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journal of the mechanical behavior of biomedical materials 46 (2015) 83 92
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Research Paper
Article history: Objectives: This study evaluated the degree of conversion, the free radical entrapment, and
Received 19 November 2014 the chemical interaction of self-adhesive resin cements mixed with pure hydroxyapatite,
Received in revised form as a function of the polymerization activation mode among a variety of commercial self-
15 February 2015 adhesive cements.
Accepted 19 February 2015 Materials and methods: Four cements (Embrace WetBond, MaxCem Elite, Bix SE, and RelyX
Available online 26 February 2015 U200) were mixed, combined with hydroxyapatite, dispensed into molds, and distributed
Keywords: into three groups, according to polymerization protocols: IP (photoactivation for 40 s); DP
Self-adhesive resin cement (delayed photoactivation, 10 min self-curing plus 40 s light-activated); and CA (chemical
Hydroxyapatite activation, no light exposure). Infrared (IR) spectra were obtained and monomer conversion
Chemical interaction (%) was calculated by comparing the aliphatic-to-aromatic IR absorption peak ratio before
FT-IR and after polymerization (n10). The free radical entrapment values of the resin cements
EPR were characterized using Electron Paramagnetic Resonance (EPR) and the concentration of
X-ray diffraction spins (number of spins/mass) calculated (n3). Values were compared using two-way ANOVA
and Tukeys post-hoc test (5%). X-ray diffraction (XRD) characterized the crystallinity of
hydroxyapatite as a function of the chemical interactions with the resin cements.
Results: The tested parameters varied as a function of resin cement and polymerization
protocol. Embrace WetBond and RelyX U200 demonstrated dependence on photoactivation
(immediate or delayed), whereas MaxCem Elite exhibited dependence on the chemical
activation mode. Bix SE presented the best balance based on the parameters analyzed,
irrespective of the activation protocol.
n
Correspondence to: Universidade Anhanguera de So PauloUNIAN SP, Programa de Mestrado em Biomateriais em Odontologia,
Rua Maria Cndida, 1.813 6.1 andar, Bloco G, So Paulo CEP: 02071-013, SP, Brazil. Tel.: 55 11 29679058/55 11 29679077.
E-mail address:
paulodalpino@yahoo.com (P.H.P. D'Alpino).
http://dx.doi.org/10.1016/j.jmbbm.2015.02.019
1751-6161/& 2015 Elsevier Ltd. All rights reserved.
84 journal of the mechanical behavior of biomedical materials 46 (2015) 83 92
Conclusions: Choice of polymerization protocol affects the degree of conversion, free radical
entrapment, and the chemical interaction between hydroxyapatite and self-adhesive resin
cement mixtures.
& 2015 Elsevier Ltd. All rights reserved.
Considering that SLCs are frequently applied to newly exposed light-curing unit (Bluephase, Ivoclar Vivadent, Schaan, Liechten-
dentin, especially in total crown preparations, and the fact that stein) having an irradiance of 1200 mW/cm2 s. Prior to testing,
the polymerization reaction in methacrylate-based resins is and throughout the experiment, the light output was monitored
radical-mediated, according to a study (Andrzejewska, 2004) to using a handheld radiometer (Model 100, Demetron Research
evaluate entrapped free radicals in the resin cements and their Corp., Danbury, CT, USA). Specimens from the chemically acti-
interaction with tooth substrates as a function of the activation vated group (CA group) were kept in the molds for 24 h at room
protocol, is of clinical relevance. temperature in the dark prior to their removal. Ten replications
Drawing upon three hypotheses, this study attempts to were made for each test condition (n10).
