diagnostics

Article
Raman Spectroscopy as Spectral Tool for Assessing the Degree
of Conversion after Curing of Two Resin-Based Materials Used
in Restorative Dentistry
Eduard Gatin 1,2 , Stefan-Marian Iordache 3, * , Elena Matei 4 , Catalin-Romeo Luculescu 5 ,
Ana-Maria Iordache 3, *, Cristiana Eugenia Ana Grigorescu 3 and Roxana Romanita Ilici 6

1 Faculty of Medicine, University of Medicine “Carol Davila”, Blv. Eroii Sanitari 8, Sector 5,
020021 Bucharest, Romania
2 Faculty of Physics, University of Bucharest, Atomistilor 405, 077125 Magurele, Romania
3 Optospintronics Department, National Institute for Research and Development for
Optoelectronics—INOE 2000, 077125 Magurele, Romania
4 National Institute of Materials Physics, Atomistilor 405A, 077125 Magurele, Romania
5 National Institute for Laser, Plasma and Radiation Physics, CETAL, 077125 Magurele, Romania
6 Faculty of Dental Medicine, University of Medicine “Carol Davila”, Plevnei Route No. 17-23, Sector 1,
020021 Bucharest, Romania
* Correspondence: stefan.iordache@inoe.ro (S.-M.I.); ana.iordache@inoe.ro (A.-M.I.)

Abstract: (1) Background: The treatment of dental cavities and restoration of tooth shape requires
specialized materials with specific clinical properties, including being easy to model, light-cured,
having a natural color, reduced shrinkage, a hardness similar to hydroxyapatite, and no leakage. The
dimensional stability of resin composite materials is affected by polymerization shrinkage, degree of
conversion (number of π carbon bonds converted into σ ones), thermal contraction and expansion,
Citation: Gatin, E.; Iordache, S.-M.;
and interactions with an aqueous environment. (2) Methods: The materials used in our investigation
Matei, E.; Luculescu, C.-R.; Iordache,
were two composite resins with similar polymer matrices, but different filler (micro/nano filler).
A.-M.; Grigorescu, C.E.A.; Ilici, R.R.
Raman Spectroscopy as Spectral Tool
To evaluate the properties of samples, we employed the pycnometer technique (pycnometer from
for Assessing the Degree of Paul Marienfeld Gmbh, Lauda-Königshofen, Germany), RAMAN spectroscopy technique (MiniRam
Conversion after Curing of Two Equipment from B&W Tek Inc., Plainsboro Township, NJ, USA; 785 nm laser source), SEM and EDX
Resin-Based Materials Used in (FEI Inspect S.). (3) Results: The size of the filler plays an important role in the polymerization: for
Restorative Dentistry. Diagnostics the pycnometric results, the larger particle filler (Sample 1) seems to undergo a rapid polymerization
2022, 12, 1993. https://doi.org/ during the 45 s curing, while the nanoparticle filer (Sample 2) needs additional curing time to fully
10.3390/diagnostics12081993 polymerize. This is related to a much larger porosity, as proved by SEM images. The lower degree of
Academic Editor: Elina A. Genina conversion, as obtained by Raman spectroscopy, in the same geometry means that the same volume
is probed for both samples, but Sample 1 is more porous, which means less amount of polymer is
Received: 30 June 2022
probed for Sample 1. (4) Conclusions: For the two composites, we obtained a degree of conversion of
Accepted: 13 August 2022
59% for Sample 1 and 93% for Sample 2, after 45 s of curing.
Published: 17 August 2022

Publisher’s Note: MDPI stays neutral Keywords: raman spectrometry; conversion rate; resin-based composite; dentistry restoration
with regard to jurisdictional claims in
published maps and institutional affil-
iations.

