pISSN, eISSN 0125-5614

Original Article M Dent J 2017; 37 (1) : 29-35

Effect of curing protocols on degree of conversion and

glass transition temperature of a dual-cured resin
cement
Kornpavee Simapronchai1, Prompong Pienpinijtham2, Pong Pongprueksa1,
Pisol Senawongse1
1
Department of Operative Dentistry and Endodontics, Faculty of Dentistry, Mahidol University, Thailand
2
Department of Chemistry, Faculty of Science, Chulalongkorn University, Thailand

Objective: The objective of this study was to investigate the effect of light-curing protocols on degree of conversion
(DC) and glass transition temperature (Tg) of a dual-cured resin cement (Variolink N). The correlation between
DC and Tg was further investigated.
Materials and methods: Different light-curing protocols (no irradiation, irradiation with light tip directly contact to
specimen, and irradiation with light tip positioned at 10 mm from specimen) were used investigate the influence
of energy density (ED) on DC and Tg of the resin cement. 15 and 45 specimens of mixed cement were prepared
for DC and Tg observation respectively, then subjected to irradiating protocols underneath a ceramic block
(10 mm length x 10 mm width x 0.95 mm thickness) and light cure for 40 sec in light curing groups. DC was
measured by Raman microspectroscopy and Tg was measured by differential scanning calorimetry at 5 min,
15 min and 24 hrs after post-polymerization. Data were submitted to two-way ANOVA. The DC and Tg data were
subjected to linear regression analysis.
Results: Increasing of distance between light tip and specimens decreased ED. Curing protocols with different
ED influenced DC (p<0.01) and Tg (p<0.01) of the cement. The increasing of ED significantly increased DC
and Tg. The DC and Tg improved significantly with the extension of post-polymerization times up to 24 hrs. A
significantly positive correlation was found between DC and Tg.
Conclusion: ED of curing light and post-polymerization times influenced DC and Tg of the dual-cured resin
cement.
Keyword: degree of conversion, energy density, glass transition temperature, light-cure, resin cement,
self-cure
How to cite: Simapronchai K, Pienpinijtham P, Pongprueksa P, Senawongse P. Effect of Curing Protocols on Degree
of Conversion and Glass Transition Temperature of a Dual-cured Resin Cement. M Dent J 2017; 37: 29-35.

Introduction cure polymerization mechanism together [2]. The

light-cure polymerization is a setting mechanism
of polymer via activation with blue visible light [2].
Resin cement is commonly used for Thus, the polymerization of the dual-cure resin
tooth restoration because of their physical and cement can be further occurred via self-cure
mechanical properties [1]. According to the mechanism as post-polymerization [3]. From the
mechanism of polymerization, this cement can benefit of dual-cure mechanism, this dual-cure
be categorized into 3 types of self-cure, light- resin cement can be used for all clinical situations
cure and dual-cure resin cement. Dual-cure resin from full metal to tooth colored restoration and
cement is a system combining self-cure and light- become mostly use in dentistry [1].

Corresponding author: Pisol Senawongse, Department of Operative Dentistry and Endodontics Faculty of Dentistry, 6 Yothi Road, Bangkok 10400 Thailand
Tel: (662)2007825-6 Email: [email protected]
Received : 4 January 2017 Accepted : 8 March 2017
Kornpavee Simapronchai, et al