investigate the effects of activation protocols on the degree of
conversion, free radical entrapment, and the integrity of the 2.3. FT-IR analysis
hydroxyapatite crystal structure, when evaluating different
SLCs. The following research hypotheses were tested: (1) the The specimens were placed and vertical pressed against a
degree of conversion will not be negatively inuenced by the horizontal diamond element of an attenuated total reec-
polymerization activation mode and brand of resin cement; tance (ATR) unit (MIRacle, PIKE Technologies, Madison, USA)
(2) the different activation mode will signicantly affect the of a Fourier transform infrared spectrometer (IRPrestige-21,
density of spins of the resin cements tested; and (3) the Shimadzu, Tokyo, Japan) in order to obtain the infrared
integrity of the hydroxyapatite (HA) crystal (as monitored in (IR) spectrum. IR spectra were collected between 1680 and
the 211 orientation) will be inuenced by the brand of SLCs 1500 cm 1 using 16 scans at 2 cm 1 resolution. The speci-
tested and by the polymerization activation mode used. mens were placed one at a time in the sample holder of the
device, and spectra were recorded. A small amount of
uncured resin cement from each material was also scanned
2. Materials and methods and its spectrum was used as unpolymerized reference. The
ratio between the peak absorbance value of the aliphatic
2.1. Experimental design (CC) at 1636 cm 1 to the aromatic C C group absorption at
1608 cm 1 in the cured and uncured states was used to
In this in vitro study, the degree of conversion, free radical calculate the degree of conversion of aliphatic (C C) into
entrapment, and the integrity of the hydroxyapatite crystal- (CC). The results were expressed as the percentage of
line structure were evaluated on resin cement mixtures aliphatic C C remaining after light exposure to that available
incorporating known amounts of hydroxyapatite, according in the unpolymerized condition (Rueggeberg et al., 1990).
to the following factors: (1) SLCs at four levels: Embrace Average conversion values were calculated, and a two-way
WetBond, MaxCem Elite, Bix SE, and RelyX U200; and (2) ANOVA was performed. Tukeys post-hoc test was used as a
activation mode at three levels: immediate photoactivation multiple comparison test, at a pre-set alpha of 0.05.
(IP), delayed photoactivation (DP), and chemical activation
(CA). The characteristics of the resin cements selected are 2.4. Magnetic properties
described in Table 1. Twelve groups were categorized and
treated according to the various polymerization protocols 2.4.1. Specimen preparation
(Table 2). Specimens were prepared for Electron Paramagnetic Reso-
nance (EPR) analysis in the same way as previously described,
2.2. Degree of conversion except that the unpolymerized resin cement/HA mixtures were
placed into a rectangular Teon mold (8 mm 2 mm 2 mm). In
2.2.1. Specimen preparation addition, three replicas were made for each test condition (n3).
Specimens were prepared by mixing 0.035 g of dry hydroxyapatite
(HA) with 0.25 g of the SLCs. As a starting compound, a HA with a
high degree of crystallinity and purity (Ca10(PO4)6(OH)2) was used. 2.5. EPR analysis
The SLCs were mixed according to the manufacturers instruc-
tions in terms of working and setting times, and then the HA was Spectra were acquired using an EPR instrument (Magnettech
gently incorporated using manual mixing. The unpolymerized Miniscope MS300, Berlin, Germany) operating at X-Band 9.43
resin cement/HA mixtures were then placed into a Teon mold GHz. The main EPR parameters were modulation amplitude
(2 mm thick, 6 mm in diameter), positioned over a polyester strip. (from 0.2 to 0.4 mT) and microwave power (0.5012 mW). The
After lling the mold to excess, the material surface was covered g-factors were determined by reference to the signal of the
with a Mylar strip and a glass slide and compressed to extrude diphenylpicrylhydrazyl (DPPH) with a known value of 2.0036.
excess material. The glass slide was then removed, leaving the The density of spins was determined by comparing the EPR
Mylar strip. The distal end of the curing light guide was placed spectrum of the unknown specimens (cements) to that of a
within 0.1 mm of the top Mylar surface. Specimens of groups IP sample with a known spin concentration (standard sample).
and DP were photoactivated for 40 s on the top and bottom Each free radical has a spin different from zero, so by measuring
surfaces. Photoactivation was performed after the working time. the spin density one is measuring the free radical density (Poole
After the photoactivation procedures (IP and DP groups), the and Charles, 1983). For that standard, an amorphous silicon
specimens were removed from the molds and then stored in sample with a calibrated spin concentration of 1.13 1015 spins/
lightproof recipients for 24 h at room temperature (22 1C). The grams was used (DAlpino et al., 2014). The number of spins in
light-curing procedure was performed using a poly-wave LED the resin cements of each experimental group was then
86 journal of the mechanical behavior of biomedical materials 46 (2015) 83 92
Embrace WetBond
Pulpdent 130711 Co-monomers (mono-, di-, and tri-functional 36.6
2.0 3.0 40
Corporation, 2015-07 methacrylate monomers, Barium, glass, 39.0
Watertown, ytterbium triuoride, inert minerals.
