d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550

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Effect of curing light emission spectrum on the

nanohardness and elastic modulus of two bulk-fill
resin composites

Yaser Issa a , David C. Watts b , Daniel Boyd c , Richard B. Price d,∗

a Faculty of Dentistry, Dalhousie University, Halifax, Nova Scotia, Canada
b University of Manchester, School of Dentistry and Photon Science Institute, Manchester, UK
c Dept of Applied Oral Sciences, Faculty of Dentistry, Dalhousie University, Halifax, Nova Scotia, Canada
d Dept of Dental Clinical Sciences, Faculty of Dentistry, Dalhousie University, Halifax, Nova Scotia, Canada

a r t i c l e i n f o a b s t r a c t

Keywords: Objective. To determine the nanohardness and elastic moduli of two bulk-fill resin based
Resin based composite composites (RBCs) at increasing depths from the surface and increasing distances laterally
Bulk fill from the center after light curing.
Light curing unit Methods. Two bulk-fill dental RBCs: Tetric EvoCeram Bulk Fill (TECBF) and Filtek Bulk Fill
Light emitting diode Flowable (FBFF) were light cured in a metal mold with a 6 mm diameter and a 10 mm long
Photo polymerization semi-circular notch. The RBCs were photo-polymerized for 10 s using a light emitting diode
Nano-indentation (LED) Bluephase Style curing light, with the original light probe that lacked the homogenizer.
Nanohardness This light has two blue light and one violet light LED emitters. By changing the probe orien-
Elastic modulus tation over the mold, the light output from only two LEDs reached the RBC. Measurements
Emission spectrum were made using: (i) the light from one violet and one blue LED, and (ii) the light from the two
blue LEDs. Five specimens of each RBC were made using each LED orientation (total 20 spec-
imens). Specimens were then stored in the dark at 37 ◦ C for 24 h. Fifty indents were made
using an Agilent G200 nanoindentor down to 4 mm from the surface and 2.5 mm right and
left of the centerline. The results were analyzed (alpha = 0.05) using multiple paired-sample
t-tests, ANOVA, Bonferroni post-hoc tests, and Pearson correlations.
Results. The elastic modulus and nanohardness varied according to the depth and the dis-
tance from the centerline. For TECBF, no significant difference was found between the spatial
variations in the elastic modulus or hardness values when violet-blue or blue-blue LEDs were
used. For FBFF, the elastic modulus and nanohardness on the side exposed to the violet emit-
ter were significantly less than the side exposed to the blue emitter. A strong correlation
between nanohardness and elastic modulus was found in all groups (r2 = 0.9512–0.9712).
Significance. Resin polymerization was not uniform throughout the RBC. The nanohardness
and elastic modulus across two RBC materials were found to decline differently according
to the orientation of the violet and blue light LED emitters within the curing light.
© 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

∗
Corresponding author at: Department of Dental Clinical Sciences, Division of Prosthodontics, Faculty of Dentistry, Dalhousie University,
5981 University Ave., P.O. BOX 15000, Halifax: +NS, Canada B3H 4R2. Tel.: +1 902 494 1912; fax: +1 902 494 1662.
E-mail address: rbprice@dal.ca (R.B. Price).
http://dx.doi.org/10.1016/j.dental.2015.12.017
0109-5641/© 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
536 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550

