Clin Oral Invest (2014) 18:1081–1088
DOI 10.1007/s00784-013-1085-1
ORIGINAL ARTICLE
Effect of radical amplified photopolymerization (RAP)
in resin-based composites
Nicoleta Ilie & Ina Kreppel & Jürgen Durner
Received: 15 March 2013 / Accepted: 31 July 2013 / Published online: 21 August 2013
# Springer-Verlag Berlin Heidelberg 2013
Abstract
Objective The objective of this study was to evaluate the
effect of irradiation time and specimens thickness on the
polymerization kinetic and variation in micro-mechanical
properties of two commercial resin-based composites
(RBCs) based on radical amplified photopolymerization
(RAP) technology™, and to compare them with four
camphorquinone (CQ)/amine-based RBCs.
Materials and methods The materials were analysed by
assessing the polymerization kinetic and the degree of cure
(DC) at 0.1 mm and 2 mm depth during 5 minutes after
photoinitiation, after curing for 10 s, 20 s and 40 s (Elipar
Freelight2). The variation in micro-mechanical properties
(Vickers hardness (HV), indentation modulus (E), and depth
of cure (DOC)) was assessed in 100 μm steps on 6-mm-high
specimens irradiated as above and stored in the water for 24 h
at 37 °C.
Results The results were statistically compared using one-way
ANOVA with Tukey HSD post hoc test (α =0.05) and a
general linear model. The parameter material exerted the
strongest effect on DC (partial eta-squared η p2 =0.83), follow-
ed by irradiation time (η p2 =0.27), and depth (η p2 =0.09). The
polymerization kinetic, well described by an exponential sum
function, showed in all materials a faster decrease in carbon–
carbon double bonds at 0.1 mm than at 2 mm depth. The
materials based on RAP achieved the highest DC values and a
N. Ilie (*) : I. Kreppel : J. Durner
Department of Operative/Restorative Dentistry, Periodontology and
Pedodontics, Ludwig-Maximilians-University of Munich,
Goethestr. 70, 80336 Munich, Germany
e-mail: nilie@dent.med.uni-muenchen.de
J. Durner
Walther-Straub-Institute of Pharmacology and Toxicology,
Nussbaumstr. 26, 80336 Munich, Germany
faster polymerization at both depths. The irradiation time
exerted the strongest effect on the mechanical properties
(DOC, η p2 =0.96; HV, η p2 =0.89; E, η p2 =0.86), followed by
depth (HV, η p2 =0.63; E, η p2 =0.54) and material (HV, η p2 =
0.40; E, η p2 =0.67). At the most favorable curing conditions
(40 s, surface), the mechanical properties of the analyzed
materials varied between 11.38 (0.80) GPa in Estelite® Sigma
Quick and 20.80 (1.42) GPa in Estelite® Posterior for E, and
between 74.33 (3.56) N/mm2 in Tetric EvoCeram® and
120.71 (6.24)N/mm2 in Estelite® Posterior for HV.
Conclusions RAP-initiated material demonstrated a higher
increase in DOC with prolonged irradiation time than the
analyzed CQ/amine based materials.
Clinical relevance An irradiation time of 20 s is also recom-
mended for RAP-initiated RBCs.
Keywords Degree of cure . Polymerization kinetic . Modulus
of elasticity . Hardness . Resin-based composites
Introduction
The physical properties of resin-based composites (RBCs) are
affected by the monomer–polymer conversion, which de-
pends on the generation of primary radicals during the initial
stage of polymerization. The frequently and most successfully
used visible-light photo-initiators in dental RBCs are based on
camphorquinone (CQ) [1, 2]. While CQ could start the poly-
merization alone, the reaction would occur at a low rate [1].
Co-initiators or accelerators are thus needed to allow a poly-
merization “on demand.” Frequently used accelerators in dental
materials are aromatic amine (ethyl 4-dimethylaminobenzoate
(EDMAB)), aliphatic amine (2-(dimethylamino)ethyl methac-
rylate (DMAEMA)), or piperidine (1,2,2,6,6-pentamethyl-
piperidine) [1, 2], while tertiary amines are considered as highly
1082 Clin Oral Invest (2014) 18:1081–1088