With dual-cure polymerization mechanism the polymer is transformed from a glassy material
of dual-cure resin cement, the influence of light into a rubberlike one. Crosslinking reduces
cure polymerization on the final properties of molecular mobility and thus gives rise to increased
dual-cured resin cement has been reported [3-6]. apparent Tg [3,4,11]. Thus, the curing protocols
The mechanical properties of a dual-cured resin may influence the regularity of the network and the
composite via light-cure polymerization are mainly crosslink density. This may be reflected in the Tg.
influenced by the amount of energy delivered To improve the performance regarding to
during irradiation [4]. The energy density (ED) or polymerizing characterization of dual-cured resin
total amount of energy per unit area is the product cement, a detailed understanding of the effects of
of the power per unit area (curing light intensity) curing protocols on DC and Tg and the correlation
by the duration of irradiation (curing time) [4]. For between Dc and Tg are necessary.
a given ED, different light-curing protocols such The aim of the study was to determine degree
as leaving polymerization with self-curing mode of conversion and glass transition temperature
(no irradiation), curing with high intensity of curing in relation with the curing protocol and post-
light and curing with low intensity of light have polymerization times. The hypothesis of present
been proposed to influence the properties of dual- study was the total energy densities caused by the
cure resin cement [4,6]. Therefore, the different different curing protocols and post-polymerization
light-curing protocols may lead to polymers of times have influence on DC and Tg properties. A
different network structure, even though the DC is further aim was to attempt to correlate the DC with
the same. Tg properties of this dual-cure resin cement.
Generally, the DC of polymers is used
to evaluate the conversion of double bonds to
single bond while forming polymer networks Materials and methods
[7]. However, DC of polymer could not be used
as a representation of complete polymerization The dual-cure resin cement used in this
characterization of polymers structures because study was Variolink N (shade yellow A3, lot
polymers of similar DC may have different extent NO.; U55161 (base), V03978 (catalyst), Ivoclar-
of crosslinking or in vice versa [3,4]. This scenario Vivadent, Schaan, Liechtenstein). It is composed
may occur in dual-cure resin cements, as a result of of base and catalyst. The compositions of base are
different light-curing protocols. This may probably Bis-GMA (bisphenol-A-glycidyl dimethacrylate),
due to the formation of relatively fewer growth UDMA (Urethane dimethacrylate), TEGDMA
centers of self-cure mode, which may result in a (Triethyleneglycol dimethacrylate), inorganic filler,
more linear polymer, with decreased crosslinking. ytterbium tri fluoride, initiator, and stabilizer. The
[4,8]. The increased concentration of crosslinking compositions of catalyst are Bis-GMA, UDMA,
has been proposed to improve physical properties TEGDMA, inorganic filler, ytterbium tri-fluoride,
and stability of polymers [6,9,10]. benzoyl peroxide, and stabilizer.
The extent of crosslinking of a polymer may For degree of conversion observation, the
be proposed to determine by measurements specimens were prepared by mixing the cement
of the glass transition temperature (Tg). Tg is an according to the manufacturer’s instruction.
important parameter for polymer characterization The mixed cement was placed onto 1 mm thick
as it marks a region of dramatic changes in the transparent microscope glass slide and between
physical properties of the polymer [6,9]. The Tg two microscope coverslips with the thickness of
value represents the temperature region at which 100 microns. These two coverslips were used for

30 M Dent J 2017 April; 37 (1): 31-37

 Effect of curing protocols on degree of conversion and glass transition temperature of a dual-cured resin cement

controlling the cement thickness. The distance determined using a Raman microspectroscopy
between two coverslips was 5 mm. Additional (DXR Raman Microscope, Thermo Scientific,
microscope coverslip was placed over the cement Waltham, MA, USA). The specimens were excited
and pressed over to displace excessive cement. using 780-nm diode laser with the power of
The excessive cement was then removed. 14 mW through a microscope objective lens
This resulted equally 100- microns thickness (x20) coupled with x10 magnification integrated
cement specimen. The totally 15 specimens were microscope (Olympus) at the spatial resolution
prepared. of ~1.9 μm and the spectral resolution of ~2.4–
Specimens were further divided into 3 4.4 cm-1. The light filter was used to protect the
groups of curing protocols; self-cure mode, dual- polymerization of cement from microscope light.
cure mode with optimal light intensity for irradiation, The specimens were placed on the computerized
and dual-cure mode with low light intensity for XYZ stage. All Raman spectra were acquired with
irradiation. Regarding to dual-cure mode, ceramic 60 sec exposure time and two accumulations,
block with a dimension of 0.95 mm thickness, 10 and then data were analyzed using OMNIC 8
mm width and 10 mm length was prepared from software (Thermo Scientific, Waltham, MA, USA).
a lithium disilicate ceramic (IPS e.max CAD, LT Remaining unreacted double bond of vinyl group
shade A1, lot NO.; U39581, Ivoclar-Vivadent, with absorbance intensity peak height at 1639
Schaan, Liechtenstein) to simulate clinical cm-1 was calculated in percentage against internal
situation. The ceramic was placed over the mixed standard, which was aromatic carbon double
cement covered by a coverslip. The cement was bond with peak height at 1609 cm-1 before and
then light-cured with a light emitting diodes curing after polymerization using the following formula.
unit (Elipa S10, 3M ESPE, Seefeld, Germany) DC% = [1-(Rcurd/Runcured)]x100
with an intensity of 1217.20±32.33 mW/cm2. For Rcurd is ratio of absorption peak at 1639 cm-1
the first curing protocol, 5 specimens were kept and absorption peak at 1609 cm-1 of the cured
in light-proof container for simulating self-cure specimens. Runcured is ratio of uncured specimens.
mode. Remaining 10 specimens were further The glass transition temperature (Tg) was
divided into 2 groups and subjected for light measured to identify the crosslinking density
activation for 40 sec with different protocols. For [3,4,6,11] using a differential scanning calorimetry
the second group, the light tip directly contacted (DSC204 F1, Netzsch GmbH, Selb, GermanyMettler
with ceramic to simulate optimal intensity of curing Toledo DSC 1). In self-cure group, resin cement
light. The distance between light tip and ceramic was mixed and delivered to the sample pan. In
was adjusted to 10 mm to simulate low intensity dual-cure group, resin cement was prepared in
of curing light for the third group. The intensity size of 1 mm height and 3 mm in diameter, then
of irradiation through the ceramic was measured covered with coverslip followed by ceramic block
using a light meter (light meter 200, Rolence and given light irradiation through the ceramic
enterprice Inc., Taoyuan, Taiwan). either directly contact or 10 mm from ceramic.
Five specimens from each curing protocol All samples were delivered to sample pan and
were subjected to observation of degree of weighted. Degree of cross-linking will be measured
conversion at 5 min after cement mixing in self- at 5 and 15 minutes after mixing of cement in self-
cure group and after light irradiation in dual-cure cure group or after irradiation in light-cure group
group, then after 15 min and 24 hrs of post- and at 24 hours of post-polymerization in every
polymerization times. group. The Tg was measured under heating rate
The degree of conversion (DC) was 10oC/min from -50oC to 100oC under nitrogen.