inhomogeneous from these broad-spectrum LCUs and this

1. Introduction can affect the resin polymerization [16,21,22].
The properties of a light-curing resin composite can be
When traditional resin based composite (RBC) materials are
significantly influenced by the amount of radiant exposure
placed and light cured in 5-mm thick bulk increments, they
received from the LCU [23]. A strong relationship exists
exhibit lower levels of hardness at the surface that is fur-
between the light curing protocol and the mechanical prop-
thest away from the light source [1]. This occurs because
erties of the resin [24], and a positive correlation has been
increases in the RBC thickness cause an exponential decrease
reported between the irradiance beam profile values from the
in the amount of light available to photo-cure the resin [2,3].
LCU and the microhardness maps of the RBC surfaces [21,22].
With the recent introduction of bulk-fill RBCs, a greater depth
Hence, the shrinkage, hardness, elastic modulus, viscosity, etc.
of cure may be achieved. It is claimed that some brands of
are also all related to the degree of conversion (DC) of the resin
bulk-fill RBCs can be polymerized in up to 4-millimeter thick
[25]. For example, a higher radiant exposure at a given irradi-
increments when light cured for 20 seconds using a high pow-
ance results in a higher DC and elastic modulus of the RBC
ered broad-spectrum curing light [4]. This increase in depth
[24]. Among several techniques, measuring the hardness has
of cure is achieved by using specific polymerization modula-
proved to be the best indicator of the extent of polymeriza-
tors, by improving the translucency, or by using more potent
tion of the RBC [26], and a strong positive correlation exists
initiator systems [5]. For example, the fillers in Tetric Evo-
between the Knoop microhardness values and the DC within
Ceram Bulk Fill (Ivoclar Vivadent, Schaan, Liechtenstein) are
each brand of RBC [15,27,28]. The hardness of RBCs has been
smaller in size and thus may increase the translucency of this
used as an indirect method to assess the depth of cure with a
RBC and enable improved polymerization at greater depths.
value of 80% of hardness at the top surface considered as the
In addition, Tetric EvoCeram Bulk Fill uses a Type I germa-
borderline between sufficient and insufficient curing [29–32].
nium based initiator system that has a higher photocuring
The hardness and elastic modulus have also been correlated
activity than traditional initiators [6–9]. These Type I pho-
with the DC, depth of cure, and clinical behavior [25,31–33].
toinitiators undergo a unimolecular reaction upon irradiation
Several factors may affect the hardness of cured RBC such
and, consequently, they are more reactive to light compared
as the radiant exposure delivered to the RBC [34], composition
to camphorquinone (CQ) and require a lower radiant expo-
and filler loading of the RBC [4], distance between the curing
sure to adequately photo-cure the RBC [6,8–12]. The depth of
light tip and the RBC [35], and delayed finishing or polishing of
cure values may also be based upon the maximum length of
the RBC specimens [36]. A correlation between the hardness
hard RBC remaining when measured using the ISO 4049 test
and elastic modulus has been suggested, and a hardness
[13], even though it has been reported that the distribution of
measurement has been used to estimate the modulus of
resin curing in opaque molds can be substantially lower at or
RBCs [31,35]. In a recent study, a new description for the
near the mold walls compared to the center of the specimen
depth of cure was proposed to be the depth at which the
[11,14–16].
resin matrix switches from a glassy to a rubbery state [37].
Optimum photoinitiator efficiency occurs at specific wave-
In this study, the resin modulus was obtained selecting the
lengths that correspond to the peak absorptivity of the
elastic modulus (E-mod) as the peak value corresponding
photoinitiator used within the RBC [10,17,18]. Light-emitting
to the resin after excluding the high modulus peak(s) that
diodes (LEDs) contain a p–n junction diode that emits light
corresponded to the fillers. A rapid decrease in E-Mod was
when a voltage is applied. Electrons move across the deple-
reported to reflect a marked change in the organic network
tion region and combine with a hole on the other side to create
of the RBC and the authors proposed that the true depth
an electron–hole pair and the electron releases its energy in
of cure is the point where the resin matrix switches from
the form of an emitted photon of light. The emission spec-
a glassy to a rubbery state [37]. This work provides a useful
trum from LEDs is neither monochromatic like a laser, nor
philosophical perspective in understanding RBC properties
is it broad spectrum as from a tungsten lamp. Instead the
as a function of curing, since many existing methodologies,
wavelengths of light emitted from LEDs are determined by
used to determine depth of cure, fail to detect this transition;
the specific bandgap of the semiconductor and the full width
consequently previous literature may have overestimated the
half maximum (FWHM) emission spectrum is typically only
depth of cure in certain RBCs. However, accurate methods
±10 nm around the peak spectral emission from the LED. Con-
to determine the modulus of RBCs are required to validate
sequently many dental LED-light curing units (LCUs) have
and enhance the potential use of this approach. Recently,
an emission peak in the 450–470 nm wavelength range, with
nanoindentation has evolved to permit continuous stiffness
virtually no emissions below 420 nm or above 510 nm [12].
measurements (CSM) to be made. This method measures
Some manufacturers have introduced broad-spectrum LED
the hardness and elastic modulus of a material from the
units that contain multiple LED chips each delivering their
indentation load–displacement data recorded during a cycle
own narrow emission spectrum. This produces a light source
of loading and unloading [38]. The indenter tip component
that delivers two or more distinct wavelength bands [12,19,20].
is conventionally made of diamond, formed into a sharp,
These types of LCUs have been referred to as dual peak,
symmetric shape such as the three-sided Berkovich pyramid.
broad-spectrum, or “polywave® lights”. The ability of these
By adding a small sinusoidally varying signal on top of the
broad-spectrum LCUs to deliver a uniform irradiance across
signal that drives the indenter tip, modulus measurements
the light emitting tips at all emitted wavelengths has recently
can be obtained at any point along the loading curve of a
been investigated. The results showed that the irradiance dis-
given specimen. The benefits of this technique are well doc-
tribution and emission spectrum across the light tip can be
umented in the literature, however the small time constant
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550 537

Table 1 – Resin composite materials [6,41].