1. Introduction
The treatment of dental cavities and restoration of tooth shape requires specialized
Copyright: © 2022 by the authors.
materials with specific clinical properties, including being easy to model, light-cured,
Licensee MDPI, Basel, Switzerland. having a natural color, reduced shrinkage, a hardness similar to hydroxyapatite, and no
This article is an open access article leakage [1]. A single unique material does not possess all these properties but by combining
distributed under the terms and an inorganic filler with a polymer matrix, one obtains a resin-based material that has all
conditions of the Creative Commons of them. Thus, since 1958, resin-based composites have been increasingly used as dental
Attribution (CC BY) license (https:// restorative materials or dental cements, because of their good esthetic and mechanical
creativecommons.org/licenses/by/ properties [2]. The first generation of composites introduced in the clinical practice was
4.0/). in the 1980s with Bis-GMA as a principal component, followed in the 1990s with the

Diagnostics 2022, 12, 1993. https://doi.org/10.3390/diagnostics12081993 https://www.mdpi.com/journal/diagnostics

Diagnostics 2022, 12, 1993 2 of 9

second generation of resin composites based on polyglass materials. First-generation

composite resin materials are limited by three drawbacks: (1) unreacted monomer left
after polymerization; (2) less than optimal hardness which limits the application, e.g.,
the material cannot be used for all teeth, only for the ones that exhibit lower masticatory
loads during chewing; and (3) fatigue and cracking of the polymer due to shrinkage after
polymerization [3,4]. Among all, the most important factor is polymerization shrinkage [5]
that causes marginal gaps between the enamel and resin and can lead to premature failure
of the restoration [2]. Debonding may create plastic deformation, marginal leakage and
staining, postoperative sensitivity, and increase the risk of secondary caries formation and
pulpal inflammation. Polymerization shrinkage will impact the adhesion of the polymer–
tooth interface, which is an inevitable effect of the curing process as monomer molecules,
converted into a crosslinked polymer network, exchange van der Waals bonds for shorter
covalent bonds [6–8]. This volumetric shrinkage causes stress in confined environments
such as tooth cavities [9,10].
Incorporation of filler into resin matrix greatly influences and improves material
properties, provided that filler particles are bonded to polymer matrix or otherwise it may
actually weaken the resin. Thus, filler–polymer matrix coupling determines, to a large
extent, the mechanical strength and clinical longevity of dental composites. Several types
of filler are commonly used in clinical practice, including glass, pyrogenic silica, zirconia,
organic filler [11], metal/alloy [12], and, lately, bioactive glass [13,14].
Despite the variety of formulations, the polymerization shrinkage following curing
of the resin presents a major problem. The longevity of the composite resin material is
determined by the degree of conversion. By analyzing the degree of conversion, one could
establish a direct correlation between the quality of polymerization and the hardness of the
composite [15]. Spectrometry is the main technique to determine the residual monomers
due to its sensitivity towards conjugated structures (e.g., aromatic rings, C=C, etc.).
The objective of this study is to understand the local stresses and their dynamics for
different intervals of polymerizations, as well as imaging the tooth–resin interface. We
employed RAMAN investigation since it is a proven method to calculate the degree of
conversion [16,17]. Our aim is to reveal the differences between two widely used dental
materials, commercialized as “nano” and “micro” photopolymerizable dental composites
and demonstrate their behavior at the boundary between dentin and enamel. Identification
of this boundary could allow dental professionals to choose the appropriate material for
the right tooth (for example, teeth used in biting need sturdier materials than teeth used
for chewing [18]). We revealed important aspects regarding the chemical specimens in the
dentin–composite and enamel–composite interface areas by EDX and mapping methods
(secondary electrons, backscattered electrons).

2. Materials and Methods

The materials used in our investigation were two composite resins (RBC) with the
same polymer matrix (BIS-GMA, TEGDMA, BIS-EMA), but different filler (micro/nano
filler) commercially available on the market in Romania. Sample 1 is ValuxTM Plus Restora-
tive 3M ESPE, a first-generation composite resin material which contains Bis-GMA and
TEGDMA resins and 66% vol. zirconia/silica inorganic filler with a particle size range
of 3.5 to 0.01 micron. Sample 2 is BrilliantTM NG Coltene, a second-generation composite
resin material which is a nanocomposite with pre-polymerized particle filling with high
nanometric particle content. Sample 1 comes in 5 shades available in 4 g syringes, while
Sample 2 has a duo shade system in the same syringe simplifying the selection of color
and inventory of syringes [16–18]. Both samples have indications for anterior and posterior
restorations including inlays, onlays, and veneers. The characteristics of the samples are
presented in Table 1.
Diagnostics 2022, 12, 1993 3 of 9

Table 1. Characteristics of the two samples investigated in the present study.

