Eur J Oral Sci 2015; 123: 53–60 Ó 2014 Eur J Oral Sci

DOI: 10.1111/eos.12167 European Journal of

Printed in Singapore. All rights reserved
Oral Sciences

Jasmina Bijelic-Donova1, Sufyan

Oxygen inhibition layer of composite Garoushi1,2, Lippo V. J. Lassila1,
Pekka K. Vallittu1,3
resins: effects of layer thickness and 1
Department of Biomaterials Science and
Turku Clinical Biomaterials Centre-TCBC,

surface layer treatment on the Institute of Dentistry, University of Turku,

Turku, Finland; 2Department of Restorative
Dentistry and Periodontology, Institute of

interlayer bond strength Dentistry, Libyan International Medical

University, Benghazi, Libya; 3City of Turku
Welfare Division, Oral Health Care, Turku,
Finland

Bijelic-Donova J, Garoushi S, Lassila LVJ, Vallittu PK. Oxygen inhibition layer of

composite resins: effects of layer thickness and surface layer treatment on the
interlayer bond strength.
Eur J Oral Sci 2015; 123: 53–60. © 2014 Eur J Oral Sci
An oxygen inhibition layer develops on surfaces exposed to air during polymeriza-
tion of particulate filling composite. This study assessed the thickness of the oxygen
inhibition layer of short-fiber-reinforced composite in comparison with conventional
particulate filling composites. The effect of an oxygen inhibition layer on the shear
bond strength of incrementally placed particulate filling composite layers was also
evaluated. Four different restorative composites were selected: everX Posterior (a
short-fiber-reinforced composite), Z250, SupremeXT, and Silorane. All composites
were evaluated regarding the thickness of the oxygen inhibition layer and for shear
bond strength. An equal amount of each composite was polymerized in air between
two glass plates and the thickness of the oxygen inhibition layer was measured using
a stereomicroscope. Cylindrical-shaped specimens were prepared for measurement
of shear bond strength by placing incrementally two layers of the same composite
material. Before applying the second composite layer, the first increment’s bonding
Dr Jasmina Bijelic-Donova, TCBC, Institute of
site was treated as follows: grinding with 1,000-grit silicon-carbide (SiC) abrasive €inen
Dentistry, University of Turku, Ita
paper, or treatment with ethanol or with water-spray. The inhibition depth was low- €katu 4 B, FI-20520 Turku, Finland
Pitka
est (11.6 lm) for water-sprayed Silorane and greatest (22.9 lm) for the water-
sprayed short-fiber-reinforced composite. The shear bond strength ranged from E-mail: jabije@utu.fi
5.8 MPa (ground Silorane) to 36.4 MPa (water-sprayed SupremeXT). The presence
of an oxygen inhibition layer enhanced the interlayer shear bond strength of all Key words: fiber-reinforced composite;
investigated materials, but its absence resulted in cohesive and mixed failures only inhibition depth; shear bond strength; surface
with the short-fiber-reinforced composite. Thus, more durable adhesion with short- treatment; unpolymerized layer
fiber-reinforced composite is expected. Accepted for publication December 2014