effective hydrogen donors. Among them, tertiary aromatic Table 1 Material, manufacturer, batch number, and filler weight and
volume percent, as indicated by the manufacturer in the information
amines with a para electron-donating substituent generate rad-
and direction for use
ical events more effectively than tertiary aliphatic amines with
an electron-withdrawing substituent [3]. Material Manufacturer Batch no. Filler
One drawback in using CQ as a photo-initiator is its intensive
Weight% Volume%
yellow color, which might influences, even at a low concentra-
tion, the final composite color [4]. Apart from the use of alter- Venus® Diamond Heraeus Kulzer 010034 81 64
native photo-initiators in RBCs, like acyl phosphonates, Tetric EvoCeram® Ivoclar-Vivadent M69649 82 54
acylphosphine oxides (Lucirin TPO, 2,4,6-trimethylbenzoyl- Filtek™ Supreme 3M ESPE N141479 78.5 63.3
diphenylphosphine oxide), bisacylphosphine oxides, or XTE
titanocenes [5] to partially or completely replace CQ, the radical Tetric® Ceram HB Ivoclar-Vivadent N03283 81 63
amplified photopolymerization (RAP technology™) is de- Estelite® Sigma Tokuyama E654M 82 71
Quick
scribed as a new attempt to reduce the amount of CQ by using
Estelite® Posterior Tokuyama W216 84 70
an innovative co-activator. While consumed during polymeriza-
tion in regular CQ/amine-based materials, CQ is said to be
recycled within the reaction of initiator generation in RAP-
based material, thus a single CQ molecule can produce multiple Teflon mold of 2 mm height and 3 mm diameter and a thin
initiator radicals (manufacturers' statement). Generally, CQ is 100 μm composite film. Specimens were cured for 10, 20, and
activated by blue light (excited state). Light-activated CQ can 40 s by applying the curing unit directly on specimen's surface
react with hydrogen donors like amines by forming amine (n =6). Measurements were made in real time (two spectra,
radicals and pinacol [6]. Whether in RAP-initiated materials 4 cm−1 resolution) with a Fourier transformation infrared
CQ was regenerated from pinacol or the light-activated CQ only (FTIR) spectrometer with an attenuated total reflectance
transfer the energy to radical starting molecules and returns to the (ATR) accessory (Nexus, Thermo Nicolet, Madison, USA)
ground state, remains unclear in manufacturer' report. Moreover, within the first 5 min after photo-initiation, by applying the
the manufacturer claim that the RAP technology implemented in nonpolymerized composite paste directly on the diamond
two commercial RBCs allows for curing the materials in approx- ATR crystal. Spectra were recorded thus at the bottom of the
imately 1/3 the exposure time required for conventional RBCs. specimens.
Therefore, the study aims to evaluate the effect of irradia- DC was calculated as the variation in peak height ratio of the
tion time and specimens thickness on the polymerization absorbance intensities of methacrylate carbon–carbon (C–C)
kinetic and variation in micro-mechanical properties of two double bond peak at 1,634 cm−1 and that of internal standard
commercial RBCs based on RAP technology™ and to com- peak at 1,608 cm−1 (aromatic C–C double bond) during poly-
pare them with four CQ/amine based RBCs. merization, in relation to the uncured material.
The null hypotheses tested were (1) there would be no 2  .  3
difference in the polymerization kinetic, degree of conversion, 1; 634 cm−1 1; 608 cm−1
6  Peak height after curing 7
and mechanical properties among the materials and (2) the DCPeak % ¼ 41−  . 5
1; 634 cm−1 1; 608 cm−1
irradiation time and the depth where parameters are measured Peak height before curing

would not affect the assessed properties.  100

Materials and methods
Six commercial available RBCs were analyzed (Table 1) by
assessing the polymerization kinetic and the degree of cure
(DC) at 0.1 and 2 mm depth after curing for 10, 20, and 40 s.
The variation in micro-mechanical properties (Vickers hard-
ness (HV), indentation modulus (E), and depth of cure
(DOC)) was measured in 100 μm steps on 6-mm-high spec-
imens irradiated as above.
Polymerization kinetic and degree of cure
DC was analyzed by considering two different specimen
geometries: one 2-mm high increment measured in a white
In each specimen, the increase in DC (=decrease of the C–C
double bonds) was described by the superposition of two
exponential functions. The correlation function is represented
by the sum of two exponential functions as:



y ¼ y0 þ a* 1−e−bx þ c* 1−e−dx
The term y 0 presents the y-intercept, depending, e.g., on
the thickness of the specimen and the composition of the
material. The parameters: a, b, c, and d (Table 2) are modula-
tion factors of the exponential function to optimize the double
exponential function on the measured curve, while “b” and
“d” are exponents and “a” and “c” factors. The measuring
points were plotted on a time DC curve.
Clin Oral Invest (2014) 18:1081–1088 1083

