuresin Figures
10 and1011.and 11.

Figure
Figure 10.10.Results
ResultsofofFTIR
FTIR mapping
mapping tests,
tests, in
in which
whichthe
thecomposite
compositesamples
sampleswere
wereexposed to to
exposed thethe
con-
tinuous mode for 5 s: (a) chemical map obtained using the correlation method based on the peak at
continuous mode for 5 s: (a) chemical map obtained using the correlation method based on the peak
the position of 2960 cm−−11, (b) 3D mapping image; (c) FTIR spectrum obtained using the specular
at the position of 2960 cm , (b) 3D mapping image; (c) FTIR spectrum obtained using the specular
reflection technique.
reflection technique.

The tests showed a much more homogeneous chemical structure of the composite after
20 s of continuous irradiation compared to the sample irradiated for 5 s in the continuous
mode. These differences are visible on both chemical maps and 3D profiles of the tested
samples. Smaller differences in the signal intensity were observed for the sample irradiated
for 20 s in the continuous mode compared to that irradiated for 5 s in the continuous mode.
Materials 2023,
Materials 16, 16,
2023, 113x FOR PEER REVIEW 1313of of
18 18

Figure 11. Results of FTIR mapping tests, in which the composite samples were exposed to the con-
Figure 11. Results of FTIR mapping tests, in which the composite samples were exposed to the
tinuous mode for 20 s: (a) chemical map obtained using the correlation method based on the peak at
continuous mode for 20 s: (a) chemical map obtained using the correlation method based on the peak
the position of 2960 cm−−11, (b) 3D mapping image; (c) FTIR spectrum obtained using the specular
at the position of 2960
reflection technique. cm , (b) 3D mapping image; (c) FTIR spectrum obtained using the specular
reflection technique.
The tests showed a much more homogeneous chemical structure of the composite
XPS Spectroscopy
after 20 s of continuous irradiation compared to the sample irradiated for 5 s in the con-
As stated before, the hardening of a resin involves terminal carbon atoms. Their
tinuous mode. These differences are visible on both chemical maps and 3D profiles of the
double bonds break, and single C-C bonds are created. Simultaneously, the hybridization
tested samples. Smaller differences in the signal intensity were observed for the sample
of these carbon atoms changes from sp2 to sp3 . “Fresh” and “hardened” resin states can be
irradiated for 20 s in the continuous mode compared to that irradiated for 5 s in the con-
detected using XPS spectroscopy because the two carbon states are distinguishable by this
tinuous mode.
method. Figure 12 presents high-resolution spectra of the following two selected samples:
“5 s continuous mode” and “20 s continuous mode”.
XPS Spectroscopy
A set of peaks used to recreate spectra envelopes was based on publications by
Koinuma As [11],
statedBriggs
before,[12],
the and
hardening
Beamson of a[13].
resin The
involves terminal
following carbon
three peaks atoms.
are ofTheir dou-
special
interest: C-C sp (blue), which corresponds to carbon atoms building the main resins’of
ble bonds break,
3 and single C-C bonds are created. Simultaneously, the hybridization
these C-H
chains, carbon atoms
(red), whichchanges from spto
corresponds 2 to sp3. “Fresh” and “hardened” resin states can be
hydrogenated terminal carbon atoms, and C=C
detected
2 using XPS spectroscopy because
sp , which corresponds to terminal, double-bonded the two carbon
carbon states
atoms.are distinguishable by this
method.
FigureFigure 12 presents
12 shows that thehigh-resolution
2
C=C sp peak is spectra of the following
significantly larger in two selected
the case samples:
of the less
“5 s continuous
irradiated, thus lessmode” and “20
hardened, firsts continuous
sample (i.e.,mode”.
“5 s continuous”), clearly indicating that
A set of
these carbon peaks
atoms areused
moreto numerous
recreate spectra envelopes
compared to thewas
more based on publications
hardened, by Koi-
second sample
(20numa [11], Briggs
s continuous). [12], and Beamson
Simultaneously, [13].peak
the C-C The following
is larger inthree peaks
the case of are
theof special
second interest:
sample;
theC-C sp3 (blue),
number of C-C sp3 atoms
which corresponds
is greaterto because
carbon atoms
they arebuilding the main
the product resins’ chains, C-H
of hardening.
(red), which corresponds to hydrogenated terminal carbon atoms, and C=C sp2, which
corresponds to terminal, double-bonded carbon atoms.
Figure 12 shows that the C=C sp2 peak is significantly larger in the case of the less
irradiated, thus less hardened, first sample (i.e., “5 s continuous”), clearly indicating that
Materials 2023, 16, x FOR PEER REVIEW 14 of 18