Properties/Samples Sample 1 (ValuxTM ) Sample 2 (BrilliantTM )

Manufacturer 3M ESPE (USA) Coltène (Switzerland)
Composition microcomposite nanocomposite
Curing light Visible light Visible light
Curing time 40 s 20 s
Resin components Bis-GMA and TEGDMA TEGDMA, BIS-EMA
Inorganic filler type zirconia/silica Amorphous silica
Filler loading (vol.) 66% 65%
Particle size interval (µm) 0.01–3.5 0.02–2.5
Filler content by volume 66% 65 %

Small discs with a diameter of 5 mm and a thickness of 1 mm were prepared in

order to investigate the density of the material. Curing was performed with an LED lamp
(light emitting diodes, λ = 420 ÷ 480 nm, Kerr Corp., Orange, CA, USA), with different
curing programs (variable light intensity, different time rates and mixed). As a first step
of the investigation, the variation in the density of the samples was examined before
and after curing (curing time 45 s) using the Archimedes’ principle (pycnometer from
Paul Marienfeld Gmbh, Lauda-Königshofen, Germany). Density correction for water was
applied to the results.
For the composite restoration, the standardized mesio-occluso-distal (MOD) cavity
preparation was performed in an extracted upper human premolar, using a medium-
grained diamond bur. The molar extraction was performed during the complex treatment of
the upper jaw, for a sinus lift augmentation of a patient as reported [19]. The same bioethical
approval was applied. Sample 1 (ValuxTM Plus Restorative 3M ESPE) was incrementally
applied and light-cured for 20 s from the LED light-curing system, shifting output intensity
from 1.100 mW/cm2 to a peak of 1.330 mW/cm2 multiple times throughout the curing cycle.
Raman spectroscopy evaluation was performed with a BTR111—785 RAMAN spec-
trometer device (λ = 785 nm, output power p = 300 mW, and spectral resolution 4 cm−1 ) in
the Raman shift range 100–2200 cm−1 . The spectrometer is equipped with BAC101 immer-
sion Raman probe, with the minimum spot size for excitation of 100 µm at 0.5 mm. The
785 nm laser power used for all measurements was 30 mW (10% from 300 mW available)
which gives an irradiance of about 382 W/cm2 . The laser spot and irradiance levels were
kept constant during Raman spectra acquisition. Energy Dispersive X-Ray Spectroscopy
(EDX) and Scanning Electron Microscopy (SEM) were performed in a Zeiss Evo 50 XVP
microscope, at room temperature (RT), equipped with a secondary electron detector in
low vacuum and a solid state BSE detector, plus an auxiliary micro analytic SDD radiation
detector [19–21].

3. Results and Discussion

The results of the density variation for the two samples are presented in Table 2.
According to these values, a variation of more than 20% was observed for both samples,
slightly lower for the microcomposite than for the nanocomposite. Variation in density
(%) is equivalent to the experimentally determined polymerization shrinkage [22] and
calculated with the formula:
Density be f ore curing − Density a f ter curing
Variation (%) = × 100 (1)
Density be f ore curing
Diagnostics 2022, 12, 1993 4 of 9

Table 2. Pycnometric results for the two investigated samples.

Properties/Samples Sample 1 (ValuxTM ) Sample 2 (BrilliantTM )

Density (kg/m3 ) before curing 1931.447 1560.784
Density (kg/m3 ) after curing 1514.511 1217.557
Variation (%) 21.58 21.99

Considering that the mass of the composite remains the same and that density = ma-
ss/volume, a decrease of 20% indicates an equal expansion of the volume. Although the
results suggest that polymerization shrinkage is higher for Sample 2 (1217.557) and lower
for Sample 1 (1514.511), by using the volume of a cylinder (V = πr2 h) and by calculating
the ∆V as the difference between Vinitial –Vfinal , we obtain a difference of 5.375 mm3 for
Sample 1 and 4.375 mm3 for Sample 2. This means that the volume increase is higher
for Sample 1, which could mean a better polymerization (almost all the monomers are
polymerized, and the volume is expanded due to polymerization) and lower for Sample 2,
with only a 4.375 mm3 increase.
Thus, the size of the filler plays an important role in the polymerization: the larger
particle filler (Sample 1) undergoes a rapid polymerization during the 45 s curing, while
the nanoparticle filer (Sample 2) needs additional curing time to fully polymerize. The
lower polymerization shrinkage could suggest an unfinished polymerization process.

