d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 13241328

available at www.sciencedirect.com

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

Optical characterization of bisphenol-A-

glycidyldimethacrylatetriethyleneglycoldimethacrylate
(BisGMA/TEGDMA) monomers and copolymer

Janne Lehtinen a, , Toni Laurila a , Lippo V.J. Lassila b , Pekka K. Vallittu b ,

Jukka Raty c , Rolf Hernberg a
a Tampere University of Technology, Institute of Physics, Optics Laboratory,
Tampere, Finland 33720
b University of Turku, Institute of Dentistry, Department of Prosthetic Dentistry

and Biomaterials Science, Turku, Finland

c University of Oulu, Measurement and Sensor Laboratory, Kajaani, Finland

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

Article history: Objective. The fundamental optical characteristics of dental polymers as a function
Received 16 October 2006 of curing time are exiguously reported in the literature. In this work the refrac-
Received in revised form tive index [1] and the extinction coefcient [2] of bisphenol-A-glycidyldimethacrylate
30 January 2008 triethyleneglycoldimethacrylate (BisGMA/TEGDMA)-based polymers of different volume
Accepted 11 February 2008 fractions have been studied as a function of the curing time. A comparison between the mea-
sured index of refraction and theoretical calculation based on molar refraction is made. Also
the temporal behavior of both the refractive index and extinction coefcient is compared.
Keywords: Methods. Index of refraction: BisGMA/TEGDMA monomer samples were cured with a
BisGMA commercial light-curing unit by using camphorquinone and DMAEMA as the photoini-
TEGDMA tiator system. Curing times of 0, 40, 60, 300, 900 and 1800 s were used. The refractive
Optical properties indices were determined with a refractometer at 470 nm wavelength, where the peak
Optical characterization absorption of the camphorquinone photoinitiator is located. Extinction coefcient: Bis-
Dental composites GMA/TEGDMA samples having different lengths were cured and the relative attenuation
Dental polymer of light at 470 nm was measured as a function of the curing time (0, 40, 60, 300, 900,
Monomer 1800 s).
Refractive index Results. The results show that in general the index of refraction increases during the pho-
Extinction coefcient topolymerization process in a time frame from 0 to 40 s and then approaches a steady-state
value, which depends on the original composition of the admixture. The detailed refractive
index change depends on the volume fractions of the constituent substances. The extinc-
tion coefcient decreases in a time frame from 60 to 900 s and reaches a steady-state value
thereafter.
Signicance. Knowledge of the fundamental optical characteristics of commonly used dental
polymers is essential in the development of advanced light-initiated curing methods.
2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +358 3 7418883; fax: +358 3 31152090.
E-mail address: janne.lehtinen@tut. (J. Lehtinen).
0109-5641/$ see front matter 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2008.02.012
 d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 13241328
1. Introduction
The light curing of dental resins and resin composites in small
volumes using halogen lamps or more modern LED (light emit-
ting diodes) units is a routine operation. However, efcient
single-step curing of larger volumes is still a technical chal-
lenge. The need for larger resin and resin composite volumes
exists in several applications. The current trend is in the use
of non-metallic materials in implants and bone repairs. More-
over, in dentistry the understanding of the behavior of the
resin systems optical properties is of importance. However,
large volume polymerization techniques may be limited by
the dimensional changes due to the polymerization shrinkage
[35].
Dental resin composites based on BisGMA (2,2-bis[4-(2-
hydroxy-3-methacrylyloxypropoxy)phenyl]propane) are com-
monly used in dental restorations and in some bone cements
[68]. However, despite the wide use of various light curable
BisGMA-based resin mixtures in dentistry, their fundamental
optical properties at the curing wavelength during the curing
process are relatively weakly covered.
The refractive index of bulk material describes how light
is refracted at the material boundaries. On the other hand,
a materials extinction coefcient describes the attenua-
tion of light per unit length as it propagates through the
material. These two wavelength-dependent coefcients are
essential in the characterization of the materials optical prop-
erties, e.g., absorbance, transmittance and reectance. In this
work the fundamental optical quantities, refractive index
and extinction coefcient, were experimentally determined
as a function of the curing time for the BisGMA/TEGDMA
monomer/polymer system. The measurements were made
using blue light of blue 470 nm wavelength. The peak absorp-
tion wavelength of the commonly used camphorquinone (CQ)
photoinitiator is located at 470 nm spectral region, and there-
fore it is the most relevant wavelength region in CQ-based
curing systems [9,10].
2. Materials and methods
Four types of BisGMA/TEGDMA monomer admixtures were
used in the measurement of the index of refraction. In
all the admixtures CQ and DMAEMA (dimethylaminoethyl
methacrylate) were used as the photoinitiator system and
TEGDMA (triethylene glycol dimethacrylate) as a diluent. Bis-
GMA/TEGDMA volume fractions were 50/50, 70/30, 80/20 and
99/1. A TRIAD 2000TM Visible Light Curing Unit (Dentsply Inter-
national Ltd.), with 275 W halogen light source, was used for
the curing.
Samples for the refractive index measurements
were fabricated using a stainless steel mold having
10 mm 40 mm 2 mm sample volume. The surface of
the steel mold was coated with mold wax to facilitate
the detachment of the cured samples. After injecting the
BisGMA/TEGDMA monomer admixture into the mold, a
borosilicate glass plate (5-mm thick) was placed on top of
the mold to ensure the smoothness and consistency of the
volume of the samples. Samples were then cured for 0, 40,
1325
60, 300, 900 or 1800 s. Cured samples were stored in a freezer
(20 C) for 3 days before the actual measurements.
The degree of monomer conversion (DC%) was monitored
with Fourier transform infrared spectroscopy (FT-IR) (Spec-
trum One, PerkinElmer) having an attenuated total reectance
(ATR) sampling accessory. Each sample was powdered and
placed on the surface of a ZnSe-ATR crystal. DC% was
calculated from the aliphatic C C peak at 1638 cm1 , and
normalized against the aromatic C C peak at 1608 cm1
according to the formula:
 