Table 2 Parameters from the double exponential approximate function assessed from the FTIR spectroscopy data as function of material, polymer-
ization time (s) and depth (mm)

RBC Time 0.1 mm 2 mm

(s)
y0 a b c d R2 y0 a b c d R2

Venus® Diamond 10 2.00 31.87 0.21 19.36 0.00 0.90 −3.25 31.30 0.27 8.59 0.02 0.86
20 −6.32 39.06 0.38 9.98 0.02 0.92 −3.79 36.01 0.20 8.03 0.02 0.92
40 1.79 36.68 0.20 12.22 0.00 0.92 1.70 34.95 0.15 10.55 0.01 0.94
Tetric EvoCeram® 10 −4.33 40.90 0.36 9.18 0.01 0.96 −3.64 38.10 0.27 9.05 0.01 0.96
20 −2.51 41.52 0.34 7.26 0.01 0.94 −0.42 36.96 0.24 10.92 0.02 0.96
40 1.03 36.96 0.27 9.51 0.01 0.94 0.23 38.55 0.22 10.99 0.02 0.97
Filtek™ Supreme XTE 10 −8.23 52.73 0.34 9.05 0.01 0.97 −4.07 41.23 0.21 8.82 0.01 0.97
20 −4.46 49.42 0.29 8.14 0.01 0.96 −0.09 40.75 0.17 8.50 0.01 0.97
40 −5.75 47.83 0.31 10.57 0.02 0.97 −1.11 41.78 0.16 8.63 0.02 0.85
Tetric® Ceram HB 10 −5.54 50.01 0.35 9.54 0.01 0.98 −1.19 41.66 0.26 8.83 0.01 0.97
20 −5.16 51.89 0.35 9.45 0.01 0.98 −3.60 50.09 0.19 10.19 0.01 0.99
40 −6.34 57.10 0.26 8.76 0.01 0.99 −3.67 51.78 0.17 9.51 0.01 0.99
Estelite® Sigma Quick 10 −10.73 59.63 0.38 9.16 0.01 0.98 −8.82 54.35 0.29 10.17 0.01 0.98
20 −9.99 60.02 0.34 8.75 0.02 0.97 −5.71 56.74 0.24 8.72 0.01 0.98
40 −9.51 60.49 0.36 9.25 0.01 0.98 −3.23 53.00 0.21 8.38 0.01 0.98
Estelite® Posterior 10 −11.35 63.23 0.34 8.48 0.01 0.98 −7.06 54.01 0.22 9.33 0.01 0.98
20 −9.45 62.65 0.33 7.77 0.01 0.98 −4.79 56.12 0.16 7.65 0.01 0.98
40 −9.81 63.35 0.33 8.59 0.01 0.98 −4.67 52.36 0.18 12.45 0.03 0.98

