d e n t a l m a t e r i a l s 2 9 ( 2 0 1 3 ) e213–e217

Available online at www.sciencedirect.com

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

Degree of conversion of bulk-fill compared to

conventional resin-composites at two time
intervals

Ruwaida Z. Alshali a,b , Nick Silikas a,∗ , Julian D. Satterthwaite a

a School of Dentistry, The University of Manchester, Higher Cambridge Street, Manchester M15 6FH, UK
b Department of Oral and Maxillofacial Rehabilitation, King Abdulaziz University, Jeddah, Saudi Arabia

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

Article history: Objective. The purpose of this study was to assess the degree of conversion (DC) over time,
Received 20 February 2013 using FTIR spectroscopy for bulk-fill flowable resin composite materials compared to con-
Received in revised form ventional flowable and regular resin composite materials.
16 May 2013 Methods. Eight resin composites were investigated including flowable bulk-fill materials
Accepted 23 May 2013 SureFil SDR (SDR), Venus bulk-fill (VBF), x-tra base (XB), and Filtek Bulk Fill (FBF). Con-
ventional flowable and regular composite materials included: Venus Diamond flow (VDF),
Grandioso flow (GRF), Venus Diamond (VD), and Grandioso (GR). Degree of conversion (DC)
Keywords: was assessed by Fourier transform infrared spectroscopy using attenuated total reflectance
Resin composite technique. DC was measured for samples immediately post-cure (n = 3), and after 24 h stor-
Bulk-fill age period at 37 ◦ C (n = 3). Results were analysed using one-way analysis of variance (ANOVA),
Degree of conversion Bonferroni post hoc test, and independent-samples t-test at ˛ = 0.05 significance level.
FTIR spectroscopy Results. Immediately post-cure, the mean DC values of the different materials were in the fol-
lowing order: GRF > VDF > SDR > VBF > XB > GR > FBF < VD and ranged from 34.7 to 77.1%. 24 h
post-cure, DC values were in the following order: GRF > VBF > VD > SDR > VDF > GR > XB < FBF
and ranged from 50.9 to 93.1%. GRF showed significantly higher DC values than all other
materials at both time intervals while XB and FBF showed significantly lower values at 24 h
post-cure.
Significance. The 24 h post-cure DC values of the bulk-fill composites SDR and VBF are gen-
erally comparable to those of conventional composites studied; however, the 24 h post-cure
DC values of XB and FBF were lower compared to the other materials.
© 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

and solubility have been shown to be directly related to the

1. Introduction
The degree of conversion (DC) of a resin composite is crucial
in determining the mechanical performance of the mate-
rial and its biocompatibility. Strength, modulus, hardness
degree of monomer conversion [1–3]. In addition, assessment
of changes of DC during polymerization is considered a use-
ful tool in characterizing and understanding polymerization
kinetics using different resin composite formulations and cur-
ing techniques.

∗
Corresponding author at: Coupland Building III, School of Dentistry, The University of Manchester, Manchester M15 6FH, UK.
Tel.: +44 1612756747.
E-mail address: nick.silikas@manchester.ac.uk (N. Silikas).
0109-5641/$ – see front matter © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dental.2013.05.011

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 e214 d e n t a l m a t e r i a l s 2 9 ( 2 0 1 3 ) e213–e217

The final DC depends mainly on intrinsic factors such as

Filler loading

UDMA: urethane dimethacrylate; EBPADMA: ethoxylated Bisphenol A dimethacrylate; TEGDMA: ttriethyleneglycol dimethacrylate; Bis-EMA: Bisphenol A polyethylene glycol diether dimethacrylate;
the chemical structure of the dimethacrylate monomer and

64.5 wt%
68 wt%

65 wt%

75 wt%

65 wt%

81 wt%

81 wt%

89 wt%
photo-initiator concentration and extrinsic factors such as
the polymerization conditions [4]. The DC of several Bis-GMA
based resin-composites has been evaluated previously using
infrared techniques. The reported DC values were in the range

Ba-Al-F-B silicate glass,

of 52–75%, with most of the materials in the 55–60% range [5,6].

Ba-Al-F silicate glass,

Ba-Al-F silicate glass,

Ba-Al-F silicate glass,

ytterbium trifluoride
The DC for adequate clinical performance has not yet been

Sr-A-F silicate glass

established. However, a negative correlation of in vivo abra-

Filler

zirconia/silica,
sive wear depth with DC has been established for DC values

YbF3 , SiO2

YbF3 , SiO2

YbF3 , SiO2
in the range of 55–65% [7]. Accordingly, at least for occlusal
restorative layers, DC values below 55% are not recommended
[8].