3.1. SEM Microscopy

Following density measurements, an imaging investigation was performed using
SEM. The samples were sectioned in depth and imaging was performed in the middle of
the section, but also on the side facing the curing lamp and the opposite side. The SEM
micrographs show that the microcomposite has a porous structure (Figure 1a), this porosity
being maintained on both the side facing the curing lamp (Figure 1b) and the opposite side
(Figure 1c). The nanocomposite shows a more compact surface, with rare and fine pores
(Figure 1d). However, there are large holes on the side facing the curing lamp (Figure 1e),
while the compactness of the back side surface is evident (few gaps in material—Figure 1f).

3.2. EDX Investigations

Sample 1 was selected as the material for the restoration of a tooth (filling up a cavity).
The tooth was sectioned and the EDX mapping was performed on the dentin–resin interface
and the enamel–resin interface (spectral accumulation was 15 min). The SEM imaging and
mapping were focused on the microcracking at the interface. Figure 2a shows the fracture
between the dentin/microcomposite. The fracture is large, probably due to the sectioning
process. The EDX mapping shows the major components of the two materials: the dentin
predominantly has P and Ca, while the composite has large amounts of Si, Al, and Ba.
Other elements (Na, F, Mg, K, Cl, and N) are present in both dentin and composite in trace
amounts, close to the limit of detection.
However, for the enamel/composite border (Figure 2b) a different situation is en-
countered. The composite shows large amounts of Si, Al, and Ba, but the enamel part
has no distinct elements (on its own). Common elements (Ca, F, Mg, K, N, Na, p, Cl,
and Zr) suggest that their concentration is similar for the two materials, both natural and
restorative.
This means that the formulation for the microcomposite is similar to the natural
formulation of the enamel. In the SEM micrographs it is evident that the border between
the enamel and microcomposite is welded whereas the dentin/microcomposite border has
an evident fracture. This fracture in the dentin/composite could also be due to the fact that
we did not use Ag+ to dry the dentin prior to the experiment.
 the section, but also on the side facing the curing lamp and the opposite side. The SEM
micrographs show that the microcomposite has a porous structure (Figure 1a), this poros-
ity being maintained on both the side facing the curing lamp (Figure 1b) and the opposite
side (Figure 1c). The nanocomposite shows a more compact surface, with rare and fine
Diagnostics 2022, 12, 1993 pores (Figure 1d). However, there are large holes on the side facing the curing lamp (Fig-
5 of 9
ure 1e), while the compactness of the back side surface is evident (few gaps in material—
Figure 1f).

(a) (b) (c)

Diagnostics 2022, 12, x FOR PEER REVIEW 5 of 10

Figure 1. SEM micrographs of the samples: (a) Sample 1-the microcomposite, seen in the middle of
the section area; (b) Sample 1-the side facing the curing lamp; (c) Sample 1-the side opposite to the
curing lamp; (d) Sample 2-the nanocomposite, in the middle of the section area; (e) Sample 2-the
side facing the curing lamp; (f) Sample 2-the side opposite to the curing lamp.