Micro-mechanical properties
The micro-mechanical properties—HV and E were deter-
mined according to DIN 50359-1:1997-10 by means of a
universal hardness device (Fischerscope H100C, Fischer,
Sindelfingen, Germany). For this purpose, 6-mm-high speci-
mens were prepared on bulk (n =6) in a Teflon mold (diam-
eter, 3 mm) and stored in distilled water after curing (10, 20,
40 s) for 24 h at 37 °C. Prior to testing, specimens were ground
and polished underwater in longitudinal direction from 3 to
1.5 mm diameter with diamond abrasive paper (mean grain
sizes, 20, 13, 6 μm) in a grinding system (EXAKT 400CS,
Exakt, Norderstedt, Germany). The micro-mechanical prop-
erties were measured on dry specimens, at 25 °C, starting from
0.1 mm under the surface, with 100 μm intervals between the
measuring points. The test procedure was carried out force-
controlled; the test load increased and decreased with constant
speed between 0.4 and 500 mN. The load and the penetration
depth of the indenter were continuously measured during the
load–unload hysteresis. The universal hardness is defined as
the test force divided by the apparent area of the indentation
under the applied test force. From a multiplicity of measure-
ments, a conversion factor (0.0945) between universal hard-
ness and Vickers hardness was calculated by the manufacturer
and implemented in the software, so that the measurement
results were indicated in the more familiar HV units. The
hardness measurements quantify the resistance of a material
to plastic deformation. E was calculated from the slope of the
tangent of indentation depth curve at maximum force. HV and
E variations with depth were calculated for each group as a
curve-fitted line, based on the data from six specimens (360
measuring points) (Fig. 1). The DOC, usually acknowledged
as the thickness of a RBC that is adequately cured [7] or rather
as the depth where HV equals the surface value multiplied by
an arbitrary ratio, usually 0.8 (=HV, 80 %) [8] was calculated.
The depth at which the 80 % hardness cutoff value in relation
to the surface hardness was reached, meaning the maximum
incremental thickness was thus calculated and defined as
DOC.
Statistical analysis
Results were statistically compared using one-way ANOVA
and Tukey HSD post hoc test (α =0.05). A multivariate anal-
ysis (general linear model with partial eta-squared statistics)
tested the influence of the parameters material, irradiation
time, and depth on the considered properties. The partial eta-
squared (η p2) statistic reports the practical significance of each
term, based upon the ratio of the variation accounted for by the
effect, and represents an index of strength of association
between an experimental factor and the dependent variable
ranging between 0 and 1. Larger values of η p2 indicate a
greater amount of variation accounted for by the model effect.
Moreover, a Pearson correlation analysis was performed
1084 Clin Oral Invest (2014) 18:1081–1088

a b HV-10s-bulk
HV-20s-bulk

Vickers Hardness [N/mm²]

Vickers Hardness [N/mm²]

140 HV-40s-bulk
120 140
120
100
100
80 80
60 60
40 40
20 20
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Depth [mm] Depth [mm]
Fig. 1 a Example of variation of the Vickers hardness as function of depth for a irradiation time of 10 s (Filtek™ Supreme XTE, Fitted line trough 360
measuring points) and b Effect of irradiation time and depth on the Vickers hardness (Estelite® Posterior)

between the filler volume amount and the parameters used to
describe the polymerization kinetic (SPSS Inc.; Chicago, IL,
USA, Version 20.0).
Results
The strongest effect on DC was exerted by the parameter
material (η p2 =0.83), followed by irradiation time (η p2 =
0.27), while the effect of depth (0.1 or 2 mm) was significant
but very low (η p2 =0.09). The two materials based on the RAP
technology—Estelite Sigma Quick® and Estelite Posteri-
or®—achieved the highest DC values at 5 min after photo-
initiation (=DC, 5 min) while the urethane-based material
Venus® Diamond, the lowest values. No significant difference
in 5 min DC by varying the irradiation time was found for
specimens of 0.1 mm thickness, while short irradiation time
(10 s) induced in 2 mm depth mostly significant lower 5 min
DC values compared to a prolonged (20 or 40 s) irradiation
(Fig. 2).
The polymerization kinetic is expressed in this study as the
decrease of the C–C double bonds during a period of 5 min
after photo-initiation and was well described by an exponen-
tial sum function (high coefficient of determination, R2;
Table 2, Fig. 3). Validity for all materials is that the decrease
in C–C double bonds was faster (higher “a” and “b” param-
eters, Table 2) at 0.1 mm than at 2 mm depth, while the
parameters “c” and “d” were less influenced by depth or
material. Estelite Posterior® and Estelite Sigma Quick®
showed a faster polymerization compared to CQ/amine initi-
ated RBCs at both 0.1 and 2 mm depths. Moreover, the
decrease in “a” and “b” values at 2 mm depth compared to
0.1 mm was faster in the posterior (packable materials: Estelite
Posterior® and Tetric Ceram HB®) than in the universal RBCs
(the rest of tested materials).
As for the mechanical properties, the irradiation time
exerted the strongest effect on the measured properties