these carbon atoms are more numerous compared to the more hardened, second sample (20
s continuous). Simultaneously, the C-C peak is larger in the case of the second sample; the
Materials 2023, 16, 113 14 of 18
number of C-C sp3 atoms is greater because they are the product of hardening.

C-H

C=C sp2
C-C sp3
intensity (a. u.)

5 sec. continuous

20 sec. continuous

291 290 289 288 287 286 285 284 283 282
binding energy (eV)

Figure 12. High-resolution XPS spectra of C1s regions: sample “5 s continuous” and “20 s continu-
Figure 12. High-resolution XPS spectra of C1s regions: sample “5 s continuous” and “20 s continuous”.
ous”.

4.4.Discussion
Discussion
The
Theexperimental
experimentalresultsresults show
show that the change in the the photopolymerization
photopolymerizationtime timehas hasa
agreat
greatimpact
impact onon
thethe mechanical
mechanical properties
properties of resin,
of the the resin,
such such as flexural
as flexural strengthstrength
and Vickersand
microhardness.
Vickers Hence, Hence,
microhardness. the null thehypothesis was rejected.
null hypothesis was Probably, the total amount
rejected. Probably, the total of
energy generated
amount of energy during
generated the during
photopolymerization of the composite
the photopolymerization of thematerials
composite is significant.
materials
isThe comparison
significant. The of different photopolymerization
comparison modes with similar
of different photopolymerization modes with photopolymeriza-
similar pho-
tion times that translate to similar total energies reveals (5
topolymerization times that translate to similar total energies reveals (5 s fast-cures fast-cure and pulse-cureand
modes—10 J/cm 2 and 10 2s fast-cure and pulse-cure modes—20 J/cm2 ) no 2statistically
pulse-cure modes—10 J/cm and 10 s fast-cure and pulse-cure modes—20 J/cm ) no statis-
significant
tically differences
significant in the in
differences mechanical
the mechanicalparameters of the of
parameters composite materials.
the composite Bauer
materials.
et al. et
Bauer demonstrated
al. demonstrated that that
the photopolymerization
the photopolymerization of composite
of composite materials
materials should
should be be
no
noshorter
shorter than
than2020
s to achieve
s to achieve values
valuesof of
flexural
flexuralstrength
strengthequal
equaltotothethe
ISO standard
ISO standard [14]. In
[14].
this study, the authors used a medium-power LED curing light (1261 mW/cm 22 ). This
In this study, the authors used a medium-power LED curing light (1261 mW/cm ). This
wasalso
was alsoconfirmed
confirmedby byBhamra
Bhamraetetal., al.,who
whoshowed
showedthat thatproviding
providingthe therequired
requireddose doseof of
irradiation is necessary for proper photopolymerization and that
irradiation is necessary for proper photopolymerization and that increasing this dose doesincreasing this dose does
notsignificantly
not significantlyimprove
improvethe the mechanical
mechanical properties
properties of the
of the material
material [15].[15]. So, higher
So, the the higher the
the lamp
lamp power,power, the shorter
the shorter the required
the required photopolymerization
photopolymerization times.times. In our
In our study,
study, valuesvalues
of
of flexural strength higher than those required for composite
flexural strength higher than those required for composite materials according to ISO materials according to ISO
4049:2010-12(80
4049:2010-12 (80MPA)
MPA)were were obtained
obtained forfor all
all photopolymerization
photopolymerization modes. modes.
Dental resins polymerized with continuous modes show bettermechanical
Dental resins polymerized with continuous modes show better mechanicalproperties
proper-
in comparison with those obtained by pulsed and step-cure
ties in comparison with those obtained by pulsed and step-cure photopolymerization photopolymerization modes,
as confirmed by Dos Santos et al. [16]. This was also confirmed
modes, as confirmed by Dos Santos et al. [16]. This was also confirmed by the results by the results of our study.
of
On the other hand, Ivanisevic et al. demonstrated that the Vickers microhardness of the
our study. On the other hand, Ivanisevic et al. demonstrated that the Vickers microhard-
surface of materials polymerized using the step-cure method is higher than that of samples
ness of the surface of materials polymerized using the step-cure method is higher than
polymerized using the continuous mode [17]. However, different results were obtained
that of samples polymerized using the continuous mode [17]. However, different results
depending on the place of microhardness measurements. In the case of measurements
were obtained depending on the place of microhardness measurements. In the case of
performed at the bottom of the samples, higher values were observed in the group of
samples that were continuously polymerized [17]. Nonetheless, the microhardness of the
outer surface appears to be of the greatest importance, as this is the surface that would
remain in contact with the oral cavity environment. Both studies agree that the longer the
Materials 2023, 16, 113 15 of 18