3.2. EDX Investigations

Sample 1 was selected as the material for the restoration of a tooth (filling up a cav-
ity). The tooth was sectioned and the EDX mapping was performed on the dentin–resin
interface and the enamel–resin interface (spectral accumulation was 15 min). The SEM
(d) (e)
imaging and mapping were focused (f) Figure 2a shows
on the microcracking at the interface.
the fracture between the dentin/microcomposite. The fracture is large, probably due to the
Figure 1. SEM micrographs of the samples: (a) Sample 1-the microcomposite, seen in the middle of
sectioning process. The EDX mapping shows the major components of the two materials:
the section area; (b) Sample 1-the side facing the curing lamp; (c) Sample 1-the side opposite to the
the dentin predominantly has P and Ca, while the composite has large amounts of Si, Al,
curing lamp; (d) Sample 2-the nanocomposite, in the middle of the section area; (e) Sample 2-the side
and Ba. Other elements (Na, F, Mg, K, Cl, and N) are present in both dentin and composite
facing the curing lamp; (f) Sample 2-the side opposite to the curing lamp.
in trace amounts, close to the limit of detection.

(a) Dentin/composite

Figure 2. Cont.
Diagnostics 2022, 12, 1993
Diagnostics 2022, 12, x FOR PEER REVIEW
6 of 9
6 of 10

(b) Enamel/composite
Figure 2. EDX measurements of the dentin/composite border (a) and enamel/composite border (b).
Figure 2. EDX measurements of the dentin/composite border (a) and enamel/composite border (b).

However,
3.3. Raman for the enamel/composite border (Figure 2b) a different situation is en-
Spectroscopy
countered. The composite shows large amounts of Si, Al, and Ba, but the enamel part has
Raman results (Figure 3) show a similar behavior for both samples 1 and 2, because
no distinct elements (on its own). Common elements (Ca, F, Mg, K, N, Na, p, Cl, and Zr)
both samples contain similar polymers. The main differences appear due to the filler:
suggest that their concentration is similar for the two materials, both natural and restora-
for the microcomposite (Figure 3a), bending of the ZrO bond appears at 1000 cm−1 [13]
tive.
and at 806 cm−1 for the bending of the Si2 O; in the case of the nanocomposite, there
This means that the formulation for the microcomposite is similar to the natural for-
are low intensity peaks at 806 cm−1 and 1200 cm−1 (associated with the stretching of
mulation of the enamel. In the SEM micrographs it is evident that the border between the
the SiO) and
enamel [11].microcomposite
Common peaks are associated
is welded with
whereas the different vibrations border
dentin/microcomposite of the has
carboxyl
an
groups: at 1300 cm −1 (stretching of the C=O bond), 1404 cm−1 (stretching of the C=CH ),
evident−fracture. This fracture in the dentin/composite could also be due to the fact that
1 (stretching of the aromatic ring), 1609 cm−1 (skeletal vibration of the aromatic
2
1446 cm not
we did use Ag+ to dry the dentin prior to the experiment.
ring), 1640 cm−1 (stretching of the C=C bond in methacrylate), and 1714 cm−1 (stretching
of3.3.
theRaman Spectroscopy
C=O bond) [11]. Comparing the spectra from uncured to 45 s curing, we can observe
variations regarding peak intensities, which suggest the presence of unreacted monomer
Raman results (Figure 3) show a similar behavior for both samples 1 and 2, because
inboth
both samples. Furthermore, considering
samples contain similar polymers. that the
The main spectra appear
differences were obtained
due to the from roughly
filler: for
the same spot, the spectra do not follow a monotonous trend because a
the microcomposite (Figure 3a), bending of the ZrO bond appears at 1000 cm [13] and atrapid
−1 saturation
is806
expected
cm−1 foron
thethe surface
bending of the
of the Si2O;sample. Additionally,
in the case the variation
of the nanocomposite, thereofare
background
low inten- is
negligible comparing to the prominent Raman peaks.
sity peaks at 806 cm and 1200 cm (associated with the stretching of the SiO) [11]. Com-
−1 −1