Fig. 2 Degree of cure 5 min after photo-initiation at 0.1 and 2 mm depth parameters: material×irradiation time (η p2 =0.09), material×depth (η p2 =
as function on material and irradiation time. The parameter material 0.07), irradiation time×depth (η p2 =0.06), and material×irradiation
exerted the strongest effect on DC (partial eta-squared η p2 =0.83), follow- time×depth (η p2 =0.04) were also significant
ed by irradiation time (η p2 =0.27) and depth (η p2 =0.09). The interaction
Clin Oral Invest (2014) 18:1081–1088 1085

a 60
b 60

50 50

40 40
DC [%]

DC [%]
30 30
2 mm, 40 s Estelite Posterior
Estelite Posterior 0 mm, 10 s
20 20
Estelite Sigma Quick 0 mm, 20 s
Filtek Supreme XTE 0 mm, 40 s
10 TetricCeram-HB 10
2 mm, 10 s
Tetric Evo Ceram
2 mm, 20 s
0 Venus Diamond 0 2 mm, 40 s

-10 -10
0 5 10 15 20 25 0 5 10 15 20 25
Time [s] Time [s]
Fig. 3 Example of DC variation with time: a comparison among the materials (2 mm depth and 40 s irradiation and b Estelite® Posterior at different
irradiation times and thickness

(DOC, η p2 =0.96; HV, η p2 =0.89; E, η p2 =0.86), followed by
depth (HV, η p2 =0.63; E, η p2 =0.54) and material (HV, η p2 =
0.40; E, η p2 =0.67).
Figure 4 presents the DOC (=80 % HV) for all six RBCs at
three irradiation times: 10, 20, and 40 s. The DOC values
indicate the thickness of an increment being proper polymer-
ized under the corresponding curing conditions. For all mate-
rials, extending the irradiation time resulted in a significant
increase in increment thickness. Estelite Sigma Quick® and
TetricEvo Ceram® reached the highest DOC values—
6 mm—at a curing time of 40 s. The posterior RBCs—Estelite
Fig. 4 Depth of cure (DOC) as function on material and irradiation time.
The parameter irradiation time exerted the strongest effect on DOC
(partial eta-squared, η p2 =0.96), followed by material (η p2 =0.74). The
interaction parameters: material×irradiation time (η p2 =0.46) was also
significant
Posterior® and Tetric Ceram HB®—showed for all curing
times significant lower incremental thickness.
HV and E values measured in 0.1 and 2 mm depth were
independent from irradiation time, while in greater depths,
values generally increased with irradiation time (Table 3).
Discussion
In the analyzed RBCs with the novel RAP initiator system—
Estelite Posterior® and Estelite Sigma Quick®—CQ is con-
sidered to be recycled and not consumed like in traditional
CQ/amine-based materials. Experimental materials with RAP
or CQ/amine initiator systems showed a higher degree of cure
when the RAP initiator was used [9], allowing thus to state
that a reduced irradiation time (10 s) would be sufficient for a
proper polymerization. This was only partially confirmed by
our data, since in thin layers (0.1 mm) 5 min DC was inde-
pendent from irradiation time but increased in 2 mm depth
when the irradiation time increased from 10 to 20 or 40 s. The
mechanical properties HV and E were maintained at both
depths. This behavior was, however, also observed in the
other analyzed materials, thus it cannot be attributed solely
to the RAP initiator system. A positive effect of the RAP
initiator might nevertheless be observed in deeper layers:
Though lowest DOC at 10 s irradiation, a prolonged irradia-
tion time (20 s), increased the DOC in Estelite Posterior® and
Estelite Sigma Quick® to a higher extent than in other mate-
rials. Since both above mentioned materials contain the
highest volumetric filler amount (Table 1), the amount of light
reaching the material in deeper layer might be lower compared
to other materials. When sufficient irradiance reached the
depth, the RAP initiator is likely to induce more free radicals
than CQ alone, improving the polymerization process and
allowing for a better polymerization in depth.
1086 Clin Oral Invest (2014) 18:1081–1088

Table 3 Statistical analysis for the variation of the micro-mechanical properties—E [GPa] and HV[N/mm2]—as function of depth [millimeter] and
polymerization time [second]

