journal of dentistry 36 (2008) 418–426

available at www.sciencedirect.com

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

Effect of curing mode on the polymerization

characteristics of dual-cured resin cement systems

Cesar A.G. Arrais a, Frederick A. Rueggeberg b, Jennifer L. Waller c,

Mario F. de Goes d, Marcelo Giannini e,*
a
Department of Operative Dentistry, School of Dentistry, University of Guarulhos, Guarulhos, SP, Brazil
b
Department of Dental Materials, School of Dentistry, Medical College of Georgia, Augusta, GA, USA
c
Department of Biostatistics, Medical College of Georgia, Augusta, GA, USA
d
Department of Restorative Dentistry, Dental Materials Section, Piracicaba School of Dentistry, University of Campinas, SP, Brazil
e
Department of Restorative Dentistry, Operative Dentistry Seciton, Piracicaba School of Dentistry, University of Campinas, SP, Brazil

article info abstract

Article history: Objectives: To evaluate the effects of different curing conditions on the degree of conversion
Received 26 July 2007 (DC) of dual-cured cementing systems [combination of bonding agent (BA) and resin cement
Received in revised form (RC)] using infrared spectroscopy.
20 February 2008 Methods: Four fourth generation products [Scotchbond Multipurpose Plus/RelyX (3M ESPE),
Accepted 21 February 2008 Optibond/Nexus 2 (Kerr), All Bond2/Duolink (Bisco), and Bond-It!/Lute-It! (Pentron)], and
three fifth generation materials [Bond1/Lute-It! (Pentron), Prime&Bond NT Dual-Cure/Cali-
bra (Dentsply), and Optibond Solo Dual Cure/Nexus 2 (Kerr)] were applied to the surface of a
Keywords: horizontal attenuated-total-reflectance unit, and were polymerized using one of four con-
Degree of conversion ditions: self-cure (SC), direct light exposure through glass slide (DLE, XL3000/3M ESPE) or
Dual-cured cementing systems through pre-cured resin discs (shades A2;A4/2 mm thick/Z250/3M ESPE). Infrared spectra of
Indirect restorations the uncured cementing systems were recorded immediately after application to the ATR,
Self-cure1 after the system was light-cured or left to self-cure, and spectra were obtained 5 and 10 min
later. DC was calculated using standard techniques of observing changes in aliphatic-to-
aromatic peak ratios pre- and post-curing. Data (n = 5) were analyzed by two-way repeated
measures ANOVA and Tukey’s test ( p = 0.05).
Results: Changes in aliphatic-to-aromatic peak ratios before and after placing RC onto the
BA demonstrated that a combined layer was created. All groups exhibited higher DC after
10 min than after 5 min, except the DLE group of Bond-it!/Lute-it!. No significant differences
in DC were observed among light-activated groups regardless of the resin disc shade in three
of the four fourth generation cementing systems. The SC groups exhibited lower DC than the
DLE groups for both fourth and fifth generation products either after 5 or 10 min.
Conclusion: The chemistry of the bonding interface changed when RCs were applied to
uncured BAs. The presence of an indirect restoration can decrease the DC of some cement-
ing systems and the self-curing mode leads to lower DC than the light-activating one.
# 2008 Elsevier Ltd. All rights reserved.