monFrom
peaksthe
areRaman spectrum
associated we can calculate
with different vibrationstheofdegree of conversion
the carboxyl groups: for the compos-
at 1300 cm−1
(stretching
ites, of the
using the C=O bond),
following 1404 [11,13,23,24]:
equation cm−1 (stretching of the C=CH2), 1446 cm−1 (stretching of
the aromatic ring), 1609 cm−1 (skeletal vibration of the aromatic ring), 1640 cm−1 (stretching
of the C=C bond
DC (in
%methacrylate),
) = 1− andI1714
(1609cm )45s (stretching
−1 /I (1640)45sof the C=O bond) [11]. Com-
× 100 (2)
paring the spectra from uncured to 45
I (1609 s curing,
)without we
curing /Ican
( observe
1640 variations
)without curing regarding peak
intensities, which suggest the presence of unreacted monomer in both samples. Further-
more, considering
Thus, for the that
twothe spectra were
composites weobtained
obtain: from59% roughly
degree of theconversion
same spot, the
for spectra
Sample 1
do not
and 93%follow a monotonous
for Sample 2, after trend because
45 s of curing.a rapid
Thesesaturation is expected
results could on the surface
be correlated with the
of the sample. Additionally, the variation of background is negligible
experimental data obtained via pycnometric measurements, but we have to consider comparing to thethat
prominent
each Raman
technique haspeaks.
its own particularity: the pycnometry gives the value of the entire
sample (by considering all the pores) whereas Raman spectroscopy measures the scattering
of photons on imperfect surfaces. Thus, the surface electronic states influence the shape of
the Raman peaks and are a “snapshot” of the irregular surfaces of the samples.
 Diagnostics 2022, 12, 1993 7 of 9
Diagnostics 2022, 12, x FOR PEER REVIEW 7 of 10

(a) (b)
Figure 3. Raman spectra of the microcomposite (a) and nanocomposite (b) following different cur-
Figure 3. Raman spectra of the microcomposite (a) and nanocomposite (b) following different
ing intervals.
curing intervals.
From the Raman spectrum we can calculate the degree of conversion for the compo-
For the restored tooth, the Raman spectra were obtained at the enamel–resin and
sites, using the following equation [11,13,23,24]:
dentin–resin interfaces and are shown in Figure 4. In this case, the Raman spectra are
𝐼(1609) ⁄𝐼 (1640) (2)
different
𝐷𝐶(%) = 1than
− the Raman spectra of the composites: ×we 100cannot identify with precision
𝐼(1609) ⁄𝐼(1640)
the components (e.g., ZrO is obstructed, while Si2 O and SiO have low intensity peaks)
Thus, for the two composites we obtain: 59% degree of conversion for Sample 1 and
and the stretching and bending of the carboxyl and carbonyl groups are shifted. The
93% for Sample 2, after 45 s of curing. These results could be correlated with the experi-
Diagnostics 2022, 12, x FOR PEER
skeletal vibration of the aromatic ring at 1609 cm−1 is shifted at 1624 cm−1 , whereas
REVIEW
mental data obtained via pycnometric measurements, but we have to consider that each8 of 10
the stretching of the methacrylate at 1640 cm−1 completely disappears, thus indicating a
technique has its own particularity: the pycnometry gives the value of the entire sample
complete polymerization.
(by considering all the pores) whereas Raman spectroscopy measures the scattering of
photons on imperfect surfaces. Thus, the surface electronic states influence the shape of
the Raman peaks and are a “snapshot” of the irregular surfaces of the samples.
For the restored tooth, the Raman spectra were obtained at the enamel–resin and
dentin–resin interfaces and are shown in Figure 4. In this case, the Raman spectra are dif-
ferent than the Raman spectra of the composites: we cannot identify with precision the
components (e.g., ZrO is obstructed, while Si2O and SiO have low intensity peaks) and the
stretching and bending of the carboxyl and carbonyl groups are shifted. The skeletal vi-
bration of the aromatic ring at 1609 cm−1 is shifted at 1624 cm−1, whereas the stretching of
the methacrylate at 1640 cm−1 completely disappears, thus indicating a complete polymer-
ization.

Figure4.4.Raman
Figure Ramanspectra
spectraofofthe
theenamel-resin
enamel-resininterface
interface and
and dentin-resin
dentin-resin interface.
interface.