Material Material Viscosity Manufacturer Resin system Filler Filler wt
Code %, vol %
Tetric TECBF High viscosity Ivoclar Vivadent, Dimethacrylate Barium aluminium silicate 80%, 61%
EvoCeram Schaan, co-monomers glass, ytterbium fluoride
Bulk-Fill Liechtenstein and mixed oxide
Filtek FBFF Flowable 3M ESPE, St. Paul, UDMA, Procrylat, Zirconia/silica and 64.5%, 42.5%
Bulk-Fill MN, USA Bis-EMA, ytterbium trifluoride
Flowable Bis-GMA

Fig. 1 – Views of the empty (A) and filled split metal mold (B & C) that was 6 mm in diameter and 10 mm in length facing a
6 mm wide 0.2 mm deep indent in the opposing metal surface. Note the asymmetrical appearance of the hard (cured) FBFF
in (D).

associated with the CSM technique makes it especially useful
to determine the modulus of polymeric materials [39].
In clinical situations, when using a broad-spectrum LED or
polywave® LCU, it is very likely that not all parts of the restora-
tion will receive the same wavelengths of light. This cannot
happen with LCUs that use filtered light from a halogen lamp
as the light source [40]. The effect of this phenomenon will
depend on the RBC, the position of the LCU guide tip related
to the RBC, the restoration size and shape, and the homoge-
nization of the light from the different LEDs within the LCU.
Two popular contemporary bulk-fill RBCs are Tetric EvoCeram
Bulk Fill (TECBF, Ivoclar Vivadent, Liechtenstein) and Filtek
Bulk Fill Flowable (FBFF, 3M ESPE, St. Paul, MN, USA). TECBF
is a high viscosity RBC and the manufacturer recommends
using a broad-spectrum polywave® LED curing light to acti-
vate the alternative photoinitiators such as Lucirin TPO and
Ivocerin that are used in this RBC [6]. In contrast, FBFF is a low
viscosity bulk-fill RBC that uses a ternary photoinitiator sys-
tem comprised of camphorquinone (light absorber/sensitizer),
ethyl-4-dimethyaminobenzoate (amine co-initiator/electron
donor) and a diaryliodonium salt. FBFF does not require a
broad-spectrum polywave® LED curing light [41]. The hypothe-
ses of this study were that for these two types of RBC, the
two different emission spectra produced by the two orienta-
tions of the light guide over the LED emitters (violet-blue) and
(blue-blue) will: (1) exhibit similar patterns of nanohardness
and elastic modulus measurements as the depth and distance
from the center increase; and (2) that there would be a strong
positive correlation between the hardness and elastic modu-
lus values for each RBC.
2. Materials and methods
2.1. Resin based composite materials
To test the hypotheses, two bulk-fill dental RBCs were used;
Tetric EvoCeram Bulk Fill (TECBF, Ivoclar Vivadent) and Filtek
538 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550

Fig. 2 – Beam profile of the two different LCU orientations (a and c) over the RBC. The images (b & d) illustrate the light
received by the RBC from the LED emitters within the LCU (b) violet-blue orientation, (d) blue-blue orientation. Spectrum
scale on the right refers to the normalized radiant emittance from the LCU when viewed through the metal mold
(red = 100%, deep violet = 0%).