Depth Time Venus® Diamond Tetric EvoCeram® Filtek™ Supreme XTE

E HV E HV E HV

0 10 15.20 (2.32)bc 93.93 (11.05)def 12.04 (1.02)cde 74.69 (4.96)de 15.73 (0.57)de 117.32 (2.04)e
def def cde cde def
20 18.01 (0.48) 96.63 (3.55) 12.17 (0.81) 74.11 (3.13) 15.76 (0.67) 118.89 (1.90)ef
40 16.90 (1.47)d 90.90 (6.52)cde 11.34 (1.06)c 74.33 (3.56)cde 15.38 (1.50)de 118.29 (3.09)ef
ef
2 10 18.54 (0.68) 102.44 (5.54)f 12.96 (0.55)de 77.51 (3.48)e 16.95 (0.48)g 123.87 (2.90)ef
20 19.34 (0.70)f 103.02 (6.30)f 13.26 (0.77)e 77.86 (3.68)e 17.17 (0.43)g 124.67 (3.10)f
f
40 18.98 (0.64) 99.23 (5.32)ef 12.97 (0.93)de
77.93 (3.35)e 16.88 (1.05)fg 123.87 (4.04)ef
de
4 10 17.34 (0.76) 89.73 (4.64)cd 11.85 (0.89)cd
68.38 (6.42)cd 14.79 (0.27)d 101.90 (2.80)d
ef
20 18.57 (0.97) 95.11 (8.94)def 13.03 (0.30)de
73.56 (3.87)cde 16.30 (0.51)efg 116.82 (4.84)e
ef
40 18.86 (0.52) 95.50 (3.17)def 13.12 (0.90)de
78.47 (4.92)e 17.20 (1.26)g 123.30 (9.22)ef
a
6 10 9.35 (2.28) 41.46 (11.95)a 6.07 (2.31)a
32.99 (13.41)a 6.23 (2.12)a 37.83 (15.05)a
20 14.65 (1.40)b 70.56 (9.08)b 9.19 (1.05)b 51.00 (5.34)b 11.08 (1.83)b 74.56 (19.66)b
cd
40 16.51 (1.49) 82.82 (8.49)c 11.68 (0.84)c
67.46 (14.23)c 13.30 (1.09)c 89.76 (7.45)c
Depth Time Tetric ®Ceram HB Estelite® Sigma Quick Estelite® Posterior
E HV E HV E HV
0 10 15.20 (0.93)def 89.59 (3.97)de 10.70 (0.84)c 78.92 (3.45)de 19.14 (2.02)de 124.37 (3.61)de
20 13.90 (1.58)cde 84.15 (10.77)de 11.15 (0.61)c 80.20 (4.59)de 20.05 (2.26)ef 125.43 (6.00)de
def
40 14.64 (2.20) 90.35 (4.37)e 11.38 (0.80)c
82.59 (5.49)de 20.80 (1.42)efg 120.71 (6.24)d
f
2 10 16.07 (0.32) 88.85 (4.29)de 11.31 (0.99)c
81.81 (6.06)de 21.90 (1.66)gh 130.31 (6.34)ef
f
20 15.73 (0.64) 92.03 (3.24)e 12.42 (0.39)d
83. 04 (4.41)de 22.92 (0.78)h 133.27 (4.02)f
40 16.03 (0.87)f 91.00 (3.25)e 12.79 (0.34)d 84.67 (4.96)e 22.78 (0.78)h 130.08 (4.23)ef
4 10 13.73 (0.51)cd 72.02 (3.56)c 11.16 (0.48)c 71.41 (3.72)c 17.79 (0.99)cd 96.64 (7.54)c
20 14.84 (0.56)def 81.44 (3.46)d 12.41 (0.28)d 82.44 (6.80)de 21.43 (0.51)fgh 117.99 (4.46)d
40 15.59 (0.51)ef 88.08 (2.76)de 12.71 (0.24)d 84.54 (5.05)e 21.85 (1.03)gh 121.25 (2.76)d
6 10 7.44 (2.96)a 36.39 (15.00)a 3.42 (0.73)a 19.21 (6.46)a 3.18 (1.35)a 14.22 (7.88)a
20 11.41 (1.62)b 60.94 (7.24)b 8.81 (1.02)b 55.88 (8.56)b 14.75 (1.75)b 76.52 (10.32)b
40 12.65 (1.72)bc 67.56 (7.62)bc 10.90 (0.63)c 77.31 (7.07)cd 17.37 (1.48)c 90.60 (6.58)c