MA, USA Automix system
69.9
MaxCem 5011290 GPDM, co-monomers (mono-, di-, and tri- 1.5 4.0 10 - 20 59.0
Elite 2015-03 functional methacrylate monomers, water,
Kerr acetone, and ethanol. Inert minerals and
Corporation, ytterbium uoride. Automix system
Orange, CA,
USA
Abbreviations: Bis-GMA: bisphenol A diglycidyl ether dimethacrylate; UDMA: urethane dimethacrylate; Gly-DMA: glycerol dimethacrylate;
GPDM: glycero-phosphate dimethacrylate. All information supplied by manufacturers.
calculated using the following formula (Poole and Charles, 1983; performed using a two-way analysis of variance (ANOVA)
Warren and Fitzgerald, 1977): followed by Tukeys post-hoc test at a pre-set alpha of 0.05.
CT
N p 1
AM 2
PA
2.6. Chemical interaction with hydroxyapatite
where N is the spin concentration (in spins); C is the standard
sample constant (1.13 1015); T is the temperature (in Kelvin); A 2.6.1. Preparation of hydroxyapatite (HA)/SLC samples
is the area under the resonance absorption curve; AM is the Samples were prepared for X-ray diffraction analysis (XRD) by
modulation amplitude; and P is the incident microwave power. mixing 0.070 g of dry HA powder (Ca10(PO4)6(OH)2) with 0.5 g
For all measurements, the microwave power and modulation of the freshly mixed but unset SLCs. The materials were
amplitude were kept constant to avoid signal saturation and manipulated according to the manufacturers instructions
distortion. and were then gently mixed with HA on a glass plate until
The identication of the free radicals was made with the a paste-like consistency was obtained. Then, the paste was
assistance of software (Easyspin 4.5.1). The ESR parameters transferred and carefully spread onto an XRD specimen
were obtained by tting the experimental data. The spin holder. A homogeneous layer in which the HA was uniformly
concentration as a function of mass according to the experi- distributed throughout the organic matrix of the resin
mental groups was calculated dividing the number of spins by cements was obtained in all cases. The specimens were then
the sample mass (in grams). The radicals were then calculated polymerized according to the activation protocols. The dry
as a function of the resin content. The concentration in the HA power was also characterized for comparative analyses. A
resin portion of each product (by mass) was obtained by different ratio was used here in order to ll out the specimen
thermal analysis (data not shown). Statistical analysis was holder to obtain the XRD patterns.
journal of the mechanical behavior of biomedical materials 46 (2015) 83 92 87
2.7. XRD analysis For the allylic radical g 2.00370.001 and a is 21.570.1 G related to
CH2. The calculated number of spins of the experimental groups,
XRD patterns were collected using an X-ray diffractometer normalized by weight (resin content), is presented in Table 4. The
(DMAX Ultima Rigaku International Corporation, Tokyo, spin concentration was found to be between 3.6 1016 spins/g for
Japan) with CuK radiation, operating at 40 kV and 20 mA. MaxCem Elite (CA), and 1,560 1018 spins/g for RelyX U200 (IP).
Scans were performed from 51 to 801 (2) at a step size of 0.021 Embrace WetBond and RelyX U200 presented signicantly higher
and a scan speed of 21/min. Qualitative phase analysis was spin concentration averages, when photoactivated immediately or
carried out by using the Joint Committee on Powder Diffrac- after 10 min (po0.05). MaxCem Elite presented signicantly higher
tionInternational Center for Diffraction Data (JCPDSICDD) averages of spin concentration when photoactivated after 10 min.
databases by comparing the peak intensity of pure HA with The same was observed for Bix SE. All of the materials tested
that of the test specimens. In addition, a quantitative phase presented signicantly lower spin concentrations when the che-
analysis was also performed by comparing the peak intensity mical activation was performed (po0.05).