–
Many studies have investigated the effect of filler load,
size, and geometry on DC of the resin-composite [9–11]. DC
was found to progressively decrease linearly with increasing

TCD-DI-HEA, UDMA
EBPADMA, TEGDMA

Bis-GMA, TEGDMA,

Bis-GMA, TEGDMA,
Organic matrix

Bis-EMA, Procrylat
UDMA, EBPADMA

UDMA, EBPADMA
opaque filler content [11]. Differences in filler geometry did

(UDMA), Bis-EMA
Bis-GMA, UDMA,
Modified UDMA,

di-methacrylate
not seem to influence DC of experimental composites. How-

Bis-GMA: Bisphenol A dimethacrylate; HEDMA: hydroxyethyl dimethacrylate; TCD-DI-HEA: Bis-(acryloyloxymethyl)tricyclo[5.2.1.02,6]decane.

ever, DC decreased in composites whose filler particles size

Aliphatic

HEDMA

HEDMA
approached the output wavelength of the curing unit (470 nm).

resins
This was explained by the scattering effect of fillers of this size
on penetrating light during photoactivation [9].
The aim of this study was to assess the DC of some bulk-fill

N377465/universal
composite materials compared to that of conventional flow-
1000830/universal

1208392/universal
Lot no./shade

010028/universal
able and regular composites using FTIR spectroscopy at two

1104372/A2

1048014/A3
time intervals: immediately post-cure, and 24 h post-cure. Two

010021/AM
010027/A3
null hypotheses were investigated: (i) there is no difference
in the DC values of the low stress bulk-fill composites SDR,
VBF, and XB in comparison to those of conventional compos-
ite materials, and (ii) there is no difference between DC values
Manufacturer

immediately post-cure and 24 h post-cure for all materials.

DENTSPLY

3M ESPE
Heraeus

Heraeus

Heraeus
VOCO

VOCO

VOCO
2. Materials and methods

2.1. Device used for assessment of DC

Flowable bulk fill

Flowable bulk fill

Flowable bulk fill

Flowable bulk fill

Table 1 – Materials, manufactures, lot numbers, and composition.

Low shrinkage
nanohybrid
nanohybrid
Type

Eight resin composite materials were investigated including

Flowable

Flowable

three flowable bulk-fill composites (Table 1). The DC was mea-

sured using FTIR (Avatar 360, Nicolet Analytical Instruments,
UK) equipped with a single reflection horizontal attenuated
total reflectance (ATR) accessory (MIRacle ATR, PIKE Technolo-
Code

gies, 6125 Cottonwood Drive, Madison). The FTIR spectrometer

VDF
SDR

GRF
VBF

FBF

VD

GR

was operated under the following conditions: 4000–500 cm−1

XB

wavelength, 6 cm−1 resolution, and 32 scans.

Venous Diamond

Venus Diamond
Grandioso Flow
Venus Bulk Fill

Filtek Bulk Fill

Material
SureFil SDR

2.2. Measurement of immediate post-cure DC

Grandioso
x-tra base

Flow

Uncured composite material was placed on the ATR crystal

making sure that the crystal was completely covered by the
material (n = 3), the FTIR spectra of the uncured samples were
Conventional regular

then collected. Each material sample was then cured at room

flowable composites
Bulk fill composites

temperature for 20 s (as recommended by the manufacturer)

using a halogen curing light (Optilux 501, Kerr Corporation,
Conventional

composites

USA) with an output irradiance of 600 mW/cm2 and standard

curing mode. The light tip was kept as close as possible to
Group

the sample. The FTIR spectra of the cured samples were then
collected immediately.

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 d e n t a l m a t e r i a l s 2 9 ( 2 0 1 3 ) e213–e217 e215