Restorative filling composite resins have been recently
improved with regard to the composition of the resin
matrix and the shape of the filler particles. Enhancing the
physical and mechanical properties of resin composites by
incorporation of millimeter-scale short-fiber fillers and a
resin matrix encompassing a semi-interpenetrating polymer
network (semi-IPN) structure has proved promising (1, 2).
Altering the chemical structure of monomers has also been
investigated, and recently dimethacrylate-based monomers
have been replaced with silorane-based ring-opening poly-
merization systems (3). This monomer system combines an
oxirane ring (which opens during polymerization) and
siloxane (that increases the hydrophobicity of the resin
composite). The most important difference between the
two monomer systems is that dimethacrylates are cured
with a free radical, whereas silorane-based composites are
cured via cationic polymerization.
The curing reaction in siloranes is a photoinitiated
cationic ring-opening polymerization reaction of epoxy
monomers with an iodonium salt, an electron donor,
and camphorquinone (CQ) as the photoinitiators. The
presence of CQ enables the usage of conventional den-
tal-curing units because of the matching light spectrum,
whereas the other two initiators are needed to generate
reactive cationic species that start the ring-opening poly-
merization. The irradiation of the photoinitiator induces
the fragmentation of the iodonium salt and subsequently
an acidic cation is released. This cation protonates the
oxirane groups of the monomer and begins cationic
polymerization by opening the oxirane ring (3).
Although the cationic ring-opening polymerization is
insensitive to oxygen (4), the formation of an oxygen
inhibition layer on the surface of the freshly polymerized
silorane-based composite is still possible (5).
54 Bijelic-Donova et al.
The polymerization reaction with dimethacrylate-
based composite materials induced by light-irradiation
leads to the decomposition of the two-component initi-
ating system (CQ and tertiary amine) and results in the
generation of reactive free radicals, which are able to
add to the double bonds of dimethacrylate groups,
thereby creating new radicals. In the propagation reac-
tion, these radicals will react until no additional mono-
mer is able to react or the propagation reaction has
terminated (6). Compared with a monomer molecule,
atmospheric oxygen has a greater ability to react with
the propagating free radicals (7), oxidizing them into
stable spaces, known as peroxides, which have low
reactivity towards the monomer. This leads to retarda-
tion or inhibition of the free-radical polymerization
reaction. Consequently, an unpolymerized monomer
layer will appear on the surface of the freshly cured
resin, when resin is cured in air. This layer is known as
the oxygen inhibition layer.
The components of the oxygen inhibition layer are
similar in composition to those of the uncured resin
with consumed or reduced amounts of photoinitiator
(7, 8). The oxygen inhibition layer is also known as an
unpolymerized (uncured) layer of resin and its thickness
as inhibition depth (9), which is affected by numerous
factors (5, 10–16). The thickness of the oxygen inhibi-
tion layer could influence the interlayer bonding prop-
erties of the composite resins because the oxygen
inhibition layer is known to: (i) impair the interfacial
homogeneity (7); (ii) permit complete interdiffusion of
the freshly overlaid composite through the oxygen inhi-
bition zone, if thin (8); and (iii) compromise the
mechanical strength, if thick (17). Hence, the thickness
of the oxygen inhibition layer is crucial for the integrity
of the layer itself and this for the quality of the inter-
layer connection. In addition, oxygen inhibition raises
the problem of interlayer adhesion (18–23).
The effect of oxygen on the bonding properties of
the newly developed short-fiber-reinforced composite
(everX Posterior) is unknown. This short-fiber-rein-
forced composite is a dimethacrylate-based composite,
in which Bis-GMA and TEGDMA are used as mono-
mers and millimeter-scale short-fiber fillers with a semi-
IPN structure (1, 2) are incorporated into the resin
matrix. Fibers are known to restrict the polymerization
shrinkage (24, 25), but as a result of the monomer com-
position, the polymerization reaction still proceeds by
free radicals. Thus, formation of an oxygen inhibition
layer on the surface of the short-fiber-reinforced com-
posite is expected, although the viscosity of the resin
matrix is high. It is also unknown how the short fibers
within the composite are affected by oxygen diffusion.
It was hypothesized that the oxygen inhibition layer
will enhance the shear bond strength of the newly cured
upper layer to the cured lower layer both of short-
fiber-reinforced composite and that the thickness of the
oxygen inhibition layer will give measurable values.
Furthermore, Silorane was not expected to develop an
inhibition layer and thus no effect was expected on the
interlayer shear bond strength between incrementally
placed layers of silorane-based composite.
The present investigation included dimethacrylate-
based composites (short-fiber-reinforced composite,
microhybrid, and nanofilled composite) and low-shrinkage
silorane-based composite. The study aims were: (i) to
assess variation in the thickness of the oxygen inhibi-
tion layer on the surface of the short-fiber-reinforced
composite in comparison with freshly polymerized mi-
crohybrid-, nanofilled-, and silorane-based composite
resins under the same conditions; and (ii) to evaluate
the interlayer shear bond strength between successive
depositions of same composite material with present,
removed, water-spray and ethanol treated oxygen inhi-
bition layer. Fracture mode evaluation of the interlayer
surface following the shear bond test was also assessed.
Material and methods
Specimen preparation
A previously suggested microscopic technique (9, 10, 26,
27) for measuring the depth of oxygen inhibition was used
in the present study. Table 1 shows the restorative com-
posite materials investigated and their composition. Three
groups were prepared for each material tested (n = 3).
Each group differed regarding the treatment used to
remove the oxygen inhibition layer from the surface of the
polymerized specimen; in addition, there was a control
group, in which the oxygen inhibition layer was left intact.
An equal amount of each composite resin was applied
onto the middle of a horizontally placed glass microscope
slide. A constant sample thickness of 0.1 mm was ensured
by placing two glass plates (20 mm 9 20 mm), as spacers,
on each side of the composite resin, which was covered by
another microscope slide as a cover slip. The specimens
were then polymerized through the cover slip for 40 s
using a light-emitting diode (LED) light-curing unit (Eli-
par S10; 3M ESPE, St Paul, MN, USA) with a tip diame-
ter of 28 mm, producing an averaged irradiance of
1,200  2.5 mW cm 2 and a wavelength range of 430–
480 nm, with a maximal peak at 455 nm. This method
secured formation of the oxygen inhibition layer only at
the outer sides of the specimens because air–resin contact
was possible only at the resin boundary between the poly-
merized composite material and the spacers.
The groups prepared for this testing were as follows:
group 1, the oxygen inhibition layer was not treated (i.e.
was left intact); group 2, the oxygen inhibition layer was
treated by wiping it from the surface of the cured specimen
using alcohol sponges soaked in 99 wt% ethanol (Etax Aa;
Altia, Rajam€aki, Finland) for 20 s and then gently air dried
for another 20 s; group 3, the oxygen inhibition layer was
treated with water applied as a water spray for 20 s from a
distance of ~5 mm perpendicular to the specimen surface
and then gently air dried for another 20 s.
The depth of the inhibition layer was measured using a
stereomicroscope (Wild, Heerbrugg, Switzerland) in 10
locations around the periphery of each specimen at a mag-
nification of 940, with a calibrated micrometer disk. The
results were recorded in micrometers between the outer
boundary of the specimen and the polymerized–unpolymerized
resin interface. In addition, micrographs were taken of
each specimen using the computer imaging program, Leica
DC Twain (Leica, Cambridge, UK), in order to provide a
visual record of the inhibition layer.
 Oxygen inhibition of short-fiber composite 55