The parameter exerting the strongest effect on HV was the depth (partial eta-squared, η p2 =0.89), followed by material (η p2 =0.85) and irradiation time
(η p2 =0.56). The interaction parameters: irradiation time×depth (η p2 =0.66), material×depth (η p2 =0.52), material×irradiation time (η p2 =0.15) and
material×irradiation time×depth (η p2 =0.21) were also significant. As for E: The parameter material exerted the strongest effect (partial eta-squared, η p2
=0.86), followed by depth (η p2 =0.82) and irradiation time (η p2 =0.52). The interaction parameters: irradiation time×depth (η p2 =0.57), material×depth
(η p2 =0.38), material×irradiation time (η p2 =0.19) and material×irradiation time×depth (η p2 =0.19) were also significant. Superscript letters indicate
statistically homogeneous subgroups within one column (one-way ANOVA with Tukey HSD test, α =0.05)

The influence of the RAP initiation was also reflected in the
polymerization kinetic assessed in this study as the decrease of
the C–C double bonds and well described by a double expo-
nential function with five parameters. In a radical polymeri-
zation process of methacrylates, different phases are distin-
guished: (a) Initiation, characterized by the formation of a free
radical able to start the polymerization process; (b) Propaga-
tion, directed by the radical attack on methacrylic monomers
leading to a larger molecule (chain growth) by preserving the
free radical; and (c) Termination, described by different mech-
anisms to stop the polymerization process like “coupling,”
when two free radicals join together, or “disproportionation,”
when one molecule abstracts a hydrogen atom from another
one, forming a C–C double bond [10]. The propagation is
subdivided into three phases, upon which the gel and the glass
phase are important in the polymerization of RBCs. The gel
phase was thus described in our model by the first exponential
function (parameters “a” and “b”), the glass phase by the
second exponential function (parameters “c” and “d”).
Like demonstrated in earlier experiments, we found that the
parameters “c” and “d” are nearly independent from the
material and the layer thickness (up to 2 mm). This indicates
that the polymerization process in the glass phase is nearly
independent from the composition of the material. The param-
eters “a” and “b,” however, vary strongly with the material.
The highest “a” values were calculated for Estelite Sigma
Quick® and Estelite Posterior® confirming, at a first glance,
the described mechanism of polymerization, when using the
Clin Oral Invest (2014) 18:1081–1088
new initiator technology (RAP). Considering the filler volume
amount, an excellent correlation with the parameter “a” was
evident (at 0.1 mm the Pearson correlation coefficient was
0.974 (10 s), 0.973 (20 s), 0.933 (40 s); at 2 mm 0.919 (10 s),
0.913 (20 s), 0.845 (40 s)), viz the higher the filler volume
amount the faster was the polymerization. In other words, a
lower matrix volume induces a faster polymerization in RBCs
since the monomers are consumed faster. This statement is
however not valid for Venus Diamond®, a material with a
moderate filler volume amount (64 %), containing exclusively
aliphatic methacrylates, merging in its monomer matrix only
UDMA and tricyclodecane (TCD)-urethane. TCD-urethane is
a hydrophobic acrylic acid ester prepared by reaction of
hydroxyalkyl (meth)acrylic acid esters with diisocyanates and
subsequent reaction with polyols [11]. Acrylates, lacking the
methyl group of the methacrylates, are less sterically hindered,
thus the monomer is described to have a high reactivity, a good
biocompatibility [12], and also a very good mechanical stability
after aging [13, 14]. On the other hand, TCD-urethane is a high
molecular weight monomer, thus the monomer mobility would
be lower, which is clearly reflected in the low “a” parameters.
While the “a” parameters calculated for Venus Diamond® were
the lowest, it is interesting to point out that the differences in the
determined kinetic parameters at 0.1 and 2 mm were also in this
material very low, attesting for a weak dependent polymeriza-
tion kinetic with depth. This was also observed in previous
studies since a relatively low decrease of DC with increasing
incremental thickness was measured in Venus Diamond, when
compared to regular Bis-GMA-based RBCs [15].
For the other materials, the parameters “a” and “b” are
varying with the incremental thickness, indicating that in thin-
ner layers the decrease of C–C double bonds is faster, which is
related to the reduced amount of light quants penetrating the
material in depth. Therefore, the initiation of polymerization is
slower in deeper layers, leading to a lower C–C double bond
conversion. Moreover, the decrease in “a” and “b” parameters
was proven to be higher in the more viscous posterior RBCs—
Estelite Posterior® and Tetric Ceram HB®—than in the other
nano-and micro-hybrid RBCs, being thus also related to the