photopolymerization times, the higher the microhardness values obtained, regardless of

the photopolymerization mode used [16,17].
Par et al. studied the effect of prolonged photopolymerization (30 s) on Vickers
microhardness values and temperature increases [18]. They showed that the total energy
delivered to the material increases with the photopolymerization time, contributing to
increased microhardness and temperature values. This is in line with the results of our study,
which demonstrate the effect of photopolymerization time on the microhardness values [19].
The increase in the composite temperature as a function of the photopolymerization times
and modes had been confirmed by our previous studies.
According to Almeida et al., the mechanical properties of composite materials can also
be improved by heating the material to 60 ◦ C before photopolymerization [20]. This will
improve both the flexural strength and the microhardness values (as measured using the
Knoop scale). These results are also consistent with those reported by other authors [21,22].
The choice of the photopolymerization device has an impact not only on the mechani-
cal properties of materials, but also, for example, on marginal leakage. As shown by Yilmaz
et al., marginal leakage was minimized with the use of a 1300 mW/cm2 LED lamp, as
compared to 500 mW/cm2 LEDs and quartz tungsten halogen lamps, despite the longer
photopolymerization times used in the case of the latter two types of devices being twice as
long [23]. The photopolymerization time can strongly influence the Vickers microhardness,
which increases with the photopolymerization times when extended from 20 to 40 and 60 s,
as demonstrated by Hammouda [24]. In contrast, Peutzfled et al. [25] and Cuevas-Suárez
et al. [26] demonstrated that short photopolymerization times with high irradiation powers
may lead to lower microhardness values, as compared to lamps with lower irradiation
power but longer photopolymerization times, if similar total energies are delivered to the
material in both cases.
During composite photopolymerization, not all double-carbon bonds are converted
into single-carbon bonds, which is considered as the degree of conversion. The literature
reports that the degree of conversion varies between 14 and 44% after the photopolymer-
ization of composite resins [27]. In turn, 10% or more of unreacted double bonds result
in the release of residual monomers [28]. The composition of the composite dental resins
influences the degree of conversion and the residual monomer. In our research, all samples
were made of the same material, which made it possible to standardize the test scheme,
but it is not known whether we would obtain similar results using materials with different
resin compositions. The resins of the matrix of composite resin are characterized by dif-
ferent degrees of conversion, as demonstrated by Gawriołek et al. [29]. The lowest degree
conversion values 24 h after photopolymerization was obtained for Bis-GMA (34.5%) and
the highest for TEGDMA (82.5%). Increasing the degree of conversion can be achieved by
extending the photopolymerization time to 40 s [30], or by changing the filler to a more UV
transmissive filler [31]. Our research also confirms the rule that the longer the photopoly-
merization time, the higher the degree of conversion. The degree of resin conversion has
a significant positive effect on the mechanical properties of composite materials, such as
flexural strength or water sorption [29]. According to various studies, the type of curing
lamp does not affect the conversion, but the amount of energy has a significant impact on
the degree of conversion, as demonstrated by Yoon et al. [32]. Our study also confirms that
longer photopolymerization times, and thus higher energy doses, increase the degree of
conversion. In addition, our research suggests that the photopolymerization mode may
affect the degree of conversion, but this needs to be tested with different composite resins.
This study has been burdened by certain limitations due to the simplified laboratory
model used. The research did not consider factors such as the residual monomer fraction,
which may affect the quality of the photopolymerization of composite resins. However,
Sonkaya et al. showed in their studies that the photopolymerization time did not affect
the residual monomer. According to this study, only the material composition influenced
the residual monomer [33]. Since we used one dental composite material in the study, we
omitted the residual monomer analysis.
Materials 2023, 16, 113 16 of 18