Table 1
Materials used in the study and their basic composition

Filler
Type of content
Composite material Manufacturer Lot No. Resin composition Filler composition wt/vol% Filler size

everX Posterior Short-fibre GC, Tokyo, 1307292 Bis-GMA, E-glass fibre, 74.2/53.6 1–2 mm of
composite Japan TEGDMA, barium the individual
PMMA borosilicate glass fibre
and 0.1–2.2 lm
of the
barium-borosilicate
filler
Filtek Z250 Microhybrid 3M ESPE, 9BN (A3) Bis-GMA, Zirconia/silica 78/60 0.01–3.5 lm
St Paul, Bis-EMA,
MN, USA UDMA,
TEGDMA
Filtek Supreme Nanofilled 3M ESPE 9AL (A3) Bis-GMA, Aggregated 78.5/59.5 20 nm of the silica
XT Bis-EMA, zirconia/ filler and
UDMA, silica cluster and 0.6–1.4 lm of the
TEGDMA non-agglomerated/ Zr/SiO2 cluster
non-aggregated particle (5–20 nm
silica filler of the primary
particle)
Filtek Silorane Microhybrid 3M ESPE OFH (A3) ECHCPMS, Quartz, yttrium 76/55 0.1–2.0 lm
silorane BECHEPMS, trifluoride
MBP, MEMSBP,
MEFDOSBP,
MASBP,
BTPFPMEPMPI

BECHEPMS, bis-3,4-epoxycyclohexylethyl-phenyl-methylsilane; Bis-EMA, bisphenol-A-dyethoxy dimethacrylate; Bis-GMA, bisphenol-

A-glycidyl dimethacrylate; BTPFPMEPMPI, borate(1-),tetrakis(pentafluorophenyl)-[4-(methylethyl)phenyl](4-methylphenyl)iodonium;
DMAEMA, dimethylaminoethyl methacrylate; ECHCPMS, 3,4-epoxycyclohexylcyclo-polymethylsiloxane; MASBP, a mixture of
alpha-substituted by-products; MBP, a mixture of other by-products; MEFDOSBP, a mixture of epoxyfunctional di- and oligo-siloxane
by-products; MEMSBP, a mixture of epoxy-mono-silanole by-products; PMMA, polymethylmethacrylate; TEGDMA, triethylene-glycol
dimethacrylate; UDMA, urethane dimethacrylate.

Interlayer shear bond strength
The shear bond strength of each composite material listed
in Table 1 was investigated. In addition to the groups
described above (groups 1–3), one further group (group 4)
was included in this investigation.
In group 4, the oxygen inhibition layer was removed by
grinding the surface with 1,000-grit Federation of European
Procedures of Abrasives (FEPA) silicon carbide (SiC) abra-
sive grinding paper (Struers, Copenhagen, Denmark) at 250
r.p.m. under water cooling using an automatic grinding
machine (LaboPol-25; Struers). After grinding, the surface
was gently dried with air-spray for 20 s.
In this experiment, the same restorative material was
used as the substrate and the adherent material. The corre-
sponding unpolymerized composite restorative material
was inserted into the round-shape retentive cavity (of 5 mm
diameter and 3 mm depth) prepared in an acrylic resin
block, flattened, and then light-cured for 40 s with an LED
polymerization light. Following polymerization, the adher-
ent material was applied onto the substrate in an increment
of 2 mm using a translucent polyethylene mold with an
inner diameter of 3.6 mm and then polymerized for 40 s.
The adherent material was polymerized on the composite
surface that had been cured in air and for which the oxygen
inhibition layer had been untreated (group 1), treated with
ethanol (group 2) or water spray (group 3), or removed
(group 4). Twelve specimens were prepared for each group.
The specimens were either dry stored at 37°C for 7 days or
thermocycled (alternating immersion of the samples in dis-
tilled water of a temperature of 5° and 55°C) for 6,000
cycles, with a dwell time of 30 s and a transfer time of 5 s
before testing. The specimens were stored in distilled water
for 48 h at room temperature (23  1°C) before thermocy-
cling and were tested immediately afterwards.
The shear bond strength test was performed using a uni-
versal testing machine (Lloyd; Lloyd Instruments, Fare-
ham, UK) at room temperature (23  1°C) and the results
were recorded using PC software (Nexygen; Lloyd Instru-
ments). The specimens were mounted in a mounting jig
(Bencor Multi-T shear assembly; Danville Engineering,
San Remon, CA, USA) with the shearing rod against and
parallel to the flat prepared substrate sites. A circular edge
blade created the shear type load positioned over the inter-
face between the substrate and the adherent material at a
crosshead speed of 1.0 mm min 1 until fracture. The shear
load at failure was recorded in N and converted to MPa
as a function of the area under test, automatically by the
software. Shear bond strength values are presented in
MPa. In order to analyse and to determine the fracture
type, all fractured surfaces were visually examined under
light microscopy at a magnification of 940.
Statistical analysis
The data were statistically analysed using ANOVA at a sig-
nificance level of P < 0.05 with SPSS version 19 (Statistical
56 Bijelic-Donova et al.