Fig. 3 – Representative surface image of a specimen of FBFF

showing an indent.
Fig. 4 – Location of the nanoindentations on each RBC from
the surface (0–4 mm) and from the centerline (0–2.5 mm).
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 5 – Elastic modulus at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for TECBF in the violet-blue
(vb) orientation.
bulk fill flowable (FBFF, 3M ESPE). The material descriptions
from the respective manufacturers are provided in Table 1.
2.2. Specimen preparation:
Specimens were prepared using a custom-made stainless steel
mold as illustrated in Fig. 1.
One half of the split metal mold had a 6 mm diame-
ter 10 mm long semi-circular notch that faced a 6 mm wide
0.2 mm deep indent in the opposing metal surface (Fig. 1A).
This indent produced a consistent excess of RBC that was
removed when the specimen was polished. The cover of the
mold had a smooth flat surface. The mold was filled with
RBC and a Mylar strip that fit into the indent was placed
over the RBC and then both parts of the mold were screwed
together (Fig. 1B). The mold was placed on a glass slide
covered by a second Mylar strip, and additional RBC was
packed into the mold. The top surface of the RBC was cov-
ered with a third Mylar strip and then compressed by a second
glass slide. The Mylar strips were used to prevent oxygen
539
inhibition of the RBC [42,43]. The RBCs were photo-
polymerized by using a polywave® LED (Bluephase Style,
Ivoclar Vivadent) for ten seconds with the tip of the light guide
0.5 mm from the top surface of the RBC. To deliver the two dif-
ferent emission spectra from the same LCU, the light source
was oriented to allow only two LED emitters out of the three
LEDs to face the RBC specimen. The third LED emitter was
oriented to face the stainless steel mold (Fig. 2), and thus no
light from this chip reached the RBC. Two configurations of
emitters were selected: either one violet and one blue emitter
(violet-blue), or two blue emitters (blue-blue). The light source
was held in a fixed position for all samples using a restrain-
ing clamp. To confirm that there was no light from the third
LED emitter reaching the RBC, the light in these two positions
was analyzed using a laser beam profiler camera as previ-
ously described [44]. In brief, the LCU guide tip was placed in
the above-described positions on one side of the mold and
the beam was examined from the other side of the mold
(Fig. 2) using a laser beam profiler camera with a 50 mm focal
length lens (USB-L070, Ophir-Spiricon, Logan, UT, USA). The
540 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 6 – Elastic modulus at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for TECBF in the blue-blue (bb)
orientation.
resulting images were viewed using Beamgage version 5.11
software (Ophir-Spiricon).
A total of 20 RBC specimens were prepared, 10 specimens
for each RBC. Specimens for each brand of resin composite
were divided into two groups (5 specimens each) depending on
the orientation of LED emitters. The nanoindenter requires a
flat and smooth surface for specimen examination. Thus, the
RBC specimens were polished using a sequence of felt cloths
with 15, 9, 3, 1, and 0.5 ␮m embedded diamond, Al2 O3 and SiO2
grains using copious amounts of water coolant to prevent any
heating of the RBC. Each step was carried out for 3 mins with
light pressure applied to the specimen against the felt cloths
on the polishing machine. The RBC specimens were ultrason-
ically cleaned in distilled water for 3 mins and then stored in
a dark container in air at 37 ◦ C for 24 h.
2.3. Surface quality verification
To ensure that the preparation and polishing techniques were
able to achieve acceptable standards for nanoindenter use,
the surfaces of the TECBF and FBFF specimens were exam-
ined before indentation using an optical microscope. Some
specimens were also measured after nanoindentation using a
Hitachi S-4700 SEM (Hitachi High Technologies America, Inc.,
Pleasanton, CA). A representative image is shown in Fig. 3.
2.4. Nano-indentation
Indentation tests were performed using an Agilent G200
nanoindentor (Agilent Technologies Canada Inc. Mississauga,
ON) equipped with a continuous stiffness measurement (CSM)
module. Indentation tests were performed at room tempera-
ture, using a calibrated and certified Berkovich diamond tip
indenter with a tip radius < 20 ␩m. The following criteria were
used to standardize the indentation tests:
1. The surface approach velocity for each indent was 10 ␩m/s.
2. The allowable drift rate was preset to 0.05 ␩m/s.
3. The surface detection (stiffness criteria) was pre-set to
200 ␩m.
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 7 – Elastic modulus at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for FBFF in the violet-blue (vb)
orientation.
4. The maximum depth limit per indent was 2000 ␩m.
5. The modulus was measured using the CSM module and
calculated based on the load–displacement curve between
an indentation depth of 400–1500 ␩m.
Prior to use, the indenter was calibrated using a certified
fused silica standard (Agilent Technologies Canada Inc. Mis-
sissauga, ON). A grid of 50 indents (Fig. 4) was used to generate
hardness and elastic modulus data for each specimen with five
valid measurements recorded at each indent. Indents were
placed along 5 lines down from the top surface of the spec-
imen at 0.1 mm, 0.25 mm, 0.5 mm, and then at every 0.5 mm
to a 4 mm depth from the surface. At each depth from the
surface, five points were selected: at the centerline, then at
0.5 mm, and 2.5 mm laterally on each side of the centerline.
In several previous studies of microhardness/depth pro-
files, a depth corresponding to 80% of maximum hardness,
representing a reduction of 20%, was considered as the bor-
derline between sufficient and insufficient curing [29–32]. In
541
the present study, the depth where 50% of the maximum
nanohardness occurred will be noted.
2.5. Statistical analysis
Five valid measurements of nanohardness and elastic modu-
lus were recorded for each of the fifty selected points in the
grid for each orientation of the blue-violet or blue-blue LEDs.
The mean and standard deviation obtained at each point were
used for the statistical analysis. To examine the effect of spec-
imen orientation beneath the LEDs, multiple paired-sample