* Corresponding author at: Department of Restorative Dentistry/Operative Dentistry, Piracicaba School of Dentistry, UNICAMP, Av.
Limeira, #901, Piracicaba, SP 13414-900, Brazil. Tel.: +55 1934125340; fax: +55 1934125218.
E-mail address: giannini@fop.unicamp.br (M. Giannini).
0300-5712/$ – see front matter # 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jdent.2008.02.014
 journal of dentistry 36 (2008) 418–426
1. Introduction
The clinical success of composite and ceramic indirect
restorations is attributed to the reliable bond between
adhesive cementing systems (resin cements/bonding agents)
and mineralized dental tissues.1,2 Light intensity reaching the
resin cement is strongly attenuated by either the distance
from the light source or by the absorbing characteristics of the
indirect restorative material. This attenuation results in low
degree of conversion (DC) and compromised mechanical
properties of the dentin/adhesive interface when only light-
cured resin materials are used to bond the restorations.3,4 In
an attempt to overcome this problem, manufacturers devel-
oped dual-cured resin materials, which contain self-curing
components to initiate the polymerization reaction in the
absence of light.5,6
Dual-cured cementing systems contain a mixture of
monomers and initiators, and are formulated to not depend
only on light activation to polymerize. Therefore, light
activation of adhesive resins prior to delivering an indirect
restoration might not be necessary. Among commercial resin-
based indirect cementing systems available, manufacturer
instructions differ widely in advocating the pre-curing of the
dentin bonding agent. Some products advocate light-curing of
the dentin bonding agent prior to cementation, others indicate
the clinician can choose to light cure or not, while others state
that light curing should not be performed prior to resin cement
application. Clinically, however, it would be advantageous not
to light-cure the dentin bonding agent separately. If the
thickness of polymerized dentin bonding layer is large, its
added dimension would result in incomplete seating of the
restoration, generating large marginal discrepancies and the
necessity to adjust occlusion.7
Acidic resin monomers from two-step total etch and self-
etching adhesives may impair the polymerization of dual-
cured cements and composites that are initiated via a
peroxide-amine binary redox system.8,9 As a consequence,
low bond strength values are reported when light activation
of the dentin bonding agent is not performed.10,11 In order to
overcome this chemical incompatibility, chemical co-initia-
tors have been introduced in the dentin bonding agent, such
as aryl sulfinic acid salts, organoboron compounds, and
barbituric acid/cupric chloride.12 These components react
with the acidic resin monomers to produce either phenyl or
benzenesulfonyl free radicals that initiate the reaction of
dual-cured resin cements when light from the curing unit is
not available.12
Several studies have demonstrated that ceramic or resin-
based composite inlays/onlays reduce the amount of light
reaching the bottom of the restoration, and therefore
compromise photo-activation of light-activated luting materi-
als.13,14 Moreover, when evaluating in vitro occlusal wear,
quantity of remaining double bonds, and cement system
hardness, some authors indicate that the chemical curing
mechanism alone is less effective than the light-activated
reaction when dual-cured resin cements were used.13,15
However, there is no information regarding the DC of such
dual-cured resin cements when they were combined with
dual-cured adhesive systems in simulated clinical conditions
when light intensity is strongly attenuated or totally absent.
419
Thus, the purpose of this study was to measure the DC of
representative commercial fourth and fifth generation dual-
cured cementing systems, when they were applied and light-
activated with little attenuation (through a microscope slide)
or when light was attenuated by passing through pre-cured
resin discs (shades A2/A4), or when light from the curing unit
was totally absent (self-cured (SC)). Most manufacturers
suggest the interval between 5 and 10 min after seating the
indirect restoration as the most appropriate moment for
occlusal adjusts, finishing, and polishing procedures, all of
which are capable of generating stress. Therefore, the 5- and
10-min DC analysis was performed to provide information
about a possible indicator of the physical properties of the
adhesive interface during such procedures. The research
hypotheses tested for each dual-cured cementing system
were: within a given dual-cured cementing system: (1)
conversion using direct light exposure (low light attenuation)
will be higher than when the systems are allowed to self-cure
only; (2) attenuation of curing light delivered to the dual-cured
cementing system by passing through pre-cured resin discs
will result in lower DC compared to when light passes through
only a glass slide (low attenuation); (3) for similar thickness of
pre-cured composite, the conversion of a dual-cured cement-
ing system, when light-cured, will be less for the darker-
shaded composite; and (4) DC after 10 min will be higher than
that measured after 5 min from polymerization initiation for
SC and all light-curing modes.
2. Materials and methods
2.1. Specimen preparation and Fourier transformed
infrared analysis
Four fourth and three fifth generation adhesive systems
(Tables 1 and 2) and their recommended dual-cured resin
cements (Table 3) were used (adhesive system/resin cement):
All Bond2/Duolink (AB2/DUO; Bisco), Bond-It!/Lute-It! (BIT/
LUTE; Pentron), Optibond/Nexus 2 (OPT/Nexus; Kerr), Scotch-
bond Multipurpose Plus/Rely X (SBMP/RelyX; 3M ESPE); Bond1/
Lute-It (B1/LUTE; Pentron); Prime & Bond NT Dual-Cure/Calibra
(NTD/Cal; Dentsply) and Optibond Solo Dual Cure/Nexus 2
(SOLOD/Nexus, Kerr), respectfully. Light-cured composite resin
discs (2 mm thick, 10 mm in diameter – A2/A4 shade – Z250, lot#
5LB; 3M ESPE) were prepared to simulate overlying laboratory-
processed composite resin restorations. The adhesive systems
and resin cements were applied as described in Tables 1 and 2 to
a horizontal diamond ATR element (Golden Gate, Specac,
Woodstock, GA, USA) in the optical bench of a Fourier transform
infrared spectrometer (FTS-40, Digilab/BioRad, Cambridge, MA,
USA). Adhesive tape (3M) was placed around the diamond
surface to act as a spacer, ensuring standard thickness for all
specimens (100–120 mm). All adhesive systems were placed
according to manufacturer instructions, but none were light-
cured prior to placement of the resin cement. The deposited
material was covered with a Mylar strip and polymerized using
one of 4 different curing modes: light activation (sn#202149,
XL3000, 3M/ESPE power density: 600 mW/cm2;) through a glass
slide (2 mm thick) (direct light exposure (DLE)); light activation
through A2 or A4-shade pre-cured resin discs (A2/A4) (Fig. 1); or
420 journal of dentistry 36 (2008) 418–426

Table 1 – Brand, composition, batch number and manufacturers’ instructions of the fourth generation dual-cured
adhesive systems used
Product (code) Composition (manufacturer supplied) Manufacturer’s instructions
(manufacturer) (batch number) and exceptions