Package for Social Sciences, SPSS, Chicago, IL, USA).
Tukey’s post-hoc analysis was performed following ANOVA
to determine differences among the groups.
Results
Thickness of the oxygen inhibition layer
Optically measurable thickness of the oxygen inhibition
layer was evaluated for all materials tested. The results
are presented in Table 2. The inhibition depth ranged
from 11.6  2.4 lm for the water-spray-treated silora-
ne-based composite to 22.9  4.7 lm for the water-
spray-treated short-fiber-reinforced composite.
The grinding procedure probably removed the oxy-
gen inhibition layer completely. For this reason the
oxygen inhibition layer thickness for all specimens of
group 4, irrespective of the material, was assumed to be
zero.
Two-way ANOVA showed that both the type of mate-
rial and the surface treatment had significant effects
(P < 0.001) on the thickness of the oxygen inhibition
layer. Although differences were observed among the
materials, treatment with ethanol and water spray did
not affect the inhibition depth when each composite
material was observed individually. An exception was
that the water spray cleaned surface of the microhybrid
composite, which showed a statistically significant dif-
ference compared with its control and ethanol-
treated counterparts.
Figure 1 shows the oxygen inhibition layer detected
on the surfaces of the investigated materials after etha-
nol treatment. Distinct lines between the oxygen
inhibition region (i), the diffusion (i.e. transition) zone
(d), and the polymerized region (p) were observed for
all specimens, regardless of the surface treatment. The
oxygen inhibition layer was present on the surfaces of
all dimethacrylate-based composites (Fig. 1A–C) and
also on the surface of the silorane-based composite
(Fig. 1D).
Interlayer shear bond strength
The results of the shear bond strength investigation
between incrementally placed composite layers are pre-
sented in Fig. 2. A three-way ANOVA (material type, sur-
face treatment, and storage condition) revealed that
only the composite material type and the surface treat-
ment had significant effects on the interlayer shear
bond strength (P < 0.001). The difference between the
dry and the thermocycled specimens was not statisti-
cally significant (P > 0.001). Furthermore, no difference
was observed between the ethanol and the water-spray
treatment, compared with each other or with their con-
trol counterparts, for any of the tested material
observed individually. All tested materials demon-
strated lower interlayer shear bond strength when the
cured surface of the underlayered composite was
ground with SiC paper.
For dry-stored specimens, the shear bond strength val-
ues ranged from 5.8  1.8 MPa for silorane-based com-
posite with a ground interface to 36.4  7.6 MPa for
microhybrid composite with a water-spray-treated inter-
face. The thermocycled specimens exhibited greater shear
bond strength values, ranging from 8.3  3.8 MPa for
silorane-based composite with a mechanically ground
interface to 42.6  8.2 MPa for the untreated interface

Table 2
Thickness of the oxygen inhibition layer of the tested materials

Thickness of the
Group oxygen inhibition
Material Group (surface treatment) abbreviation layer (lm)

everX Posterior Group 1 (untreated surface) Ex-1 20.1 (5.5)*

Group 2 (ethanol-treated surface) Ex-2 20.8 (5.7)*
Group 3 (water-spray-treated surface) Ex-3 22.9 (4.7)*
Group 4 (ground surface) Ex-4 –
Filtek Z250 Group 1 (untreated surface) FZ-1 14.5 (2.6)a
Group 2 (ethanol-treated surface) FZ-2 15.2 (4.2)a
Group 3 (water-spray-treated surface) FZ-3 18.8 (3.0)b
Group 4 (ground surface) FZ-4 –
Filtek Supreme XT Group 1 (untreated surface) FS-1 17.1 (3.0)+
Group 2 (ethanol-treated surface) FS-2 19.2 (3.1)+
Group 3 (water-spray-treated surface) FS-3 18.5 (2.6)+
Group 4 (ground surface) FS-4 –
Filtek Silorane Group 1 (untreated surface) FSi-1 13.8 (3.4)#
Group 2 (ethanol-treated surface) FSi-2 12.0 (2.2)#
Group 3 (water-spray-treated surface) FSi-3 11.6 (2.4)#
Group 4 (ground surface) FSi-4 –

Values are given as mean (SD).

The grinding procedure was assumed to remove the oxygen inhibition layer from the composites’ surfaces. Thus, the oxygen inhibition
layer thickness for all specimens in group 4 was assumed to be zero.
The same superscript letters or symbols within a value represent a homogenous subset (P > 0.05) among the groups for each material
individually.