When assessing the aging of materials, chemical and thermal factors associated with
food consumption and the effect of brushing were not considered. The pH of the drinks
and meals that we consume can have a great influence on the mechanical properties of
composite materials [34]. Brushing, particularly using hard brushes and abrasive whitening
pastes, may also lead to changes in the microhardness of composites. According to the
study by Salam et al., most of the whitening toothpastes tested contributed to the increased
microhardness of composite materials; however, some of them reduced the values of this
parameter in a statistically significant manner [35].
The appropriate choice of the mode and duration of photopolymerization of compos-
ite resins affects the mechanical properties of the resin. Particularly regarding the final
composite filling layers, the clinicians should choose longer photopolymerization times
(10; 20 s) to obtain the best mechanical properties and degree of conversion. As a result, the
survival of dental restorations within the oral cavity could be extended.

5. Conclusions
Within the limitation of this study that examined only one dental resin, the following
conclusions can be drawn:
1. Flexural strength and Vickers microhardness of the tested resin are mainly determined
by the duration of photopolymerization. A shorter duration of curing led to lower
values of flexural strength and Vickers microhardness.
2. The best mechanical properties of the tested resin before and after aging were obtained
in the 20 s fast-cure mode.
3. The values of flexural strength and Vickers microhardness of the tested resin decreased
after artificial aging, in particular in the pulse-cure 5 s mode.
4. The values of the degree of conversion of the tested resin were higher using the pulsed
and slow-start mode, compared to the continuous mode photopolymerization.
5. The values of the degree of conversion of the tested resin increased with increasing
duration of continuous mode photopolymerization.
6. The chemical structure of the tested resin was more homogenous with a longer
duration of photopolymerization.

Author Contributions: Conceptualization, L.S. and I.R.-K.; methodology, L.S., W.S.-C. and M.K.;
validation, L.S. and D.W.; formal analysis, D.W. and W.S.-C.; investigation, L.S., W.S.-C. and M.K.;
resources, L.S. and D.W.; data curation, D.W.; writing—original draft preparation, L.S., D.W. and W.S.-
C.; writing—review and editing, M.K. and I.R.-K.; visualization, L.S., W.S.-C. and M.K.; supervision,
I.R.-K.; project administration, L.S. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We would like to express special thanks to Jan Kutnik (Institute of Psychology,
the John Paul II Catholic University of Lublin) for their assistance with the statistical analysis and
Paweł Jarosz (Engineering Studies Centre, the Institute of Technical Sciences and Aviation, the State
School of Higher Education in Chełm) for their assistance in conducting the experimental research.
Conflicts of Interest: The authors declare no conflict of interest.

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