2.3. Measurement of 24 h post-cure DC

Table 2 – Mean DC of materials immediately post-cure
and 24 h post-cure (same superscript letters indicate non
To assess the DC of the materials after 24 h storage at 37 ◦ C, significant differences within the same column).
thin samples (n = 3) were prepared by applying a small amount
Material DC% (standard DC% (standard
of each material on a piece of glossy transparent polyester deviation) deviation) 24 h
film set on a glass microscope slide. The material was then immediately post-cure
covered with another piece of polyester film and pressed with post-cure
another glass slide until a thin film was created. Each sam- SDR 58.4 (0.5)a,b 76.1 (0.7)a
ple was checked to ensure consistent thickness. The sample VBF 55.7 (0.6)a,b,c 79.2 (1.8)a
was then cured with the curing light exit window against the XB 53.9 (1.0)a,c 62.1 (0.4)
glass slide. The samples were then stored for 24 h at 37 ◦ C in a FBF 49.5 (1.9)c 50.9 (1.5)
lightproof oven within a sealed glass container with silica gel VDF 62.0 (3.3)b 70.6 (2.1)b
GRF 77.1 (3.5) 93.1 (0.2)
(to prevent water adsorption onto the surface of the samples
VD 34.7 (2.6) 79.0 (1.3)a
and avoid the potential source of noise in an FTIR). After 24 h, GR 50.0 (0.5)a,b,c 69.1 (0.6)b
each sample was carefully placed on the ATR crystal plate and
pressed with a clamp to maintain good contact between the flowable composite GRF has statistically significant higher
sample and the ATR crystal. An FTIR spectrum of the sample DC value (77.1%) than all other materials (p < 0.001), while VD
was then collected. had a statistically significant lower DC value of 34.7% than
all other materials (p < 0.001). Within the flowable bulk-fill
2.4. DC calculation materials group, there was no significant difference in the DC
values when materials were compared to each other except
For all samples, DC was measured by assessing the variation between SDR and FBF (p = 0.002).
in the ratio of the absorbance intensities of aliphatic C C peak After 24 h storage at 37 ◦ C, XB and FBF showed statistically
at 1638 cm−1 and that of an internal standard peak of aro- significant lower DC (62.1 and 50.9% respectively), while GRF
matic C C at 1608 cm−1 of the uncured and cured samples. had a statistically significant higher DC value (93.1%) than
Due to the lack of aromatic C C, internal standard peaks at other materials. Both bulk-fill SDR and VBF showed DC com-
1600 cm−1 and 1720 cm−1 were used in the case of SDR and parable to the rest of the materials.
VD respectively. The percentage DC was calculated for each
sample using the following equation:
  
(1638 cm−1 /interrnal standard) peak area after curing)
DC% = 1 − × 100
(1638 cm−1 /interrnal standard) peak area before curing

In the immediately post-cure investigation, DC was cal-

culated using the pre-cure and post-cure absorption values
of the same sample. For the 24 h post-cure investigation, DC
was calculated using the 24 h post-cure absorption values of
each sample against the absorption values of a separate single
pre-cure sample of each material.
Independent-sample t-test to assess the difference
between the immediate post-cure and 24 h post-cure DC
values for each material, showed that the mean DC of all the
materials (excluding FBF) after 24 h storage at 37 ◦ C were sta-
tistically higher than those obtained immediately post-cure

2.5. Statistical analysis

Data were entered in to statistical software (SPSS 16.0, Chicago,

IL, USA). For the data from samples used to assess the imme-
diate post-cure and 24 h post-cure DC, values of each material
were compared using a one-way analysis of variance (ANOVA)
and Bonferroni post hoc test at ˛ = 0.05 level. Data obtained
from the samples to assess immediate post-cure DC were
compared to those of the 24 h post-cure DC using an inde-
pendent T-test.

3. Results

DC values and standard deviations (SD) of the materials are

presented in Table 2 and Fig. 1. Immediately post-cure, the
mean DC values of the different materials were in the fol-
lowing order: GRF > VDF > SDR > VBF > XB > GR > FBF > VD.
24 h post-cure, they were in the following order: Fig. 1 – Mean degree of conversion (DC) of materials
GRF > VBF > VD > SDR > VDF > GR > XB > FBF. Immediately immediately post-cure and 24 h post-cure at 37 ◦ C. The bars
post-cure, Post hoc analysis showed that the conventional represent the standard deviation.