A B
C D
Fig. 1. Microscopy images (940 magnification) of the inhib-
ited zone from: (A) nanofilled composite (Filtek Supreme
XT); (B) microhybrid composite (Filtek Z250); (C) short-
fiber-reinforced composite (everX Posterior); and (D) silorane-
based composite (Filtek Silorane) (all after ethanol treatment).
The lower-case letters denote the inhibited layer (i), the diffu-
sion (i.e. the transition) zone (d), and the polymerized mate-
rial (p).
of the microhybrid composite. The higher bond-strength
values obtained following thermal aging could be
ascribed to the post-curing allowed by the prestorage of
specimens in distilled water for 48 h at room temperature
(23  1°C) before subjecting them to the thermal cycling
procedure.
Failure mode analysis (Fig. 3) showed three fracture
types: adhesive (including breaks at the interface); cohe-
sive (including failures within the substrate or the
adherent composite); and mixed [including small
60
50
Shear bond strength (MPa)
40
30
20
10
0
Ex-1 Ex-2 Ex-3 Ex-4
Fig. 2. Shear bond strength of incrementally placed composite layers, with the oxygen inhibition layer present or removed, after
dry storage (dark-grey bars) and thermal cycling (light-grey bars). The horizontal lines and the same superscript letters above the
bars represent homogenous subsets (P > 0.05) among the groups. Ex, everX Posterior; FS, Filtek Supreme XT; FSi, Filtek Silora-
ne; FZ, Filtek Z250. The numbers indicate the type of treatment applied to the oxygen inhibition layer on the polymerized speci-
men: 1, untreated; 2, ethanol treatment; 3, water-spray treatment; 4, ground.
Oxygen inhibition of short-fiber composite 57
portions of the substrate (base) and interfacial surface
in the fracture surface].
Discussion
When composites are cured in air, as in clinical prac-
tice, an oxygen inhibition layer is formed on the surface
of the freshly cured composite resin. In the present
study, the inhibition of polymerization by oxygen was
determined as the thickness of the low-polymerized
outer layer on composite resin specimens, which were
cured in the presence of air and at ambient tempera-
ture. The differences observed among the dimethacry-
late-based composites could be a result of the filler
content (13) and type (13, 15), which, in addition to the
network density of the resin composite (10, 11), deter-
mined by the content of the diluent (TEGDMA) (5),
also affect the oxygen inhibition depth. However, when
a composite is reinforced with fibers, then the fibers
and their orientation should also be considered as fac-
tors influencing the oxygen inhibition depth (27). The
short-fiber composite used in the present investigation
consisted of a cross-linked polymer network derived
from dimethacrylate monomers (Bis-GMA and TEG-
DMA) and PMMA. During the polymerization pro-
cess, this polymer matrix forms a semi-IPN structure
(28). The differences between the short-fiber-reinforced
composite and both dimethacrylate-based composites
may be explained by the presence of fibers in short-
fiber-reinforced composite, which are shown to affect
the oxygen inhibition depth (27) and the internal void-
space formation (29). Orientation of the fibers in the
previous study favoured the passage of oxygen (27),
but it should be noted that the short-fiber-reinforced
composite used in this study had randomly oriented
short fibers, with length varying between 1 and 2 mm,
and their influence on the oxygen inhibition depth
could be less than in composites with oriented fibers.
a
a
b
c
FZ-1 FZ-2 FZ-3 FZ-4 FS-1 FS-2 FS-3 FS-4 FSi-1 FSi-2 FSi-3 FSi-4
58 Bijelic-Donova et al.

100

90

Failure type distribuon of specimens (%)

80

70

60

50

40

30

20

10

0
dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC dry TC
Ex-1 Ex-2 Ex-3 Ex-4 FZ-1 FZ-2 FZ-3 FZ-4 FS-1 FS-2 FS-3 FS-4 FSi-1 FSi-2 FSi-3 FSi-4

Fig. 3. Failure type distribution of specimens after the shear bond test. A significant finding was the high frequency of cohesive
and mixed breaks (75%) with the everX Posterior applied on the surface of the ground substrate [i.e. that in which the oxygen
inhibition layer has been removed (Ex-4)]. The corresponding treatment for the other materials (FZ-4, FS-4, and FSi-4) resulted
in predominantly adhesive failures. Yellow bars indicate adhesive failures, grey bars indicate mixed (adhesive and cohesive) fail-
ures, and black bars indicate cohesive failures. Ex, everX Posterior; FS, Filtek Supreme XT; FSi, Filtek Silorane; FZ, Filtek
Z250. The numbers indicate the type of treatment applied to the oxygen inhibition layer on the polymerized specimen: 1,
untreated; 2, ethanol treatment; 3, water-spray treatment; 4, ground.