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Kornpavee Simapronchai, et al

Data gaining from the calorimetry was analyzed Results

with Proteus software (Netzsch GmbH, Selb,
Germany). The Tg is determined from endothermic
parallel transition of base line, finding Tg point Light intensity and energy density of the
at the heat flow/temperature or specific heat/ curing unit is shown in Table 1. The light intensity
temperature curve. Intersection of estimated heat measured by the light meter was reduced from
flow/temperature is taken as Tg, line drawing from 1217.20±32.33 mW/cm2 down to 570.80±5.81
low temperature end, and the tangent of the slope mW/cm 2 when irradiated through 0.95 mm of
up curve, at the inflection point. ceramic and 243.00±7.31 mW/cm2 when irradiate
Normal distribution and equality of variances 10 mm above ceramic. These caused reducing
of DC and Tg were checked using Kolmogorov- in energy density from 22,832.00±232.21 mJ/cm2
Smirnov test and Levene’s test respectively. The to 9,720.00±292.57 mJ/cm2, respectively when
data of DC and Tg were further statistical analysis curing for 40sec through ceramic.
at 95% confident interval using Two-way ANOVA The data of degree of conversion (DC) and
and Tukey’s multiple comparison. The correlation glass transition temperature (Tg) are demonstrated
and regressive model between Dc and Tg were in Table 2 and 3. The 2-way ANOVA of DC and Tg
analysis. analysis demonstrated significant effect of curing

Table 1 Light intensity and energy density (mean±standard deviation)

Groups Irradiated condition Intensity (mW/cm2) Energy density (mJ/cm2)
Group I No irradiation 0 0
Group II Irradiation with light tip directly contact 570.80±5.81 22,832.00±232.21
to ceramic
Group III Irradiation with light tip positioned 243.00±7.31 9,720.00±292.57
at 10 mm from specimen

Table 2 Degree of conversion (%) (mean±standard deviation)

Groups Post-polymerization times
5 min 15 min 24 hrs
Curing protocols Group I 20.85±1.05g
49.93±1.23 f
78.50±0.72c
Group II 77.79±0.87c, d 78.32±1.13c 84.71±1.09a
Group III 72.19±1.42e 76.21±0.80d 80.97±0.41b

Table 3 Glass transition temperature (oC) (mean±standard deviation)

Groups Post-polymerization times
5 min 15 min 24 hrs
curing protocols Group I -26.72±0.80g
39.07±1.03f 42.43±1.46e
Group II 49.08±1.38c 49.94±1.19c 66.88±1.79a
Group III 43.80±0.97e 46.50±1.01d 63.41±1.19b