All Bond 2 (AB2) Primer A: acetone; ethanol; Na-N-tolylglycine;
(Bisco Inc., glycidylmethacrylate (0500003574); Primer
Schaumburg, B: acetone; ethanol; biphenyl dimethacrylate
IL, USA) (0500003579); Pre-Bond Resin: bis-GMA,
TEGDMA; benzoyl peroxide; BHT (0500004345)
Bond-It! (BIT) Primer A: NTG-GMA magnesium salt in
(Pentron Corp., acetone, acetone (123280). Primer B:
Wallingford, mixture of PMGDM, a condensation product
CT, USA) of PMDA and glycerol (126514). Unfilled dual
resin activator: mixture of UDMA and HDDMA
resins with self-curing initiator, stabilizer,
benzoyl peroxide (110743). VLC adhesive:
dental methacrylate resin mixture with
photoinitiator, amine, and stabilizer (128389)
Optibond (OPT) Primer: ethyl alcohol, alkyl dimethacrylate
(Kerr Corp., resins, water (423435). Dual Cure Paste (3B):
Orange, CA, USA) uncured methacrylate ester monomers;
triethylene glycol dimethacrylate (424560);
inert glass filler, pigment and stabilizers. Dual
Cure Activator Resin (3A): uncured methacrylate;
ester monomers; benzoyl peroxide (423073)
Scotchbond Primer: water; 2-hydroxyethyl methacrylate;
Multipurpose copolymer of acrylic and itaconic acids (5AT).
(SBMP) (3M ESPE, Activator: ethyl alcohol; sodium benzenesulfinate
St. Paul, MN, USA) (5KT). Catalyst: bis-GMA; 2-hydroxyethyl
methacrylate; benzoyl peroxide (3AP)
Mix primers A and B. Apply five consecutive
coats to dentin; dry all surfaces for 5–6 s with
an air syringe; light-cure 20 s*; apply thin layer
of Pre-Bond Resin immediately prior to
cementation. Air thin. Do not light-cure
Mix equal parts of primer A and B. Apply five
coats to the etched surface to achieve a shiny
appearance; dry only after final coat. Mix equal
parts of Bond-It Light cure resin and Dual-Cure
Activator and apply.
Surface may be light cured or allowed to self-cure
Apply Optibond Prime (bottle 1) to dentin and
enamel surfaces with microbrush, scrubbing
the surface for (30) s; air dry for 5 s; dispense
Optibond Dual Cure paste (3B) and 1 drop of
Dual Cure Activator (3A) and thoughtfully mix
them for 15 s; apply a thin coat of the mixed
dual cure to the dentin surface. Do not air thin
and do not light cure
Apply activator (1.5) to enamel and dentin. Dry
gently for 5 s; apply primer (2.0) to enamel and
dentin. Dry gently for 5 s; apply catalyst (3.5) to
enamel and dentin; mix and apply a self-cure or
dual-cure luting material to the bonding surface
of the restoration; seat the restoration.
If a dual-cure cement was used, light-cure the margins

TEGDMA, Triethylene glycol dimethacrylate; bis-GMA, bisphenol A diglycidyl ether methacrylate; UDMA, urethane dimethacrylate; PMDA,
pyromellitic dianhydride; HADDMA, 1,6-hexanediol dimethacrylate; PMGDM, pyromellitic glycerol dimethacrylate; NTG-GMA, N-tolyl-glycine-
glycidylmethacrylate; BHP, butylated hydroxytoluene. *The adhesive systems were not light-activated before the cementation of indirect resin
composite disc.

they were allowed to self-cure under a Mylar strip and glass
slide (SC), with no curing light exposure. In the light-activated
groups, light exposure was provided according to manufac-
turers’ instructions (Table 3) just after placing all components of
the cementing systems and the pre-cured resin discs or the
glass slide on the ATR.
2.2. Monomer conversion
Infrared spectra were collected between 1680 and 1500 cm 1 at
a rate of 1 s 1 at 2 cm 1 resolution, from the moment when the
first layer of adhesive resin was applied to the ATR surface
through the next 10 min. Five replications were made for each
test condition. When the resin cement was applied to the
previously placed, unpolymerized adhesive, a slow change in
aliphatic to-aromatic C C absorption ratio indicated the
presence of the resin cement at the adhesive-covered
diamond surface (Fig. 2). The time at which the first stabilized
aliphatic to-aromatic C C absorption ratio was seen served to
supply the infrared spectra of the uncured mixed resin
(adhesive resin/resin cement) interface. Monomer conversion
was calculated by standard methods using changes in the
ratios of aliphatic-to-aromatic C C absorption peaks in the
uncured and cured states obtained from the infrared spec-
tra.16,17 The DC of all curing modes was compared within each
product at 5 and 10 min from the time the resin cement was
applied to the adhesive system, as well as between the two
time periods. All polymerized specimens were carefully
removed from the ATR plate and measured for thickness to
the nearest 0.01 mm using a digital micrometer (Series 406;
Mitutoyo America Corp., Aurora, IL, USA) to ensure that
pressure applied to either the microscope slide of pre-
polymerized resin disc provided similar thickness for all
specimens.
2.3. Curing light irradiance
The irradiance (mW/cm2) of the curing unit was determined
using a laboratory-grade spectral radiometer (DAS 2100,
Labsphere, N. Sutton, NH, USA) with a 7.62 cm diameter
integrating sphere. Five measurements were obtained when
the glass slide or the A2/A4 pre-cured resin discs were placed
between the integrating sphere aperture and the light guide
tip. Irradiance values were obtained between 350 and 600 nm
by dividing the total emitted power (mW) by the optical area of
the light guide end.
 journal of dentistry 36 (2008) 418–426 421

Table 2 – Brand, composition, batch number and manufacturers’ instructions of the fifth generation dual-cured adhesive
systems used
Product (code) Composition manufacturer supplied) Manufacturer’s instructions and exceptions
(manufacturer) (batch number)