The oxygen inhibition layer was optically observed in silane agent restrict the use of particular fillers, result-
this study (Fig. 1) for both dimethacrylate- and silora- ing in a formulation with decreased filler content and
ne-based composites. The generation of radicals with distinct filler morphology (32). The irregularly shaped
silorane composite is possible because of the presence filler particles and the lower filler load might limit the
of CQ. The absorption of light by CQ leads to an wettability, which alters the thickness of the oxygen
excited CQ formation and initiates an electron-transfer inhibition layer (33, 34). This, in addition to the silora-
photosensitization reaction, which reduces the iodoni- ne chemistry (expoxy-based ring opening system), could
um salt. Consequently, an iodonium salt free radical explain the variations of the effect of the oxygen inhibi-
and a photosensitizer (CQ) cation-radical are yielded. tion layer on the interlayer shear bond strength within
The latter usually generates a strong acid, whereas the the groups for the silorane-based composite and its dif-
former decomposes (30). The acid generated in the fur- ferences from the dimethacrylate-based composites.
ther reaction donates a proton (hydrogen cation) to the Oxygen inhibition layer-free surfaces have been pro-
epoxy ring, which is unstable and prone to combine duced for research purposes by curing the specimens at
with available hydrogen, therefore opening the ring elevated temperatures (13), or in air-free argon (17, 22),
(31). By protonating the oxirane groups, the acidic nitrogen (5, 8, 21, 23), or carbon dioxide (15, 16) atmo-
cation initiates the cationic polymerization. In other spheres. Water spray and ethanol treatments were used
words, the polymerization of silorane-based composite in the present study as momentary treatments for clean-
involves two stages: an initial free-radical phase and a ing the surface of the oxygen inhibition layer, because
cationic phase. The radical concentration is significantly they are clinically more practical methods. All dimeth-
reduced (but not completely eliminated), which conse- acrylate-based composites studied showed an insignifi-
quently leads to formation of a remarkably thinner cantly thicker oxygen inhibition layer after both
oxygen inhibition layer on the surface of the silorane- treatments, which means that those treatments did not
based composite than observed with dimethacrylate- remove the oxygen inhibition layer from the exposed
based composites. The finding of the present study is in surface. The silorane-based composite exhibited a thin-
agreement with the finding of SHAWKAT et al. (5). ner oxygen inhibition layer after both types of surface
The differences observed between the two types of treatment. This could be a result of the aforementioned
composites (dimethacrylate vs. silorane) could be attrib- explanation regarding the silorane chemistry, its filler
uted to distinct differences in their composition. Besides content and morphology, and also the more hydropho-
the filler content, which is lower for the silorane-based bic nature of silorane’s resin matrix than the dimethac-
composite, other differences include: (i) the resin phase rylates’ resin matrix.
[i.e. organic matrix (dimethacrylate-based vs. epoxy Both the composite material and the surface layer
based)]; (ii) type of initiator system [i.e. type and con- treatment affected the interlayer shear bond strength.
centration of photoinitiator (CQ and tertiary amine vs. The outcome for both composite types was improved in-
CQ, iodonium salt and electron donor)]; and (iii) the terlayer shear bond strength when the oxygen inhibition
type of polymerization reaction (radical vs. cationic layer was present. This finding supports the influence of
ring-opening). The specific characteristics of the silora- the physical surface properties of the oxygen inhibition
ne-based organic matrix and the epoxy-functional layer on the bond strength between incrementally placed