of HA attributed to the 211 diffraction (highest peak of
crystallinity of pure HA) before and after mixing HA with 3.3. XRD analysis
the SLCs. The results were expressed in peak intensity of the
mixture resin cement/HA (in cps) and also in the percent The panels in Fig. 2 displays the X-ray diffraction patterns of
decrease in crystallinity of HA using the strongest diffraction SLCs tested. In each diffractogram, the crystalline peaks of pure
orientation (2 1 1) as a guide (1730 cps), in comparison to that HA, as well as those of the resin cements/HA mixtures, are
of pure HA. displayed. The peaks and associated planes of HA diffracto-
grams match the crystallographic data sheet (74-0565) of
calcium hydroxide phosphate, Ca10(PO4)6(OH)2, obtained from
3. Results the PCPDFWIN database. In accordance with this database, the
crystalline pattern has a hexagonal cell with the following
3.1. FT-IR analysis parameters: a9.424 and c 6.879 . With respect to the HA/
resin cement interactions, X-ray diffraction patterns indicate
Experimental results are displayed in Table 3. The degree of the presence of a hexagonal HA phase and an organic,
conversion ranged between 16.5% for RelyX U200 to 59.6% for amorphous phase (seen as a broad hump in the baseline) at
MaxCem Elite, when both cements were chemically activated. 2 between 101 and 301, associated with Embrace WetBond
When the cements were compared, signicantly lower conver- (Fig. 2A). Similar ndings were observed in the diffractograms
sion averages were observed for Bix SE when immediately of the mixture Bix SE/HA (Fig. 2C), irrespective of the activa-
photoactivated, and for RelyX U200 when chemically activated tion protocol. The diffractograms indicating the interaction
or photoactivated after 10 min (po0.05). On the contrary, Max- between HA and RelyX U200 (Fig. 2D) show the presence of
Cem Elite presented signicantly higher degree of conversion peaks related to both Ca10(PO4)6(OH)2 and an unidentied
averages, irrespective of the activation protocol (po0.05). In crystalline component at 2 17.91. In the diffractograms of
terms of conversion, both Embrace WetBond and RelyX U200 the mixture of MaxCem Elite and HA, two crystalline fractions
demonstrated dependence on the photoactivation (immediate are present: one related to HA and another related to ytterbium
or delayed), whereas MaxCem Elite exhibited signicantly higher uoride (YbF3). These additional peaks in the diffractograms of
conversion averages when chemically activated. On the other the MaxCem Elite/HA mixture were attributed to the presence
hand, Bix SE presented signicantly higher conversion averages of the orthorhombic crystalline phase of YbF3. The peaks and
when chemically activated and for delayed photoactivation over the crystalline planes associated match the crystallographic
those seen in immediate photoactivation. data sheet of ytterbium uoride (711161).
Table 5 displays the results of peak intensity of the resin
3.2. Free radical entrapment cement/HA mixture (in cps) and also in terms of percentage
reduction in comparison to that of pure HA at (2 1 1) diffraction
The panels in Fig. 1 display characteristic electron paramagnetic (1730 cps). The greatest reductions in peak intensity were
resonance spectra of the SLCs. The EPR spectra are characterized obtained when Bix SE was mixed to HA, irrespective of the
by 9 lines. For the propagating radical g 2.00370.001 and isotropic activation protocol. The percentages varied from 61.8 (DP group)
hyperne constant a is 21.570.1 G for CH3 and 11.770.1 G for CH2. to 69.2 (CA group). On the other hand, the lowest reductions were
Table 3 Percent monomer conversion (%) (sd) of products tested using various polymerization protocols.
PRODUCT Immediate photoactivation (IP) Delayed photoactivation (DP) Chemical activation (CA)
Embrace WetBond 32.3 (1.8) a,B 31.7 (0.8) a,B 27.5 (3.0) b,C
MaxCem Elite 52.3 (1,5) b,A 52.8 (3.1) b,A 59.6 (1.6) a,A
Bix SE 27.3 (1.7) b,C 39.9 (1.6) a,B 40.8 (1.8) a,B
RelyX U200 28.3 (3.9) a,B 25.4 (1.0) a,C 16.5 (1.5) b,D
(n 10).
Groups identied using similar letters (upper case for columns and lower case for rows) are not signicant (p40.05).
88 journal of the mechanical behavior of biomedical materials 46 (2015) 83 92
4. Discussion
Table 4 Mean entrapped free radical concentrations normalized by weight (sd)*, with respect to brand of self-adhesive
resin cements and polymerization activation mode.