Bond 1 (B1) Activator: methacrylate monomers in ethanol
(Pentron Corp.) and/or acetone, benzoyl peroxide, acetone
(128878). Resin: mixture of PMGDM, a condensation
product of PMDA and glycerol, dimethacrylate
HEMA and TMPTMA in ethanol and/or acetone
with photoinitiator, amine accelerator and stabilizer,
pyromellitic dianhydride (129121)
Prime & Bond NT Resin: acetone, urethane dimethacrylate resin,
(NTD) (Dentsply dipentaerythritol pentaacrylate phosphate,
Caulk, Milford, polymerizable dimethacrylate resins, polymerizable
DE, USA) trimethacrylate resins (050413). Activator: aromatic
sodium sulfinate (self-cure initiator), acetone,
ethanol (041110)
Optibond Solo Adhesive resin: ethyl alcohol, alkyl dimethacrylate
(SOLOD) resins, barium aluminoborosilicate glass, fumed
(Kerr Corp.) silica (silicon dioxide), sodium hexafluorosilicate
(428904). Activator: ethyl alcohol, alkyl
dimethacrylate resins, sodium salt of benzene
sulfinic acid (428260)
PMDA, Pyromellitic dianhydride; PMGDM, pyromellitic glycerol dimethacrylate; BHP, butylated hydroxytoluene; TMPTMA, trimethylolpropane
trimethacrylate; HEMA, 2-hydroxyethyl methacrylate.
a
The adhesive systems were not light-activated before the cementation of indirect resin composite disc.
Mix one drop of Bond1 Dual Cure Activator with 2 drops
of Bond1 Primer/Adhesive. Using a fully saturated brush
tip each time, apply two coats of Bond1 Primer/Adhesive
to tooth within 10 s; apply a gentle stream of air for a
minimum of ten (10) s. Hold air syringe 1 in. from site,
positioned so as not to disturb resin surface. Avoid
excess of Bond1 Primer/Adhesive in internal line angles
or point angles
Place 1–2 drops of the adhesive and equal number of
drops of Self-Cure Activator into a mixing well; mix
contents for 1–2 s with a clean, unused brush tip; using
the disposable brush supplied, immediately apply
mixed adhesive/activator to thoroughly wet all the tooth
surfaces. These surfaces should remain fully wet for 20 s
and may necessitate additional applications of mixed
adhesive/activator; remove excess solvent by gently
drying with a dental syringe for at least 5 s. Surface
should have a uniform glossy appearance. Cure mixed
adhesive/activator for 10 s using a curing light unita
Dispense one drop of Optibond Solo Plus and Optibond
Solo Activator into a disposable mixing well. Mix for 3 s;
apply mixture to dentin with a light brushing for 15 s to
cover dentin surface; lightly air thin for 3s. Light-cure
for 20 sa

2.4. Statistical analyses product when the DC was the variable selected, and one-way
ANOVA was performed to compare the differences in light
A two-way repeated measures analysis of variance (ANOVA) intensity. All statistical tests were performed at a pre-set alpha
(effect of curing mode and time) was performed for each of 0.05 and followed by Tukey’s post hoc test.

Table 3 – Brand, composition and batch number of the dual-cured resin cements used
Product (manufacturer) Composition (batch number) Time of light
exposure (s)

Duolink (DUO) Base: bis-GMA; TEGDMA; glass filler; urethane dimethacrylate. Catalyst: bis-GMA; TEGDMA; 40
(Bisco Inc.) glass filler (0500003751)
Nexus 2 (Nexus) Activator: ethyl alcohol; alkyl dimethacrylate resins; benzene sulfinic acid sodium salt 40
(Kerr Corp.) monomers of methacrylic acid esters, Ba–Al–borosilicate glass, chemical and
photoinitiators (base: 423638; catalyst: 423975)
Lute-It! (LUTE) In both base and catalyst: UDMA, HDDMA, amine and inorganic pigments (in base only), 40
(Pentron Corp.) benzoyl peroxide (in catalyst only), UV stabilizers (in both base and catalyst), barium glass,
inorganic fluoride*, borosilicate glass, silane silica zirconia (base: 130666; catalyst: 126388)
Calibra (CAL) Base paste: barium boron fluoroalumino silicate glass, bis-GMA resin, polymerizable 30
(Dentsply Caulk) dimethacrylate resin, polymerizable dimethacrylate resin, hydrophobic amorphous fumed
silica, titanium dioxide, other colorants are inorganic iron oxides. Catalyst paste: barium
boron, fluoroalumino silicate glass, bis-GMA resin, polymerizable dimethacrylate resin,
hydrophobic amorphous fumed silica, titanium dioxide, benzoyl peroxide (base: 0504111;
catalyst: 0505121)
Rely X (Rx) Paste A: silane treated ceramic, triethylene glycol dimethacrylate (tegdma), bis-GMA, silane 40
(3M ESPE) treated silica, functionalized dimethacrylate polymer, paste B: silane treated ceramic,
TEGDMA, bis-GMA, silane treated silica, functionalized dimethacrylate polymer (EYFH)
TEGDMA, Triethylene glycol dimethacrylate; bis-GMA, bisphenol A diglycidyl ether methacrylate; UDMA, urethane dimethacrylate; HDDMA,
1,6-hexanediol dimethacrylate
422 journal of dentistry 36 (2008) 418–426

Fig. 1 – Illustrative diagram demonstrating the interaction between the infrared beam and the specimen, as well as the
position of the pre-cured resin discs or the glass slide and the light-curing unit tip.