composite layers and also its influence on the failure
mode. Therefore, it can be suggested that the surface
wettability provided by the oxygen inhibition layer is
crucial for adhesion of the adherent surface. Factors
influencing wettability, such as the surface free-energy of
the solid and the surface tension of the liquid, have been
discussed in detail elsewhere (33, 34). The finding of the
present investigation is in accordance with studies (33,
34) which showed that both the physical and chemical
surface properties of the oxygen inhibition layer depend
on its thickness; if relatively thin, as in this study, the
oxygen inhibition layer allows diffusion of the photoini-
tiator into the overlaying composite, thus improving the
bond strength. In addition, owing to the presence of a
proton donor, the oxygen inhibition layer mediates
higher bond strengths to both enamel (34) and dentin
(33).
The ethanol and the water-spray treatments were
applied for a controlled time of 20 s, and adverse bond-
ing effects were not observed following either surface
treatment. Cleaning the surface of the oxygen inhibition
layer with ethanol and water-spray may have extracted
some unpolymerized monomers. This might have influ-
enced the bond strength, which was also evident in the
more frequent occurrence of cohesive breaks observed
with these groups. Predominantly cohesive fractures
were observed for the ground short-fiber-reinforced
composite surface (i.e. the oxygen inhibition layer was
completely removed). This could be a result of the
micro-mechanical interlock between the monomer from
the overlaying composite and the fibers of the underlay-
ing composite, which were exposed during the grinding
procedure. In other words, the resin–fiber interaction
was enabled at the interface of the successively placed
short-fiber-reinforced composite layers, although the
oxygen inhibition layer was removed by grinding.
The ground surface resulted in the lowest interlayer
bond strength in all groups, and adhesive failures were
typical for the rest of the particulate filler composites
with ground surfaces, irrespective of the storage condi-
tion. The grinding procedure has probably eliminated
the oxygen inhibition layer and compromised the bond
strength, owing to an inadequate wetting of resin to the
fillers (18, 35).
In general, our results are in agreement with the
majority of other studies (14, 18, 20), in which the pres-
ence of an oxygen inhibition layer with adequate thick-
ness at the surface between the adjacent composite
layers improved the interfacial bonding. However,
ELIADES & CAPUTO (7) reported inefficient polymeriza-
tion within the oxygen inhibition layer that reduced the
interfacial strength, which contradicts our results. The
authors suggested that in order to achieve a strong
bond with a new composite layer, this catalyst-free
monomer layer should be removed. The silorane-based
composite exhibited the lowest bond strength, which
could be a result of the lower filler load as well as of
the formation of a thin oxygen inhibition layer that led
to defective interlayer connection.
The present investigation supports acceptance of the
first hypothesis regarding the influence of the oxygen
Oxygen inhibition of short-fiber composite 59
inhibition layer on the bonding properties of the short-
fiber-reinforced composite and rejection of the second
hypothesis regarding the influence of the oxygen inhibi-
tion layer on the bonding properties of the silorane-
based composite. The presence of an oxygen inhibition
layer on the surface of the cured short-fiber-reinforced
composite underlayer improved the bond strength to the
adjacent short-fiber-reinforced composite layer and the
inhibition depth gave measurable results. In contrast to
the second hypothesis, the oxygen inhibition layer was
also required for improving the interlayer bond strength
with the silorane-based composite and its absence caused
significant reduction of the bond strength values, from
28.8 (7.8) MPa to 5.8 (1.8) MPa.
In conclusion, the oxygen inhibition layer, acting as
an intermediate layer, is retained on the surface of the
composite after treatment with either ethanol or water-
spray. The water-spray treatment would probably have
no effect on removal of the oxygen inhibition layer,
because of the oxygen dissolved in water, whereas treat-
ment with ethanol could remove the oxygen inhibition
layer, but probably a longer application time is needed.
The presence of an oxygen inhibition layer improved
the interlayer shear bond strength of adjacent compos-
ite layers and led to more durable adhesion, whereas
the absence of an oxygen inhibition layer adversely
affected the bond strength and led to adhesive interfa-
cial failures. Hence, the oxygen inhibition layer should
be provided and left intact after polymerization.
Similarly to conventional composites, the oxygen
inhibition layer also remained on the surface of the
short-fiber-reinforced composite and did not adversely
affect the bond strength to a successive layer of short-
fiber-reinforced composite. The interlayer bond strength
of short-fiber-reinforced composite was within the same
range as that observed for the conventional dimethac-
rylate-based filling composites. However, the short-
fiber-reinforced composite showed a tendency for cohe-
sive breaks, regardless of whether the oxygen inhibition
layer was present or removed. This finding supports the
clinical reliability of adhesion of the short-fiber-rein-
forced composite and more durable adhesion should be
expected with this composite material.
Acknowledgements – The authors thank Adjunct Professor Niko
Moritz for technical assistance with the figures and Robert M.
Badeau, PhD, for the English language editing of this manuscript.
We are also grateful to the 3M ESPE and GC for providing the
materials used in this investigation. This study is part of the BioCity
Turku Biomaterials Research Program (www.biomaterials.utu.fi).