lower DOC values measured in this materials.
Besides allowing to assess the polymerization kinetic, DC
measurement were proved to be a valuable analyzing tool
since the DC was shown to correlate directly with the irradi-
ation time and inverse with the amount of elutable substances
in RBCs. [16] The above mentioned study emphasize the
importance of an adequate polymerization (20, 40 s), since
short curing times (5, 10 s) were shown to result in lower DC
and higher amount of eluted substances with toxic potential.
Moreover, the type and amount of eluates were proven to be
strongly dependent from the material and the irradiation pro-
tocol [17]. The data of the present study are in accordance with
the above mentioned studies since the DC was shown to
increase in all materials with increased polymerization time.
1087
However, it must also be considered that when the chain
growth is terminated by a disproportionation mechanism in a
radical initiated polymerization, a new carbon–carbon double
bond is formed, which cannot be separated in the FTIR
analysis from the monomer carbon–carbon double bonds
[18]. Thus, DC measurements must be associated by compli-
mentary analysis methods to avoid a misinterpretation of the
data. Therefore, to assess the postpolymerization in this study,
measurements of the micro-mechanical properties were
performed after 24 h of maturation of the specimens. More-
over, an immanent attribute of FTIR spectroscopy is that the
method is not clearly able to differentiate between the C–C
double bonds generated by matrix monomers or resulted from
the methacrylate functional groups of the silane coupling
agents. It has to be mention that higher amounts of C–C
double bonds are belonging to monomers and comonomers.
Though, a high degree of conversion of the C–C double bonds
belonging to the silane agents is of great importance for the
mechanical stability of an RBC since they are coupling the
fillers in the monomer matrix. The electronic surrounding of
C–C double bonds belonging to different chemical substances
(Bis-GMA, silane coupling agent, etc.) is different but did not
differ enough to give a singular signal in the FTIR spectra.
Thus, the different kinds of C–C double bonds might contrib-
ute to a spreading of a singular peak. This effect might
contribute to small differences whether DC is assessed by
peak area or by peak height measurements. Since preliminary
studies showed no differences in the variation in peak height
or peak area ratio of the absorbance intensities of methacrylate
carbon–carbon (C–C) double-bond peak (1,634 cm−1) and
that of the internal standard peak at (1,608 cm−1) during
polymerization, in relation to the uncured material, we chose
for evaluation in this study the faster first method.
As already shown in previous studies [19–22], the mechan-
ical properties of RBCs are related to their filler content. The
material containing pre-polymerized filler particles (Tetric
EvoCeram®) had the lowest filler volume content while com-
posites with round particles (Estelite Posterior®) the highest
(Table 3). Generally, filler loading is influenced among others
by filler morphology, with spherical filler allowing for a
higher packing density and generally to improved mechanical
properties [21, 22]. Despite the high degree of cure and the
second highest filler content (82 wt%, 71 vol%) inferior
mechanical properties were measured for Estelite Sigma
Quick® in comparison with the other tested materials. A
possible reason could be a less advantageous filler packing.
As an RBC for posterior restorations showed Estelite Posteri-
or® indeed the best mechanical properties within the mea-
sured RBCs, confirming other studies [23]. A particularity of
the material is the highest filler load within all tested RBCs,
containing exclusive spherical shaped fillers. This also allows,
besides an increased filler load [24], to enhance materials
fracture strength compared to materials with irregular shaped
1088
fillers since mechanical stresses tend to concentrate on the
angles and protuberances of the filler particles [25].
Conclusions
Within the limitations of the present experiment, the following
can be concluded: The polymerization kinetic was in all
materials well described by an exponential sum function (R 2
varied within the 36 groups between 0.86 and 0.98). The
materials based on RAP technology™ achieved the highest
DC values and a faster polymerization at both 0.1 and 2 mm
depths and showed micro-mechanical properties (DOC) in-
creasing to a higher extent at prolonged irradiation times
compared to traditional CQ/amine-initiated RBCs. Therefore,
an irradiation time of 20 s is recommended also for RAP-
initiated RBCs.
Acknowledgments The measurements of the mechanical properties in
this study were supported in part by the company Tokuyama-Dental.
Conflict of interest The authors declare that they have no conflicts of
interest
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