Table 4 displays DC results of all fourth and fifth generation

3. Results
3.1. Monomer conversion—within dual-cured cementing
systems
For most dual-cured cementing systems, a decrease in
aliphatic-to-aromatic C C absorption ratio was noted when
the dual-cured resin cements were applied to the ATR surface
containing uncured bonding agents (Fig. 1). The only exception
was observed for SOLOD/Nexus, which showed an increase in
this ratio when the resin cement was applied.
dual-cured cementing systems, respectively. No significant
differences in DC were observed when A2 values were
compared to DLE for the fourth generation cementing systems,
except for OPT/Nexus at 5 min, where DC of A2 was significantly
lower. However, with the fifth generation systems, the A2
groups exhibited lower DC than the DLE groups for all materials
(Table 4). The DC of A4 specimens was significantly lower than
that of the DLE group in most of the dual-cured cementing
systems. The only exception was when AB2/DUO, BIT/LUTE (at
10 min) and SBMP/RelyX were used, which showed no
significant differences in DC between DLE and A4 groups.

Fig. 2 – Representative spectra exhibiting changes in composition after placing the resin cement on the uncured bonding
agent (solid line: spectrum of the bonding agent; dotted line: spectrum after adding the resin cement to the bonding agent).
The increase in peaks corresponding to the aromatic C C bonds demonstrates the formation of a combined layer
composed of bonding agent and resin cement (dotted line).
 journal of dentistry 36 (2008) 418–426 423

Generation Table 5 – Power density (mW/cm2) measured through

Within an adhesive/cement system only, similar letters indicate no significant difference among values (capital letters, columns; lower case letters, rows). DLE, Direct light exposure; A2; A4, system
light-cured through 2 mm thick pre-cured composite disc of specific shade; SC, no light exposure, total self-curing. AB2, All Bond 2; DUO, Duolink; BIT, Bond-it!; LUTE, Lute it!; OPT, Optibond; Nexus,
Nexus 2; SBMP, Scotchbond Multipurpose Plus; RelyX, Rely X; B1, Bond 1; NTD, Prime & Bond NT Dual Cure; Cal, Calibra; SOLOD, Opitbond Solo Dual Cure. No comparisons were performed among
Fourth

Fourth

Fourth

Fourth
glass slide and through 2 mm thick A2/A4-shade pre-

Fifth

Fifth

Fifth
cured resin discs (mean (S.D.))
Glass slide A2 A4

545.4 (6.3) 60.8 (0.2) 45.4 (0.3)

All values were significantly different from one another ( p < 0.05).
N = 5 replications per test condition.

Ad
Ab

Ab
Ac

Ac

Ac

Ac
Bb

Bb

Bb
Bc

Bc

Bc

Bc
(4.3)
(1.0)
(9.7)
(3.2)
(2.4)
(0.7)
(3.0)
(2.4)
(0.7)
(0.9)
(2.2)
(1.7)
(2.0)
(1.9)
SC

For most of the fourth and fifth dual-cured cementing

37.1
49.5
45.7
57.3
39.5
55.9
36.2
44.3
48.3
56.1
46.6
52.6
61.1
65.8
systems, the SC group exhibited lower DC than DLE, A2, and A4
experimental groups at either 5- or 10-min (Table 4). The only
exceptions were observed for BIT/LUTE at 10 min, which
showed no significant differences among SC, A2, and A4
groups, and for B1/LUTE and SOLOD/Nexus, which showed no
significant difference among SC and A4 groups at 10 min. The
thickness of all specimens ranged from 100 to 120 mm.
Bab

Bbc

Bbc
Ab

Ab

Ab

Ab
Aa

Aa

Ac
Bb

Bb
Ba

Ba
(1.2)
(0.9)
(3.2)
(2.0)
(0.6)
(0.5)
(1.1)
(1.3)
(0.8)
(0.7)
(1.5)
(0.9)
(1.8)
(1.7)
A4

3.2. Monomer conversion—within curing modes

58.4
61.5
53.5
59.3
62.0
64.7
48.1
52.6
52.3
57.4
54.6
57.8
65.8
68.8

All fourth and fifth generation cementing systems exhibited

lower DC at 5 min than at 10 min in all curing modes. The only
exception was seen in DLE of BIT/LUTE where no difference in
DC was found between 5 and 10 min (Table 4).

3.3. Light attenuation of pre-cured resin discs

Aab
Bab

Bab
Ab

Ab

Ab

Ab
Aa

Aa

Bb

Bb

Bb
Ba

Ba
(0.4)
(0.6)
(2.8)
(2.0)
(0.8)
(0.5)
(3.4)
(3.1)
(0.5)
(0.2)
(1.1)
(0.9)
(1.2)
(1.2)
A2

Table 5 presents irradiance values measured when light

Table 4 – Degree of conversion (%) (DC) for adhesive/resin cement systems (mean (S.D.))