32 M Dent J 2017 April; 37 (1): 31-37

 Effect of curing protocols on degree of conversion and glass transition temperature of a dual-cured resin cement

protocols and post-polymerization times to DC and (66.88 oC) was observed for the group II at 24 hrs
Tg (p<0.01). The significant interaction (p<0.01) post-polymerization time. Whereas, the lowest Tg
between curing protocols and post-polymerization (-26.72 oC) was observed for the group of self-cure
times was found both with DC and Tg. protocol at 5 min post-polymerization time.
The data (mean±standard deviation) with the The correlation between DC ang Tg were
same superscripts show no statistically significant calculated and demonstrated in Table 4. The high
difference (P>0.05). (Group I: no irradiation, correlation between DC and Tg were observed for
Group II: irradiation with light tip directly contact all groups. Regressive model for group I showed
to specimen and Group III: irradiation with light tip less unstandardized coefficients (1.20) than Group
positioned at 10 mm from specimen) II (2.43) and Group III (2.14). This means that for
The DC of light irradiated specimens was each group within 24 hrs of post irradiation times,
significantly higher than those of self-cure protocol Group I showed lower degree of increasing of
for each post-polymerization time. Furthermore, Tg than other groups. Finally, the low degree of
the highest DC of each post polymerization time crosslinking with the self-cure mode than other
was observed for Group II. Increasing of post- groups at 24 hrs of post irradiation times may be
polymerization times significantly improved DC in implied.
the same curing protocol except between 5 min
and 15 min post-polymerization times of Group II,
which specimens were irradiated with the curing Discussions
tip contact directly to the ceramic. The highest DC
(84.71%) was observed for the group II at 24 hrs In this study, a dual-cure resin cement was
post-polymerization time. Whereas, the lowest DC cured with three different protocols: no irradiation,
(20.85%) was observed for group I or self-cure irradiation with light tip directly contact to specimen,
protocol at 5 min post polymerization time. and irradiation with light tip positioned at 10 mm
The T g of light irradiated specimens of from specimen. These protocols affected different
group II was significantly higher than those of light intensity of curing light caused different energy
irradiated specimens of group I and III for each post- density as demonstrated in Table 1. The less
polymerization time. Thus, the Tg of all light irradiated energy density of curing light, the lower DC and
specimen was higher than those of specimen with the lower Tg was observed as showed in Table 2
self-cure protocol for each post-polymerization and Table 3. The lowest DC and Tg were observed
time. Increasing of post-polymerization times for the group polymerized without light curing
significantly improved Tg except between 5 min (chemical cure mode).
and 15 min post-polymerization times of Group The results confirm that the DC of a dual-
II that specimens were irradiated with the curing cure resin cement which polymerization process is
tip contact directly to the ceramic. The highest Tg partially initiated by light are significantly influenced

Table 4 Correlation between DC (%) and Tg (oC)

Groups R Regressive model
Group I 0.89 Tg = -41.51+1.20DC
Group II 0.96 Tg = -139.88+2.43DC
Group III 0.91 Tg = -112.68+2.14DC

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Kornpavee Simapronchai, et al

by the amount of energy delivered to the cement were demonstrated. The Tg of group I at 24 hrs
during irradiation. This is in an agreement with (42.43 oC) was less than group II at 5 min (49.08
previous studies [3-5] that showed DC increased o
C) and group II at 15 min (49.94 oC), and the
with increasing of ED. The increasing in DC same event was observed between group III at 15
with energy density may be incorporated by the min and group II at 5 min, which Tg were 46.33 oC
increasing in crosslinking. Thus, the significant and 49.08 oC respectively. The decreased Tg may
relationship between DC and Tg was observed. be interpreted as the manifestation of a polymer
This observation agrees with previous studies [4, structure having fewer crosslinking [3, 4, 6]. The
11, 12]. The increasing of DC and Tg influenced less crosslinking network formation of group I at 24
increasing of elastic modulus of polymers has been hrs compared with group II at 5 min and 15 min,
proposed [4]. The improvement of mechanical and group III at 15 min compared with group II at
properties of dual-cure resin cement might be 5 min might be expected.
expected by light irradiation the cement with The crosslinking of polymers has been
optimal intensity of light to increase DC and Tg proposed that relate to a multitude of growth
[4]. The irradiation of the dual-cure resin cement centers. Many growth centers will increase the
with blue visible light might produce a higher tendency to form a branched polymer. On the
concentration of radicals and rate of polymerization other hand, a relatively linear polymerization will
compared with the cement polymerized only with be observed with the less growth centers [4, 6].
chemical cure [8]. This effect might be ED relating Thus, many growth centers might be expected
[4] that leads DC and Tg to increase in the groups for dual-cure resin cement polymerized with light
with light activation in this study. irradiation. The improvement of sustainability of
The characterization of polymerization such the resin cements by increasing of crosslinking [6,
as the degree of conversion and the crosslinking 9] might be a positive effect of light curing of the
network formation were observed in this study. dual-cure resin cement.
The results of this study showed different rate of In conclusion, high DC and high T g of
polymerization at which DC was growing with time. the dual-cure resin cement could be initiated
Therefore, the heterogeneity of polymerization by additionally curing the cement with optimal
was found that might be related to the mode of intensity of curing light. The tip of light curing unit
curing and the intensity of irradiation light as should be placed onto the surface of restoration
shown in Table 2 and 3. The low rate of degree of as close as possible to gain high energy density
conversion was found in the group polymerized of curing light that directly influence to DC and
with chemical curing. The activation with blue Tg. Nevertheless, it must be realized that the
visible light increased rate of degree of conversion polymerizing characteristic of polymers is also
that was light intensity dependence. This confirmed depended on the compositions and the specific
results of previous studies [3-5]. chemistry of the initiator systems too [13-15].
The apparent of unequal reactivity of
polymerization to DC and Tg was observed. Even Acknowledgement: None
though, the same DC was observed among group Funding: None
I at 24 hrs (78.50%), group II at 5 min (77.79%) Competing interests: None declared
and group II at 15 min (78.32%) and between Ethical approval: None
group II at 5 min (77.79%) and group III at 15 min
(76.21%). The different of Tg among these groups