t-tests were used to compare each value at the side (−2.5, −0.5,
0.5 and 2.5) with the corresponding value at the centerline
at the same depth from the surface. The nanohardness and
modulus values were compared separately.
One and two-way ANOVA followed by Bonferroni post-hoc
analysis (alpha = 0.05) were used to determine if signifi-
cant changes occurred in the nanohardness and elastic
modulus measurements as the depth from the surface
542 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 8 – Elastic modulus at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for FBFF in the blue-blue (bb)
orientation.
increased. Results were compared separately for each RBC
and light orientation (violet-blue and blue-blue). Simi-
larly, comparisons were carried out for each point com-
pared to a value that was 50% of the highest recorded
nanohardness value for each RBC material. The coefficient
of determination (r2 ) between nanohardness and elastic
modulus for all four groups of RBC specimens was also
reported.
3. Results
In general, both elastic modulus and nanohardness of post-
cured and polished RBC specimens declined as the depth
increased from the surface, and also as the distance from
the center increased, notably at 2.5 mm from the center
(Figs. 5–14).
Table 2 shows that the two RBCs behaved differently
according to the two different emission spectra produced by
the two orientations of the light guide over the LED emitters
(violet-blue) or (blue-blue). For TCEBF, the nanohardness and
the elastic modulus measurements were statistically the same
for both LED emitter orientations, and no difference (p > 0.05)
was found between the measurements of nanohardness or
elastic modulus on the left and on the right side of the spec-
imen centerlines (Figs. 5, 6, 9 and 10). When the violet-blue
orientation of the curing light was selected, no statistically
significant differences were found (p > 0.05) between the mod-
ulus and nanohardness values at the center and at 0.5 mm
from center on both sides for measurements at all depths
(from 0.1 to 4 mm from the top of the RBC surface). At −2.5 mm
(mostly violet light) and +2.5 mm (mostly blue light) laterally
from the center, there were no significant differences (p > 0.05)
between both the nanohardness and the modulus measure-
ments made down to 2 mm depth from the surface. However,
for TECBF from the 2.5 mm depth measurements onwards, the
nanohardness and the elastic modulus values at the 2.5 mm
distance from the center were significantly reduced compared
to measurements made at equivalent depths at the center
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 9 – Nanohardness at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for TECBF in the violet-blue (vb)
orientation.
(p < 0.05). There was a statistically significant difference at
the 2.5 mm depth and beyond on both sides from the center
(p = 0.04 at the 2.5 mm depth). The statistical significance of
this reduction increased at 3.5 mm to p = 0.02, and at 4 mm
p = 0.005 where this also resulted in at least a 50% reduc-
tion (magnitude 0.445 GPa) from the highest nanohardness
value. When the blue-blue orientation of the curing light was
selected, the results were more consistent as depth and dis-
tance from the center increased. Only at the 4 mm depth, and
on both sides at 2.5 mm from the center, were there statisti-
cally significant reductions in both the nanohardness and the
modulus compared to the center measurement made at the
same depth (p = 0.01).
FBFF behaved differently. Using different (violet-blue)
wavelengths resulted in significant non-symmetrical out-
comes in the hardness and the elastic modulus measurements
on both sides from the center (Figs. 7 and 11). When the
violet-blue orientation of the curing light was used, dissim-
ilar outcomes started to appear at the 2 mm depth from the
top surface. Statistically significant differences were found
543
between the measurements of nanohardness and elastic mod-
ulus on the left and on the right side of the specimen centers
(p < 0.001). Comparing to the center: on the left (violet) side,
the modulus and nanohardness for FBFF were significantly
reduced starting from 1-mm from the top surface (p = 0.04 at
1 mm and p < 0.01 at increased depths); whereas on the right
(blue) side, at all depths, there was no significant difference
from the center measurements made at the same depth. A
50% reduction of nanohardness values compared to the high-
est value (0.23 GPa) was statistically significant at 2.5 mm from
the center from the 1.5 mm depth onwards on the side exposed
to the violet light LED (p < 0.001), and from 3.5 mm (p = 0.02) and
4 mm (p = 0.002) from the top surface at both the centerline and
on the right side that was exposed to the blue light.
In contrast, when the same wavelengths (both sides
blue emitters) were used to light cure the FBFF specimens
(Figs. 8 and 12), the measurement outcomes were more sym-
metrical for both nanohardness and elastic modulus, such
that there were no statistically significant differences between
left and right sides of the RBC specimens. Furthermore,
544 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 10 – Nanohardness at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for TECBF in the blue-blue (bb)
orientation.
hardness and elastic modulus values were higher as the depth
increased compared to when the RBC received light mostly
from the violet-blue emitter. At the 2.5 mm measurement
locations on either side from the centerline, a greater than 50%
reduction in the nanohardness values compared to the high-
est value became only statistically significant at the 3.5 mm
(p = 0.02) and 4 mm (p = 0.002) depths from the top surface.
This was almost identical to blue side when the violet-blue
orientation was used.
There was a very strong correlation (r2 ) between nanohard-
ness and elastic modulus for all four groups of RBC specimens:
TECBF with violet-blue (r2 = 0.9712 with a p value <0.0001),
TECBF with blue-blue (r2 = 0.9512 with a p value <0.0001), FBFF
with violet-blue (r2 = 0.9584 with a p value <0.0001), and FBFF
with blue-blue (r2 = 0.9526, with a p value <0.0001).
4. Discussion
Both the elastic modulus and nanohardness of post-cured
RBC specimens declined with increasing depth from the
surface. Similarly, the elastic modulus and nanohardness val-