58.6
61.7
58.5
62.8
62.2
65.2
50.1
53.8
54.1
58.3
55.3
58.1
66.6
69.2

passed through the microscope glass slide, as well as through

A2- and A4-shade pre-cured resin discs. When the A2-shade
pre-cured resin disc was used, irradiance decreased approxi-
mately 89%, while 92% lower irradiance was noted when using
the A4 disc.
Aa

Aa
Aa
Aa

Aa

Aa

Aa

Aa
Ba

Ba

Ba

Ba

Ba

Ba

4. Discussion
(0.8)
(0.9)
(1.2)
(0.8)
(0.3)
(0.3)
(2.5)
(2.4)
(0.7)
(0.9)
(0.7)
(0.9)
(1.9)
(1.8)
DLE

61.2
63.4
63.4
66.3
65.0
66.8
52.0
55.1
59.3
62.2
59.0
61.5
70.5
72.6

The results demonstrate that the effect of all curing modes on

DC depends on both product and the evaluation period. The
first research hypothesis stated that conversion using direct
light-cure within a given dual-cured cementing system would
be higher than when the systems were allowed to self-cure
within the same dual-cured cementing system. This hypoth-
Time after mixing
or exposure (min)

esis was accepted for both cementing system generations, at 5

and 10 min. This finding agrees with other reports, which
showed that the self-curing mode was less effective when
10

10

10

10

10

10

10
5

compared to the dual-cured or photo-cured ones.13,15 One

possible explanation for this finding may be related to an
inability of radicals to migrate, due to the change in viscosity
during the polymerization, so the monomer conversion at
10 min is impaired as a consequence.18 Studies comparing the
DC developed in the SC mode with that obtained with DLE
mode after 24 h were not evaluated in the present work, but
Bonding agent/