Conflicts of interest – All authors have agreed with the concept of
the manuscript and they confirm that there is no economical bene-
fit or any financial interest to report. Authors do not have con-
flicts of interests. Author Vallittu is a consultant to the Stick Tech
Ltd., a member of the GC Group.
References
1. GAROUSHI S, VALLITTU PK, LASSILA LVJ. Short glass fiber rein-
forced restorative composite resin with semi-inter penetrating
polymer network matrix. Dent Mater 2007; 23: 1356–1362.
60 Bijelic-Donova et al.
€
2. GAROUSHI S, SAILYNOJA E, VALLITTU PK, LASSILA L. Physical
properties and depth of cure of a new short fiber reinforced
composite. Dent Mater 2013; 29: 835–841.
3. WEINMANN W, THALACKER C, GUGGENBERGER R. Siloranes in
dental composites. Dent Mater 2005; 21: 68–74.
4. TEZVERGIL-MUTLUAY A, LASSILA LVJ, VALLITTU PK. Incre-
mental layers bonding of silorane composite: the initial bond-
ing properties. J Dent 2008; 36: 560–563.
5. SHAWKAT ES, SHORTALL AC, ADDISON O, PALIN WM. Oxygen
inhibition and incremental layer bond strengths of resin com-
posite. Dent Mater 2009; 25: 1338–1346.
6. BURTSCHER P. Stability of radicals in cured composite materi-
als. Dent Mater 1993; 9: 218–221.
7. ELIADES GC, CAPUTO AA. The strength of layering technique
in visible light-cured composites. J Prosthet Dent 1989; 61:
31–38.
8. SUH BI. Oxygen-inhibited layer in adhesion dentistry. J Esthet
Restor Dent 2004; 16: 316–323.
9. VALLITTU PK. Unpolymerized surface layer of autopolymeriz-
ing polymethyl dimethacrylate resin. J Oral Rehab 1999; 26:
208–212.
10. RUYTER IE. Unpolymerized surface layers on sealents. Acta
Odontol Scand 1981; 39: 27–32.
11. LEE TY, GUYMON CA, SONNY JONSSON € E, HOYLE CE. The
effect of monomer structure on oxygen inhibition of (met)ac-
rylates photopolymerization. Polymer 2004; 45: 6155–6162.
12. FINGER WJ, LEE KS, PODSZUN W. Monomers with low oxy-
gen inhibition as enamel/dentin adhesives. Dent Mater 1996;
12: 256–261.
13. GAUTHIER MA, STANGEL I, ELLIS TH, ZHY XX. Oxygen inhi-
bition in dental resins. J Dent Res 2005; 84: 725–729.
14. KIM JS, CHOI YH, CHO BH, SON HH, LEE IB, UM CM, KIM
CK. Effect of light-cure time of adhesive resin on the thick-
ness of the oxygen-ihibited layer and the microtensile bond
strength to dentin. J Biomed Mater Res Part B Appl Biomater
2006; 78B: 115–123.
15. STUDER K, DECKER C, BECK E, SCHWALM R. Overcoming oxy-
gen inhibition in UV-curing of acrylate coatings by carbon
dioxide inerting. Part I. Prog Org Coat 2003; 48: 92–100.
16. STUDER K, DECKER C, BECK E, SCHWALM R. Overcoming oxy-
gen inhibition in UV-curing of acrylate coatings by carbon
dioxide inerting, Part II. Prog Org Coat 2003; 48: 101–111.
17. RUEGGEBERG FA, MARGESON DH. The effect of oxygen inhibi-
tion on an unfilled/filled composite system. J Dent Res 1990;
69: 1652–1658.
18. LI J. Effects of surface properties on bond strength between
layers of newly cured dental composites. J Oral Rehab 1997;
24: 358–360.
19. BOYER DB, CHAN KC, TORNEY DL. The strength of multilayer
and repaired composite resin. J Prosthet Dent 1978; 39: 63–67.
20. TRUFFIER-BOUTRY D, PLACE E, DEVAUX J, LELOUP G. Interfa-
cial layer characterization in dental composite. J Oral Rehab
2003; 30: 74–77.
21. DALL’OCA S, PAPACCHINI F, GORACCI C, CURY AH, SUH BI,
TAY FR, POLIMENI A, FERRARI M. Effect of oxygen inhibition
on composite repair strength over time. J Biomed Mater Res
Part B Appl Biomater 2007; 81B: 493–498.
22. SEHGAL A, RAO YM, JOSHUA M, NARAYANAN LL. Evaluation
of the effect of the oxygen-inhibited layer on shear bond
strength of two resin composites. J Conserv Dent 2008; 11:
159–161.
23. PAPACCHINI F, DALL’OCA S, CHIEFFI N, GORACCI C, SADEK
FT, SUH BI, TAY FR, FERRARI M. Composite-to-composite
microtensile bond strength in the repair of a micofilled hybrd
resin: effect of surface treatment and oxygen inhibition. J Ad-
hes Dent 2007; 9: 25–31.
24. TEZVERGIL A, LASSILA LVJ, VALLITTU PK. The effect of fiber
orientation on the polymerization shrinkage strain of fiber-
reinforced composites. Dent Mater 2006; 22: 610–616.
25. GAROUSHI S, VALLITTU PK, WATTS DC, LASSILA LVJ. Poly-
merization shrinkage of experimental short glass fiber-rein-
forced composite with semi-interpenetrating polymer network
matrix. Dent Mater 2008; 24: 211–215.
26. LEKKA MP, PAPAGIANNOULIS L, ELIADES GC, CAPUTO AA. A
comparative in vitro study of visible light-cured sealants. J
Oral Rehab 1989; 16: 287–299.
27. VALLITTU PK. Oxygen inhibition of autopolymerization of
polymethyldimethacrylate-glass fiber composite. J Mater Sci
Mater Med 1997; 8: 489–492.
28. VALLITTU PK. Interpenetrating polymer networks (IPNs) in
dental polymers and composites. In: MATINLINNA JP, MITTAL
KL, eds. Adhesion aspects in dentistry. Leiden, the Nether-
lands: CRC Press, 2009; 63–74.
29. VALLITTU PK. The effect of void space and polymerization
time on transverse strength of acrylic-glass fibre composite.
J Oral Rehabil 1995; 22: 257–261.
30. CRIVELLO JV. Design of photoacid generating systems.
J Photopolym Sci Tec 2009; 22: 575–582.
31. BOWEN RI. Use of epoxy resins in restorative materials. J
Dent Res 1956; 35: 360–369.
32. LEPRINCE J, PALIN WM, MULLIER T, DEVAUX J, VREVEN J, LE-
LOUP G. Investigating filler morphology and mechanical prop-
erties of new low-shrinkage resin composite types. J Oral
Rehabil 2010; 37: 364–376.
33. KOGA K, TSUJIMOTO A, ISHII R, IINO M, KOTAKU M, TAKAM-
IZAWA T, TSUBOTA K, MIYAZAKI M. Influence of oxygen inhi-
bition on the surface free-energy and dentin bond strength of
self-etch adhesives. Eur J Oral Sci 2011; 119: 395–400.
34. OYAMA K, TSUJIMOTO A, OTSUKA E, SHIMIZU Y, SHIRATSUCHI
K, TSUBOTA K, TAKAMIZAWA T, MIYAZAKI M. Influence of
oxygen inhibition on the surface free energy and enamel
bond strength of self-etch adhesives. Dent Mater J 2012; 31:
26–31.
35. VANKERCKHOVEN H, LAMBRECHTS P, VAN BEYLEN M, DAVIDSON
CL, VANHERLE G. Unreacted dimethacrylate groups on the
surfaces of composite resins. J Dent Res 1982; 61: 791–795.
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