ues declined at the sides of the specimens (at 2.5 mm from
the center) compared to the centerline values. The highest
values of elastic modulus and hardness were similar to those
observed in previous studies [45,46]. Similar to previous stud-
ies [37], the highest values were found at 0.25 mm below the
top surface. Up to the first 2.0 mm depth, the nanohardness
and the elastic moduli were comparable among the differ-
ent distances from the centerline; they then started to decline
as the depth increased, but to different extents according to
the distance from the center of the RBC. The outer values at
2.5 mm from the center declined more rapidly than measure-
ments made along the centerline of the sample. For TECBF,
using different emission spectra (violet or blue) resulted in
nanohardness and elastic modulus measurements that were
statistically the same when using either LED emitter ori-
entation, and no significant difference was found between
the measurements of nanohardness or elastic modulus on
the left and on the right side of the specimen centerlines
(Figs. 5, 6, 9 and 10). FBFF behaved differently. For FBFF,
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 11 – Nanohardness at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for FBFF in the violet-blue (vb)
orientation.
using different emission spectra (violet or blue wavelengths)
resulted in significant non-symmetrical outcomes in the hard-
ness and the elastic modulus measurements on both sides
from the center (Figs. 7 and 11). Thus, the first hypothesis that
for both LED orientations both RBCs would exhibit similar pat-
terns of nanohardness and elastic modulus measurements as
the depth and distance from center increased was rejected.
Similar to previous studies [25,33], a good correlation between
hardness and elastic modulus was found in all four groups of
specimens (r2 = 0.9512–0.9712) and the second hypothesis was
accepted.
Nanoindentation has been used to determine the elastic
moduli and nanohardness of several dental materials, includ-
ing resin composites [45,46]. Nanoindentation is subject to
some variability because of the exact location of the indent
within the filler/resin matrix. The larger standard deviations
observed in the nanoindentation technique can be attributed
to the smaller indent contact area and the ability to indent
either a filler particle or a region of resin between the particles
[47]. Some authors have obtained the modulus by selecting
545
the E-mod as the peak value corresponding to the resin and
excluding high modulus peak(s) that corresponded to the filler
particles [37]. However, the microstructure of the material may
affect the results of the mechanical properties of the RBC [47].
For example larger filler sizes tend to render the RBC stiffer
and using irregular filler shapes results in higher modulus val-
ues than when spherical fillers are used [46]. A recent study
evaluated the elastic properties of a commercial RBC in con-
junction with its microscopic structure and composition [48].
It was reported that nanoindentation revealed no relevant dif-
ference in the elasticity between the filler particles and the
surrounding areas. This suggested that the RBC had a uniform
material structure composition across the surface and that the
RBC had relatively isotropic properties at the nanostructural
level. However, the properties of the RBC could be also have
been affected by the composition of the material beneath the
imaged surface because the resin may cover different sizes of
particles fillers at different locations.
Nanoindentation is primarily a surface measurement and
the very low applied loads and the limited penetration depths
546 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
Fig. 12 – Nanohardness at increasing depths (0–4 mm) and laterally ±2.5 mm from the center for FBFF in the blue-blue (bb)
orientation.
give little information about the nature of bulk of the material.
Sample flaws, such as the presence of pores that may affect
the bulk properties of materials when measured with other
techniques, are unlikely to affect the nanoindentation modu-
lus values [46]. It is commonly considered that as long as the
surface microhardness is at least 80% of the maximum hard-
ness, then the RBC has an adequate hardness value. Previous
results comparing Knoop microhardness (KHN) and degree of
conversion (DC) from the bottom and top surfaces of RBC sam-
ples have shown a linear relationship between DC and KHN
for each composite type [15,27,28] and a bottom/top hardness
ratio of 80% has been reported to correspond to a bottom/top
DC ratio of 90%. Although nanoindentation can be charac-
terized as a form of instrumented indentation, because the
quantitative results of elastic modulus were in agreement with
microindentation [48], the bottom:top ratio of nanohardness
measurements that correspond to any adequate depth of cure
has yet to be clarified. Data from previous studies [4,32,49]
have shown that TECBF was able to achieve the 80% value
of VHN at depths of 4 mm or more in polished samples of
RBC. However, the nanohardness value in the current study
at 4 mm depth of the center for TECBF was only equivalent
to 50% of the highest nanohardness measurement. This may
reflect the difference in the nature between nanohardness and
microhardness measurement techniques.
A previous study, using a halogen curing light that delivered
the same emission spectrum across all of the RBC, reported
that the distribution of resin curing in opaque molds was
substantially lower at or near the mold walls than at the cen-
ter, and the depth of cure was dependent on the size of the
mold [14]. In the present study, the pattern of cured RBC also
formed a bullet shape (Fig. 1D) as previously described [15,16].
The observation that the nanohardness and elastic modu-
lus across two RBC materials decline differently according to
the orientation of the violet and blue light emitters applies
to the specific LED curing light and light guide used in this
study. The manufacturer has since introduced a light guide
with a light homogenizer (Ref #636240, Ivoclar Vivadent) that
reduces the light beam inhomogeneity. The position of the
three LED emitters of the Bluephase Style® LCU used in the
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550 547