would help understand the long-term implications among

SOLOD/Nexus

these products.
SBMP/RelyX
OPT/Nexus

Compared to the power density delivered through the glass

products.
AB2/DUO

BIT/LUTE
cement

NTD/Cal
B1/LUTE

slide, only 11 and 8% of the total irradiance reached the

cementing systems when pre-cured A2 and A4 shade resin
discs were used, respectively (Table 5). However, even when
424 journal of dentistry 36 (2008) 418–426
light intensity decreased by approximately 92% (A4 disc), no
difference in DC was observed for most of the fourth
generation cementing systems when compared to the values
of DLE groups after 10 min. Therefore, the research hypothesis
stating that the attenuation of curing light delivered to the
dual-cured cementing system by passing through pre-cured
resin discs will result in lower DC when compared to when
light passed through only a glass slide within a given dual-
cured cementing system was invalidated for the fourth
generation products evaluated after 10 min. Considering the
fact that the main feature of such cementing systems is the
presence of benzoyl peroxide not only in the resin cements,
but also in the adhesive systems, the composition of the
mixture obtained from resin cements and adhesive systems
has higher content of self-curing components than that of
these materials when they are not mixed together. Because
the higher content of the self-curing components affect the DC
of self-cured materials,19 the higher amine/benzoyl peroxide
content may have ensured that differences in light intensity
did not affect the DC of the cementing systems.
The importance of the dual-cure nature of bonding agents
with respect to conversion of the combined layer when light is
attenuated by the presence of indirect restoration might be
confirmed when the results of the current study were
compared with the results of El-Mowafy and Rubo20 and
Hofmann et al.21 In those studies, the effects of light intensity
attenuation on mechanical properties (hardness and flexural
strength) of dual-cured resin cements without their respective
dual-cured bonding agents were evaluated. It was found that
the self-curing components of most resin cements were not
capable of compensating for the attenuation of light intensity.
El-Mowafy and Rubo also evaluated the light intensity after it
passed through a 2 mm thick indirect ceramic restoration, and
observed a decrease in light intensity from 700 mW/cm2 to
approximately 100 mW/cm,2,20 which was higher than that
observed in the current study (Table 5). However, in contrast to
the results observed by these authors, in the present work,
such attenuation did not affect the DC of the fourth generation
dual-cured cementing systems in comparison to the DC of the
same products when light-activation was delivered directly
through a glass slide. Therefore, the coupling of fourth
generation dual-cured bonding agents with dual-cured resin
cements was shown to be important for not only avoiding any
chemical incompatibility, but also for providing more effective
monomer conversion when the curing light was severely
attenuated.
On the other hand, use of pre-cured resin discs resulted in
lower DC than the use of glass slide (DLE group) after 10 min
for each fifth generation dual-cured cementing system. Thus,
the same research hypothesis discussed above was confirmed
for the fifth generation systems. In contrast to the fourth
generation cementing systems, the fifth generation dual-
cured cementing systems use benzoyl peroxide only in the
resin cements and contain parabenzene sulfinic acid sodium
salts in the adhesive components. These aryl sulfinic acid salts
are used to reduce or even eliminate the incompatibility
between acidic monomers within the adhesive system and the
tertiary aromatic amine from the resin cement.12,22 Therefore,
the lower content of self-curing components in the fifth
generation systems may have not been capable of compensat-
ing for the decrease in light intensity promoted by the
presence of pre-cured resin discs.
Among all fifth generation adhesive systems evaluated, B1
was the only adhesive system containing benzoyl peroxide
instead of aryl sulfinic acid salts in its composition. However,
the DC of this dual-cured cementing system was also affected
by the presence of the pre-cured resin discs. One possible
explanation for this finding may be related to the lack of the
aryl sulfinic acid salts in its composition. Although the total
amount of benzoyl peroxide was increased due to its presence
in both the resin cement and adhesive system, it may be
speculated that the chemical incompatibility between the
adhesive resin and dual-cured resin cement may have
impaired formation of initiating radicals and consequently
the self-curing reaction was compromised.10,23 Thus, the
polymerization may have relied mostly on light exposure,
which was drastically reduced by the presence of pre-cured
resin discs. This speculation might also explain the lower DC
of A4 experimental group when compared with that of A2
when B1/LUTE was used at 5 min interval. Despite the lower
light intensity observed when the A4-shade pre-cured resin
disc was used (Table 5), B1/LUTE was the only cementing
system showing significantly lower DC values of A4 compared
to A2 groups at the 5 min interval. However, the effects of self-
curing mechanisms in compensating for light attenuation can
only be confirmed when comparing the DC of light-activated
and dual-cured adhesive systems applied together with dual-
cured resin cements.
This study compared DC at 5 and 10 min after initial mixture
of components. Most manufacturers advise the clinician to wait
at least five min prior to adjusting a newly cemented indirect
restoration. Except for BIT/LUTE, in which no significant
difference in DC was observed between 5 and 10 min in DLE
group, all other dual-cured cementing systems exhibited lower
DC after 5 min than the values observed after 10 min within A2,
A4, and SC experimental groups. Thus, the research hypothesis,
that the cementing systems would show higher DC at 10 min
than at 5 min, was confirmed in almost all experimental groups.
When light was not available, the difference in DC between 5-
and 10 min intervals ranged from 4 to 17% approximately
(Table 4). As a consequence, mechanical properties, such as
flexural and compressive strengths, elastic moduli, and hard-
ness may be proportionally affected by this change in DC.24,25
Therefore, a longer time period prior to performing occlusal
adjustment or removing excess marginal resin cement may be
indicated over what is currently advocated (5 min).
The results of this study need to be considered with respect
to many aspects related to testing conditions. Because
penetration of the infrared beam into the materials placed
above the crystal ranges from 1 to 7 mm (depending on the
refractive index, the wavelength, and the angle of incidence),26
changes in resin content upon introducing the uncured cement
paste into the unpolymerized dentin bonding agent were only
observed within this thickness. However, the area of infrared
observation, and thus characterization of conversion, is
considered to be clinically relevant, as it is similar to that of a
hybrid layer that would be present on acid etched dentin. Also,
some of the dentin bonding agents used in this study are acidic
in nature.10 It has been demonstrated that the acidity of self-
etching adhesive systems is neutralized after placement by the
 journal of dentistry 36 (2008) 418–426
dissolution of hydroxyapatate-containing dentin matrix.27
Such neutralization is thought to optimize conversion, as
opposed to when polymerization takes place at low pH values.8
The ATR plate upon which the acidic bonding agents were
placed could not provide any buffering capacity to the dentin