PRODUCT Immediate Photoactivation (IP) Delayed Photoactivation (DP) Chemical Activation (CA)
Embrace WetBond 231 (2.4) a,C 281 (3.1) a,C 63 (2.2) b,D
MaxCem Elite 21 (0.2) b,D 66 (0.3) a,D 3.6 (0.1) c,C
Bix SE 494 (2.9) b,B 594 (1.2) a,B 318 (0.9) c,A
RelyX U200 1560 (15.4) a,A 1400 (14.8) a,A 159 (3.2) b,B
(n 3).
Values denoted using similar letters (upper case for columns and lower case for rows) are not signicantly different (p40.05).
n
( 1016 spins/g).
study, the volumetric ller content varied from 39.0 to 59.0%, percentage of the monomers that convert into polymers is
whereas the variation in weight content was between 39.9 and calculated.
72.0%. During polymerization, portion of the methacrylate groups EPR spectroscopy is a very useful technique for studying
involved in the formation of the cross-linked matrix remains the structure of free radicals and for following the radical
unreacted, especially in the case of higher molecular weight molecule through various physically or chemically modied
monomers (DAlpino et al., 2007). This fact, associated with high pathways (Poole and Charles, 1983). In addition to qualitative
ller levels decreases polymer radical mobility, and as a conse- measurements, EPR is also quantitative. The absorption of
quence, there is a decrease in its reactivity: it tends to become microwave energy in a sample is directly proportional to the
entrapped within the viscous, cured polymer network and is number of spins present. The area under the EPR absorption
incapable of causing additional chain lengthening or cross- spectrum is proportional to the number of free radicals
linking. The products with higher ller loading (such as RelyX (spins) in the sample, and the number of free radicals is
U200) react more slowly, and this fact may explain why this resin proportional to the radiation energy absorbed in the sample.
cement exhibited a signicantly lower degree of monomer Thus, the radiation dose may be determined by measuring
conversion and a dependence on the delay time prior to photo- the relative concentration of radiation-generated free radicals
activation (Pereira et al., 2010). in a given material using EPR spectroscopy (Sagstuen and
Previous studies recommended immediate photoactiva- Hole, 2009).
tion for SLCs, solely based on the degree of conversion Free radicals are created during the photoactivation of resin-
parameter (Aguiar et al., 2010; Arrais et al., 2014). In dual- based materials (Leprince et al., 2009). Some radicals terminate
cured cements, both light and chemical activation procedures by encountering other radical species and others become
generate reactive free radicals by cleavage of the initiator trapped by vitrication of the system (Trufer-Boutry et al.,
molecules (Rueggeberg, 1999). In the propagation reaction, 2003a). EPR spectroscopy is an analytical tool which applies to
these radicals are able to add to the double bonds of molecular systems having either an odd number of electrons
methacrylate groups, thereby creating new radicals. This free (free radicals) or more unpaired electrons. Two types of trapped
radical polymerization reaction occurs very rapidly, until no free radicals are detectable by EPR in polymerized composites:
additional monomer is able to react or the propagation propagating and allylic radical types (Trufer-Boutry et al.,
reaction is stopped by termination (Trufer-Boutry et al., 2003b). The former gives rise to an EPR spectrum with nine
2003a). The mobility of the developing polymer chains weak and broad peaks, and the latter (allylic) to ve strong and
becomes progressively more restricted, due to the increase sharp peaks. Both spectra superimpose, resulting in a nine-line
in the viscosity, the reduction in free volume, formation of spectrum with peaks of alternating intensities (Leprince et al.,
microgels, and chain entanglement (Neves et al., 2005). In this 2009). As free radicals can be trapped in a solid matrix, they are
way, the polymer network becomes rigid enough, its chains unable to recombine and the nine-line EPR spectrum persists
become essentially immobile, and the propagation of free during a period of variable length, from a couple of days to
radical reactions becomes diffusion limited, decreasing the many months, depending on the storage conditions (Leprince
overall conversion value (Andrzejewska, 2004). This change et al., 2009).