Fig. 13 – Elastic modulus of TECBF and FBFF at 0.1 mm and at 4 mm depths from the sample surface and laterally ±2.5 mm
from the center. (a) TECBF with violet-blue emitter orientation, (b) TECBF with blue-blue emitter orientation, (c) FBFF with
violet-blue emitter orientation and (d) FBFF with blue-blue emitter orientation.

present study could be seen when viewed through the end
of the light guide and the two selected orientations of the
LEDs are reflected in the irradiance beam profile correspond-
ing to the LED emitters (Fig. 2). The orientation of the LEDs
had a positive correlation on the nanohardness and on the
elastic modulus of FBFF. It has been previously reported that
the irradiance beam profile can show a similar distribution of
“irradiance and wavelength hot spots” and temperature hot
spots corresponding to the position of the LED emitters within
the LCU [16,40,44,50] and even though the specimen size was
comparable to dental restorations (3 × 6 mm), the light out-
put from the violet and the blue emitters did not overlap to
deliver a uniform distribution of wavelengths across the sam-
ple surface. At depths greater than two millimeters, the effect
of this inhomogeneous light distribution increased markedly,
most notably with the FBFF material. For TECBF, there was no
statistically significant difference between the nanohard-
ness or the elastic modulus values reported on the two
sides of the specimens corresponding to the two LED
emitters.
In contrast, for FBFF, starting at 1 mm from the top surface,
the influence of the emission spectrum from the LED emitter
had an obvious and very significant effect on the nanome-
chanical properties of the specimens. The nanohardness and
the moduli on the short-wavelength (violet) side of the sample
were significantly less than on the longer-wavelength (blue)
side. The 50% value was equivalent only to the 1-mm depth
on the side receiving the violet light, whereas it was down
to 3 mm at the center, and reached a depth of 3.5 mm on the
side receiving the blue light. This formed a trapezoid shape
of cured RBC material. In contrast, using the blue-blue orien-
tation, for FBFF all the lateral positions were above the 50%
value as deep as 3.5 mm from the surface. This supports the
observation that the depth of cure of RBCs that primarily use
CQ materials can be greater than those that include the lower
wavelength activated photoinitiators [8]. It also illustrates that
548 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550

Fig. 14 – Nanohardness of TECBF and FBFF at 0.1 mm and at 4 mm depths from the sample surface and laterally ±2.5 mm
from the center. (a) TECBF with violet-blue emitter orientation, (b) TECBF with blue-blue emitter orientation, (c) FBFF with
violet-blue emitter orientation and (d) FBFF with blue-blue emitter orientation.