34 M Dent J 2017 April; 37 (1): 31-37

 Effect of curing protocols on degree of conversion and glass transition temperature of a dual-cured resin cement

Reference 8. Moraes RR, Boscato N, Jardim PS, Schneider LF.

Dual and self-curing potential of self- adhesive resin
cements as thin films. Oper Dent. 2011; 36: 635-42.
9. Asmussen E, Peutzfeldt A. Influence of pulse-delay
1. Rickman LJ, Satterthwaite JD. Considerations for the curing on softening of polymer structures. J Dent
selection of a luting cement. Dent Update. 2010; 37: Res. 2001; 80: 1570-3.
247-8, 251-2, 255-6. 10. da Silva EM, Poskus LT, Guimaraes JG, de Araujo
2. Kwon TY, Bagheri R, Kim YK, Kim KH, Burrow MF. Lima Barcellos A, Fellows CE. Influence of light
Cure mechanisms in materials for use in esthetic polymerization modes on degree of conversion and
dentistry. J Investig Clin Dent. 2012; 3: 3-16. crosslink density of dental composites. J Mater Sci
3. Abedin F, Ye Q, Camarda K, Spencer P. Impact of light Mater Med. 2008; 19: 1027-32.
intensity on the polymerization kinetics and network 11. Lovell LG, Berchtold KA, Elliott JE, Lu H, Bowman CN.
structure of model hydrophobic and hydrophilic Understanding the kinetics and network formation of
methacrylate based dental adhesive resin. J Biomed dimethacrylate dental resins. Polym. Adv. Technol.
Mater Res B Appl Biomater. 2016; 104: 1666-78. 2001; 12: 335-45.
4. Dewaele M, Asmussen E, Peutzfeldt A, Munksgaard 12. Lovell LG, Lu H, Elliott JE, Stansbury JW, Bowman CN.
EC, Benetti AR, Finne G, et al. Influence of curing The effect of cure rate on the mechanical properties
protocol on selected properties of light-curing of dental resins. Dent Mater. 2001; 17: 504-11.
polymers: degree of conversion, volume contraction, 13. Aguiar TR, Di Francescantonio M, Arrais CA,
elastic modulus, and glass transition temperature. Ambrosano GM, Davanzo C, Giannini M. Influence of
Dent Mater. 2009; 25: 1576-84. curing mode and time on degree of conversion of one
5. Silikas N, Eliades G, Watts DC. Light intensity effects conventional and two self-adhesive resin cements.
on resin-composite degree of conversion and Oper Dent. 2010; 35: 295-9.
shrinkage strain. Dent Mater. 2000; 16: 292-6. 14. Tezvergil-Mutluay A, Lassila LV, Vallittu PK. Degree of
6. Soh MS, Yap AU. Influence of curing modes on conversion of dual-cure luting resins light-polymerized
crosslink density in polymer structures. J Dent. 2004; through various materials. Acta Odontol Scand. 2007;
32: 321-6. 65: 201-5.
7. Pianelli C, Devaux J, Bebelman S, Leloup G. The 15. Arrais CA, Giannini M, Rueggeberg FA. Kinetic
micro-Raman spectroscopy, a useful tool to determine analysis of monomer conversion in auto- and dual-
the degree of conversion of light-activated composite polymerizing modes of commercial resin luting
resins. J Biomed Mater Res. 1999; 48: 675-81. cements. J Prosthet Dent. 2009; 101: 128-36.

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