causes a signicant percentage of the methacrylate groups It has been previously established that the degree of
(between 25 and 60%) to remain unreacted (Cook et al., 1999). conversion is related to the number of unpolymerized term-
In resin-based restorative materials, mostly bifunctional inal groups in which double bonds are present (Rueggeberg,
monomers are used and are able to react with four other 1999). On the other hand, the conversion reaction proceeds
monomer molecules leading to the formation of polymer through the formation of radicals under irradiant light, which
chains and cross-linking. Although the network of a com- corresponds to the EPR spectrum. In this way, an increase in
posite includes not only the remaining double bonds but the EPR signal intensity as a function of irradiation time
also free radicals, which are located at functional groups correlates to the propagation of the conversion reaction
that have reacted with only one methacrylate group, it is (Leprince et al., 2009). In this way, recombination of radicals
expected that cross-linked polymers present lower free can occur, either by bimolecular termination or due to
radical densities. When the degree of conversion is the reactive diffusion, resulting in an increase of the degree of
only parameter assessed, these radical-mediated reaction conversion was observed 24 h after the photoactivation
issues are not taken into consideration, because only the procedure (2%) (Leprince et al., 2009). The various SLCs differ
90 journal of the mechanical behavior of biomedical materials 46 (2015) 83 92
Table 5 Quantitative analysis of intensity peak of HA attributed to the (2 1 1) diffraction after mixing HA with the self-
adhesive resin cements. (One specimen tested per group).
PRODUCT Immediate photoactivation (IP) Delayed photoactivation (DP) Chemical activation (CA)
Peak height (AU) % Reduction Peak height (AU) % Reduction Peak height (AU) % Reduction
dentinal tubules (Vaz et al., 2012). In addition, it was also considered. For the development of future SLCs, studies
proven that this adhesion strategy relies not only on micro- are necessary to evaluate the longevity of indirect restora-
mechanical retention, but also on chemical interactions tions cemented with this category of resin cement over
between monomer acidic groups and hydroxyapatite (Gerth longer evaluation times.
et al., 2006). According to the results of the present study, it can
be speculated that the dynamic process, in which the acidity of
5. Conclusions
the cements is progressively neutralized, as well as the poly-
merization process, is inuenced by the SLCs and by the
Within the limitations of this study, the following conclu-
activation protocol. These events start immediately after mix-
sions can be made:
ing the base and catalytic pastes, and due to their rheological
properties, the cements are able to ow according each
1. Choice of polymerization protocols affects the degree of
material. Therefore, it is of paramount importance to compare
conversion of SLCs;
the results in the light of the parameters analyzed. In general,
2. Entrapped, unreacted free radical density of SLCs varies as
the resin cement Bix SE presented higher dependence on the
a function of the resin cement and of the activation;
chemical activation, in which higher conversion averages,
3. Brand of SLC and its polymerization activation mode can
lower free radical density, and higher reduction in HA crystal-
alter its interaction with the crystalline structure of
linity are observed. Although the cement MaxCem Elite also
hydroxyapatite; and
demonstrated a chemical dependence in terms of conversion
4. Based on the parameters evaluated, one of the tested
efciency and lower free radical density, this product inter-
products provided more optimal characteristics than did
acted less with the HA when chemically activated. In this
the others: improved degree of conversion, lower density
case, MaxCem Elite was more effective when immediately
of free radicals, and higher interaction with hydroxyapa-
photoactivated or after a delay of 10 min. On the other
tite, regardless of the activation mode.
hand, the cement RelyX U200, as previously discussed,
showed a higher dependence on delay time prior to
photoactivation in terms of conversion efciency. Conver-
sely, the EPR and XRD analyzes showed a higher depen- Acknowledgements
dence on chemical activation, considering the signicantly
lower spin (free radical) density and higher interaction of This study was partially supported by grants from CNPq nos.
479744/2010-6 and 163102/2011-2 (P.I. Paulo H. P. DAlpino)
the resin with HA. Although a higher dependence on the
This study was developed as partial fulllment of the
chemical activation in terms of free radical concentration
was observed, the cement Embrace WetBond showed requirements of Dr. Silvas Master degree (UNIANSP). The
higher dependence on the photoactivation, in terms of authors are grateful to Prof. Dayse Iara dos Santos (UNESP
degree of conversion and higher interaction with HA. Thus, Bauru) for the technical support in the XRD analysis.
the cement Bix SE presented the best balanced formula-
tion based on the parameters analyzed, demonstrating r e f e r e nc e s
higher effectiveness to demineralize hydroxyapatite, a
higher degree of conversion, and lower density of free
radicals, irrespective of the activation protocol. Aguiar, T.R., Di Francescantonio, M., Arrais, C.A., Ambrosano, G.M.,
Davanzo, C., Giannini, M., 2010. Influence of curing mode and
This study investigated the inuence of the different activa-
time on degree of conversion of one conventional and two self-
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