Table 2 – Summary of nanohardness and elastic modulus measurements of the two bulk-fill RBCs (TECBF and FBFF) after
light curing for 10 s using two different orientations of the light probe over the violet-blue or the blue-blue LEDs.
LED orientation Material Modulus (GPa) Nanohardness (GPa)

Mean (SD) Minimum (SD) Maximum (SD) Mean (SD) Minimum (SD) Maximum (SD)
Violet-Blue TECBF 14.67 (2.15) 8.14 (1.53) 16.70 (1.33) 0.65 (0.17) 0.21 (0.09) 0.90 (0.14)
FBFF 6.35 (2.90) 0.46 (0.53) 10.18 (1.53) 0.23 (0.15) 0.01 (0.01) 0.44 (0.10)

Blue-Blue TECBF 14.24 (1.63) 10.64 (1.73) 16.64 (1.22) 0.64 (0.14) 0.37 (0.09) 0.87 (0.11)
FBFF 7.60 (1.71) 3.94 (0.52) 9.62 (0.51) 0.29 (0.11) 0.10 (0.04) 0.44 (0.10)

where the depth of cure is measured on the RBC specimen and
the emission spectrum received by the specimen at that spe-
cific location can have a significant effect. The results of this
study suggest that although a single peak blue/blue LED LCU
can be used to photocure both TECBF and FBFF, a polywave®
LED light is not the optimum LCU to photocure FBFF. This
may help explain why the manufacturer of FBFF produces a
‘single peak’ blue LED curing light whereas the manufacturer
of TECBF produces a broad-spectrum polywave® violet:blue
LED curing light.
Several factors such as the wavelength of light, filler size
and type can influence the light absorption and light transmit-
tance of resin composites [3,10,51]. The correlation between
light wavelength and filler particles size is well understood.
 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 535–550
As the RBC thickness increases, exponentially fewer photons
reach the bottom of the RBC. This effect is more pronounced
with shorter wavelengths (410 nm) compared to longer wave-
lengths (460 nm) [19,52] and this explains the increase in light
transmittance and the improved micromechanical properties
when the FBFF received the longer wavelengths of light [3].
Unfortunately, the photoinitiator content of RBC materials
is not always disclosed [18,53] making it difficult to predict
the performance of the RBC when exposed to different wave-
lengths of light. Thus, ideally, the LCU should deliver a broad
spectrum of light that is homogeneously distributed across
the light tip.
TECBF was chosen for this study because it is known
to contain three different types of photoinitiators with
different maximum absorption peaks (max ); Lucirin
TPO (max = 385 nm), Ivocerin (max = 418 nm) and Cam-
phorquinone (max = 468 nm) [6,53,54]. The Bluephase Style®
LCU was chosen because it uses three LED emitters: one violet
and two blue, with spectral emissions peaking near 410 nm
(violet) and near 457 nm (blue) [21,44]. These wavelengths
correspond to the peak absorptivity of the photoinitiators
used in TECBF and they responded efficiently even to the
reduced amounts of violet light. This helps explain its com-
parable behavior for both LED orientations: violet-blue and
blue-blue. FBFF was chosen because it does not contain
Ivocerin or Lucirin TPO and it was anticipated that it would
not polymerize as well when it received only the lower wave-
lengths of violet light. This was indeed the case because the
reduced nanohardness and modulus values in the violet-blue
orientation indicate that the photoinitiators used in this RBC
do not respond efficiently to the reduced amounts of shorter
wavelength (violet) light penetrating down into the resin as
the thickness of FBFF increased.
The designs and emission spectra of broad-spectrum
multi-peak LED curing lights vary between manufacturers
who use different arrangements of LED emitters within the
LCU [19,20,44]. Thus, when using a broad-spectrum multi-
peak LED curing light, depending on the position of the light
guide tip and the size and shape of the restoration, the resin
may receive different emission spectra at different locations
across the restoration. Consequently, depending on the brand
of RBC, the type, and the orientation of the LCU used, the resin
restoration may exhibit less than optimal micromechanical
properties at different locations.
5. Conclusions
Within the limitations of this study that measured the effect
of different emission spectra on the nanohardness and elastic
moduli of polished samples of two RBCs made in metal molds,
it was concluded that:
• The elastic modulus and nanohardness of post-cured RBCs
declined not only with the increase of depth, but also as the
distance laterally from the center increased.
• The two different bulk RBCs investigated responded in dif-
ferent ways to the two different emission spectra produced
by the orientation of the light guide over the LEDs within
the LCU (emitting violet-blue or blue-blue wavelengths).
549
• For FBFF, delivering mostly lower wavelength violet light
adversely affected its mechanical properties. Delivering
mostly longer wavelength blue light improved the mechan-
ical properties of FBFF.
• Ideally the LCU should deliver a spectrally homogeneous
distribution of light to the RBC.
Compliance with Ethical Standards
Funding
This was an unfunded study.
Ethical approval
This article does not contain any studies with human par-
ticipants or animals performed by any of the authors.
Conflicts of interest
The authors declare that they have no conflicts of interest.
The authors would like to thank Ivoclar Vivadent and 3M ESPE
for kindly supplying the resin composites used in this study.
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