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 e216 d e n t a l m a t e r i a l s 2 9 ( 2 0 1 3 ) e213–e217
(˛ = 0.05) with an average of 36% increase for each material. P
values for the Independent sample t-test for the two different
time intervals were: <0.001 for SDR, VBF, XB, VD, and GR, 0.018
for VDF, 0.001 for GRF, and 0.544 for FBF.
4. Discussion
4.1. Methodology
In this study, the DC of different commercially available den-
tal composites was assessed using FTIR spectroscopy. Unlike
indirect techniques which rely on measuring changes in the
mechanical performance of the material to assess relative DC,
FTIR spectroscopy allows the direct detection of the amount
of unreacted C C in the resin matrix [12,13].
DC was assessed at two-time intervals (immediately post-
cure and 24 h post-cure). Different samples were used in the
two experiments. Samples used for the immediate post-cure
assessment could not be used for assessing the 24 h post-cure
DC for two reasons. Firstly, removal of cured samples from
the ATR crystal plate to be reassessed results in damage of
the samples which consequently results in very poor spectra,
collected from these samples. Secondly, when these samples
were left undisturbed on the ATR crystal for 24 h and then
measured, the loss of contact between the samples and the
ATR crystal due to polymerization shrinkage results in highly
distorted spectra with high level of noise.
4.2. DC changes over 24 h
Most of post-irradiation polymerization has been shown to
take place in the first few minutes or one hour after removal of
the irradiation source [14,15], with subsequent slower increase
up to a maximum of 24 h post-irradiation [16]. In this study, all
the materials (except FBF), showed significant increase of DC
at 24 h post-irradiation and storage at 37 ◦ C when compared
to those obtained immediately post-cure.
The DC values of some of the materials have been previ-
ously assessed using spectroscopy techniques. Values of 58.9%
(±2.9) and 65.0% (±1.9) have been reported for SDR and VBF
respectively. These were obtained 5 min after curing using a
curing light of an irradiance of 1226 mW/cm2 for 10 s [17].
When compared to the values obtained immediately post-cure
in this study, 58.4% (±0.5) and 55.7% (±0.6) for SDR and VBF
respectively, these values are comparable considering differ-
ences in light irradiance and post-irradiation time. DC of VDF
immediately post-cure has been assessed using Raman spec-
troscopy with a DC value of 68% (±1.0) when specimens were
cured for 40 s using an LED light [18]. This is comparable to the
immediate post-cure DC value of VDF, 62% (±3.2), obtained in
this investigation.
4.3. Effect of chemical composition on ultimate DC
Since polymerization conditions were kept standardized in
this study, differences in the DC of the materials can be
attributed to variations in the chemistry of their resin matrix.
The main two features of a monomer that affect the degree
of conversion and reactivity are the initial monomer viscosity
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and flexibility of its chemical structure [19] and the ultimate
degree of conversion of different monomer systems increases
in the following order: Bis-GMA < Bis-EMA < UDMA < TEGDMA
[20]. Bis-GMA is considered the most viscous and least flexible
monomer due to the strong intramolecular hydrogen bond-
ing via its pendant hydroxyl groups OH and the presence of
rigid aromatic nuclei in its structure. UDMA is also a viscous
monomer due to the hydrogen bond intramolecular interac-
tion between its imino ( NH ) and carbonyl groups ( C O).
However, the viscosity of UDMA is much lower than that of
Bis-GMA because of the weak hydrogen bond of its imino
( NH ) group compared to that of hydroxyl groups ( OH) [21].
Also, the presence of imino groups ( NH ) in the urethane
structure of UDMA monomer is responsible for the charac-
teristic chain transfer reactions that provide an alternative
path for the continuation of polymerization. These reactions
result in increased mobility of radical sites on the network and
consequently enhanced polymerization and monomer con-
version [20]. This explains the high reactivity and ultimate
DC of UDMA based monomer systems (SDR, VBF, VDF, and
VD) when compared to that of Bis-GMA based composites (GR,
XB, and FBF). However, when Bis-GMA is diluted with the low
viscosity TEGDMA monomer, a synergistic effect on the rate
of polymerization, network plasticization, and DC has been
observed [20]. This might explain the significantly higher DC
of GRF than that of other materials since it may contain a
higher TEGDMA/Bis-GMA ratio to enhance its flowable con-
sistency. The significantly lower 24 h post cure DC of XB and
FBF materials than all other tested composites may be due to
the presence of the high molecular weight Bis-EMA monomer
mixed with UDMA. Although this bulky monomer with its
stiff central phenyl ring core might enhance the mechanical
performance of the material, it can significantly restrict the
mobility of UDMA monomers and decrease their reactivity and
ultimate conversion value. Also, for XB, its high filler loading
might contribute toward a lower DC.
4.4. Immediate post-cure DC
Polymerization shrinkage stress can be effectively reduced by
decreasing the rate of polymerization either by controlling
the initial curing light intensity or by modifying the polymer-
ization inhibitor concentration, which manifests as low DC
values at early stages of polymerization [22–24]. The relatively
low immediate post-cure DC values of the bulk-fill materials
SDR, VBF, FBF and XB when compared to those of conven-
tional flowable materials GRF and VDF may be the effect of
altered polymerization behavior of the former and may con-
tribute to reduced shrinkage stress upon polymerization as
was shown for SDR [25]. However, more studies are required
to kinetically assess the immediate DC values of bulk-fill com-
posites and effect on their shrinkage stress values compared
to conventional materials.
5. Conclusions
Within the limitation of this study the following can be con-
cluded:
 d e n t a l m a t e r i a l s 2 9 ( 2 0 1 3 ) e213–e217
(1) The ultimate DC values of the bulk-fill composites SDR and
VBF were generally comparable to those of conventional
composites studied. The resin chemistry does not seem to
negatively influence the polymerization process in these
materials.
(2) Although clinically acceptable (>55%), the ultimate DC of
the bulk-fill composite XB was significantly lower than the
other materials.
(3) The conventional flowable composite GRF showed a signif-
icantly higher DC than that of other materials that may be
attributed to its high concentration of TEGDMA monomer.
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