bonding agents, and thus could not truly simulate the clinical
situation. For this reason, no self-etching adhesive systems
were evaluated in this study. As both fourth and fifth generation
adhesive systems are applied to previously acid-etched,
demineralized dentin, which does not contain hydroxyapatite,
no change in pH is expected in the clinical situation, considering
the evidence that resin monomers do not fully infiltrate the
demineralized dentin and therefore do not react with hydro-
xyapatite.28,29 Thus, the experimental system used seems to not
be different from the in vivo condition when applying acidic
bonding agents to dentin regarding pH and environmental
conditions. However, other limitations of the method, such as
differences in the surface energy, temperature, and humidity of
the surfaces contacting the cement systems in comparison to
those of demineralized dentin, may lead to some differences in
monomer conversion. Only methodologies capable of evaluat-
ing monomer conversion of bonding agents within deminer-
alized dentin itself would confirm the effects of these conditions
on the degree of conversion.
This in vitro study was based on well-controlled laboratory
conditions. However, other variables, such as the presence of
water and quality of resin infiltration into demineralized dentin,
can affect DC and the resulting mechanical properties of
polymer created when they are applied to teeth.30,31 Monomer
conversion values for dentin bonding agents applied and light
cured alone were not determined in this study. Because the
chemistry of the analyzed interface changed when the resin
cement was applied and diffused into the uncured bonding
agent, direct comparison of conversion values between the
light-cured bonding agent alone and that of the mixture of
bonding agent and cement cannot be made. Thus, the
significance of these differences is not known. Only additional
testing, such as bond strength comparison among specimens of
similar curing modes, would reveal the importance of these
factors.
references
1. Inokoshi S, Willems G, Van Meerbeek B, Lambrechts P,
Braem M, Vanherle G. Dual-cure luting composites. Part I.
Filler particle distribution. Journal of Oral Rehabilitation
1993;20:133–46.
2. Sjogren G, Molin M, van Dijken J, Bergman M. Ceramic inlays
(Cerec) cemented with either a dual-cured or a chemically
cured composite resin luting agent. A 2-year clinical study.
Acta Odontologica Scandinavica 1995;53:325–30.
3. Strang R, McCrosson J, Muirhead GM, Richardson SA. The
setting of visible-light-cured resins beneath etched
porcelain veneers. British Dental Journal 1987;163:149–51.
4. Ruyter IE. Methacrylate-based polymeric dental materials:
conversion and related properties. Summary and review.
Acta Odontologica Scandinavica 1982;40:359–76.
5. Milleding P, Ortengren U, Karlsson S. Ceramic inlay systems:
some clinical aspects. Journal of Oral Rehabilitation
1995;22:571–80.
425
6. Nathanson D. Etched porcelain restorations for improved
esthetics. Part II. Onlays. Compendium 1987;8:105–10.
7. Frankenberger R, Sindel J, Kramer N, Petschelt A. Dentin
bond strength and marginal adaptation: direct composite
resins versus ceramic inlays. Operative Dentistry 1999;24:
147–55.
8. Yamauchi J. Study of dental adhesive containning
phosphoric acid methacrylate monomer. Japanese Journal of
Dental Materials 1986;5:144–54.
9. Tay FR, Suh BI, Pashley DH, Prati C, Chuang SF, Li F. Factors
contributing to the incompatibility between simplified-step
adhesives and self-cured or dual-cured composites. Part II.
Single-bottle, total-etch adhesive. The Journal of Adhesive
Dentistry 2003;5:91–105.
10. Sanares AM, Itthagarun A, King NM, Tay FR, Pashley DH.
Adverse surface interactions between one-bottle light-cured
adhesives and chemical-cured composites. Dental Materials
2001;17:542–56.
11. Giannini M, De Goes MF, Nikaido T, Shimada Y, Tagami J.
Influence of activation mode of dual-cured resin composite
cores and low-viscosity composite liners on bond strength
to dentin treated with self-etching adhesives. The Journal of
Adhesive Dentistry 2004;6:301–6.
12. Ikemura K, Endo K. Effect of adhesion of new
polymerization initiator systems comprising 5-
monosubstituted barbituric acids, sulfinate amides, and ter-
butyl peroxymaleic acid in dental adhesive resin. Journal of
Applied Polymer Science 1999;72:1655–68.
13. Blackman R, Barghi N, Duke E. Influence of ceramic
thickness on the polymerization of light-cured resin
cement. The Journal of Prosthetic Dentistry 1990;63:
295–300.
14. Cardash HS, Baharav H, Pilo R, Ben-Amar A. The effect of
porcelain color on the hardness of luting composite resin
cement. The Journal of Prosthetic Dentistry 1993;69:620–3.
15. Hasegawa EA, Boyer DB, Chan DC. Hardening of dual-cured
cements under composite resin inlays. The Journal of
Prosthetic Dentistry 1991;66:187–92.
16. Ruyter IE, Svendsen SA. Remaining methacrylate groups in
composite restorative materials. Acta Odontologica
Scandinavica 1978;36:75–82.
17. Rueggeberg FA, Hashinger DT, Fairhurst CW. Calibration of
FTIR conversion analysis of contemporary dental resin
composites. Dental Materials 1990;6:241–9.
18. Rueggeberg FA, Caughman WF. The influence of light
exposure on polymerization of dual-cure resin cements.
Operative Dentistry 1993;18:48–55.
19. Asmussen E. Setting time of composite restorative resins
versus content of amine, peroxide, and inhibitor. Acta
Odontologica Scandinavica 1981;39:291–4.
20. El-Mowafy OM, Rubo MH. Influence of composite inlay/
onlay thickness on hardening of dual-cured resin cements.
Journal of Dentistry 2000;66:147.
21. Hofmann N, Hindle AR, Agee KA, Carvalho RM, Tay FR,
Rueggeberg FA, et al. Comparison of photo-activation versus
chemical or dual-curing of resin-based luting cements
regarding flexural strength, modulus and surface hardness.
Journal of Oral Rehabilitation 2001;28:1022–8.
22. Tay FR, Pashley DH, Yiu CK, Sanares AM, Wei SH. Factors
contributing to the incompatibility between simplified-step
adhesives and chemically-cured or dual-cured composites.
Part I. Single-step self-etching adhesive. The Journal of
Adhesive Dentistry 2003;5:27–40.
23. Ruyter IE. Unpolymerized surface layers on sealants. Acta
Odontologica Scandinavica 1981;39:27–32.
24. Ferracane JL, Berge HX, Condon JR. In vitro aging of dental
composites in water—effect of degree of conversion, filler
volume, and filler/matrix coupling. Journal of Biomedical
Materials Research 1998;42:465–72.
426 journal of dentistry 36 (2008) 418–426
25. Lovell LG, Lu H, Elliott JE, Stansbury JW, Bowman CN. The
effect of cure rate on the mechanical properties of dental
resins. Dental Materials 2001;17:504–11.
26. Wendl B, Droschl H, Kern W. A comparative study of
polymerization lamps to determine the degree of cure of
composites using infrared spectroscopy. European Journal of
Orthodontics 2004;26:545–51.
27. Hume WR. Influence of dentine on the pulpward release of
eugenol or acids from restorative materials. Journal of Oral
Rehabilitation 1994;21:469–73.
28. Hashimoto M, Ohno H, Kaga M, Sano H, Tay FR, Oguchi H,
et al. Over-etching effects on micro-tensile bond strength
and failure patterns for two dentin bonding systems. Journal
of Dentistry 2002;30:99–105.
29. Tay FR, Gwinnett JA, Wei SH. Micromorphological spectrum
of acid-conditioned dentin following the application of a
water-based adhesive. Dental Materials 1998;14:329–38.
30. Paul SJ, Leach M, Rueggeberg FA, Pashley DH. Effect of water
content on the physical properties of model dentine primer
and bonding resins. Journal of Dentistry 1999;27:209–14.
31. De Munck J, Van Meerbeek B, Yoshida Y, Inoue S, Vargas M,
Suzuki K, et al. Four-year water degradation of total-etch
adhesives bonded to dentin. Journal of Dental Research
2003;82:136–40.