4.4.Conclusions
Conclusions
Twotypes
Two typesofofcomposites
compositeswere
werestudied
studied and
and the
the degree
degree of
of curing
curing was
was assessed.
assessed.The
The
results from the pycnometric data seem to conclude that Sample 1 (microcomposite)has
results from the pycnometric data seem to conclude that Sample 1 (microcomposite) has
a degree of conversion higher than Sample 2 (nanocomposite). The SEM and EDX micro-
graphs showed that Sample 1 has a porous surface while Sample 2 presents with a more
compact surface, although not completely without holes. The elemental dispersion for the
tooth restoration showed that a good bonding is obtained at the enamel–resin interface
because of its predominant inorganic structure, while a new kind of bonding is required
Diagnostics 2022, 12, 1993 8 of 9

a degree of conversion higher than Sample 2 (nanocomposite). The SEM and EDX micro-
graphs showed that Sample 1 has a porous surface while Sample 2 presents with a more
compact surface, although not completely without holes. The elemental dispersion for the
tooth restoration showed that a good bonding is obtained at the enamel–resin interface
because of its predominant inorganic structure, while a new kind of bonding is required
for the dentin–resin interface (the polymer is vulnerable at the dentin–composite interface).
Both samples have the same variation in density during polymerization (~21%). The den-
sity difference comes from fillers, as Sample 1 contains ZrO2 /SiO2 versus SiO2 only for
Sample 2 (ZrO2 density is 5.68 g/cm3 while SiO2 density is 2.65 g/cm3 ). After calculating
Vinitial –Vfinal , we obtained a difference of 5.375 mm3 for Sample 1 and 4.375 mm3 for Sam-
ple 2. The larger increase of the volume for Sample 1 is related to a much larger porosity
as proved by SEM images. This reasoning also explains the lower degree of conversion as
obtained by Raman spectroscopy in the same geometry. This means that the same volume
is probed for both samples, but Sample 1 is more porous, which means less amount of
polymer is probed for Sample 1. Further investigations are necessary to assess the influence
of water and nitrogen upon shrinkage and conversion rate.

Author Contributions: Conceptualization, E.G.; methodology, C.-R.L. and S.-M.I.; software, E.G.
and S.-M.I.; validation, R.R.I.; formal analysis, E.G. and E.M.; investigation, S.-M.I. and C.-R.L.;
resources, R.R.I. and E.M.; data curation, C.E.A.G. and A.-M.I.; writing—original draft preparation,
A.-M.I.; writing—review and editing, E.G., C.E.A.G. and C.-R.L.; visualization, S.-M.I.; supervision,
C.E.A.G.; funding acquisition, E.G. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: The study was conducted in accordance with the Declaration
of Helsinki and approved by the Ethics Committee of the Faculty of Dental Medicine (protocol code
14 date 5 June 2013).
Informed Consent Statement: Informed consent was obtained from all subjects involved in the
study. Written informed consent has been obtained from the patient to publish this paper.
Data Availability Statement: Not applicable.
Acknowledgments: Part of the financial support was obtained from B&W Tek Company USA, by
equipment parts acquisition. A.M. Iordache was supported by a grant from the Romanian Ministry
of Education and Research, CNCS—UEFISCDI, project number PN-III-P1-1.1-PD-2019-1134 (Ctr. No.
PD87/2020), S.M. Iordache and C.E.A. Grigorescu were supported by grants from the Romanian
Ministry of Education and Research, CNCS—UEFISCDI, project number PN-III-P2-2.1-PED-2019-
2551 (Ctr. No. 393PED/2020), CORE Program, Ctr. 18/N/2019 within PNCDI III and by the
Ministry of Research and Innovation through Program I—Development of the National R&D System,
Subprogram 1.2—Institutional Performance—Projects for Excellence Financing in RDI, contract no.
18PFE/30.12.2021. E. Matei was supported by the Core Program PN19-03 (Ctr. No. 21N/08.02.2019)
funded by the Romanian Ministry of Research, Innovation and Digitization. C.R. Luculescu was
supported by the Core Program LAPLAS VI (Ctr. No. 16N/2019) funded by the Romanian Ministry
of Research, Innovation and Digitization. The authors wish to express their gratitude to the UMF
Carol Davila, Faculty of Medicine, Bucharest, Romania for supporting the APC for this paper.
Conflicts of Interest: The authors declare no conflict of interest.

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