Caliphatic /Caromatic
DC% = 1 100% (1)
Ualiphatic /Uaromatic
where Caliphatic = absorption peak at 1638 cm1 of the cured
sample, Caromatic = absorption peak at 1608 cm1 of the cured
sample, Ualiphatic = absorption peak at 1638 cm1 of the
uncured sample, Uaromatic = absorption peak at 1608 cm1 of
the uncured sample.
The fraction of the remaining double bonds for each spec-
trum was determined by using a standard baseline technique,
in which the heights of aliphatic and aromatic peaks are com-
pared.
The index of refraction was measured in the Measurement
and Sensor Laboratory (Kajaani, Finland) using a commercial
ABBE-refractometer (ABBE 60/ED, Bellingham & Stanley Ltd.)
[11]. As a light source a broadband xenon lamp (Oriel Ltd.,
66002) was used. The lamp light was coupled to the refrac-
tometer through a monochromator (Oriel Ltd., 77250) in order
to select the desired blue 470 nm spectral range. The band-
width of the blue light was 5 nm. In the refractometer the
blue light beam was directed to the front end of the sample
volume and the critical angle of total internal reection was
measured [12]. The refractive index can be calculated from the
angle of the total internal reection. To enhance diffuse scat-
tering of the cured solid polymer samples, the front surface of
each sample plate was roughened with abrasive paper. Diffuse
scattering at the front surface was necessary to improve the
accuracy of the measurement.
The index of refraction of an amorphous polymer can be
calculated approximately by using the molar properties of
a single-polymer structural unit. For every chemical bond
that contributes to the structural unit, bond refraction can be
dened. Summing of these properties gives the molar refrac-
tion of a molecule, from which an approximate value of the
bulk index of refraction can be obtained with several meth-
ods. One of these methods is the molar refraction according

to Vogel, which is dened as RV = R = nM, where RV is
i V,i
the total molar refraction, RV,i the bond refraction of the con-
stituent, n the index of refraction and M the molar mass of
the particular polymer molecule. The indices of refraction for
BisGMA and TEGDMA were calculated based on the molar
masses and tabulated values for bond refractions of the con-
stituent bonds [13]. The bond refraction values determined
at the standard yellow Fraunhofer line of sodium (589 nm)
were used. The refractive index of the heterogeneous Bis-
GMA and TEGDMA polymer admixtures were calculated by
weighing the two compounds indices of refraction with their
volumetric fractions [14]. With this method, the heteroge-
neous index of refraction is calculated with the following lower
1326 d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 13241328

Table 1 Theoretical refractive indices with their lower

and upper boundaries for the BisGMA/TEGDMA polymer
admixtures studied in this work
BisGMA/TEGDMA (%) n

50/50 1.5451.547
70/30 1.5611.563
80/20 1.5691.571
99/1 1.585


and upper limits for the refractive index: 1/n2low = (v /n2 ),
 2 i i i
n2high = v n
i i i
, where nlow and n high are the lower and upper
limit for the index of refraction, i is the volumetric fraction of
each compound in a heterogeneous polymer and ni the refrac-
tive index of each compound.
For the measurement of the extinction coefcients half-
cylindrical Teon molds with borosilicate glass plate ends
were made. The sample lengths were 13, 5, 7 and 10 mm. Bis-
GMA/TEGDMA admixtures (50/50, 70/30, 99/1) were injected
into the molds and cured with the TRIAD 2000TM light-curing
unit. Curing times were 0, 40, 60, 300, 900 and 1800 s and the
extinction coefcients were measured immediately after each
curing. In the measurement of the extinction coefcient a con-
ventional 55 W broadband halogen lamp was used as a light
source. A monochromator (Lomo MDR-2) was used to separate
a 4-nm spectral band around the central 470 nm wavelength.
After traversing the sample the light beam was focused to a
photodiode (Ophir Ltd., PD300-UV). For each cured sample the
relative attenuation of the blue light intensity was measured
as a function of the sample length. The extinction coefcient
was then calculated for each sample from the BeerLambert
law: Fig. 1 (a) Index of refraction as a function of curing time
I  1
with different BisGMA/TEGDMA admixtures. Standard
1
 = ln deviation caused by the ABBE-refractometer was negligible
Ii Li L1
so it is not indicated in the gure. (b) The difference
where  is the extinction coefcient, I1 is the measured between the index of refraction for the unpolymerized and
intensity from the 1-mm long sample, which was used as a 1800 s cured resin as a function of the BisGMA
reference, Ii is the measured intensity from the samples with concentration.
lengths i = 2, 3, 5, 7 and 10 mm.

3. Results
The dependence of the indices of refraction on curing time
and on BisGMA concentration are shown in Fig. 1a and b,
respectively. From Fig. 1a it can be observed that for all the
admixtures a similar change in the refractive index appears
during the curing from 0 to 40 s. During this time interval
the index of refraction increases rapidly and then stabilizes
to a nal value thereafter. Refraction indices are dependent
on the molar ratio of the monomer system. Fig. 1b shows that
an increase in the BisGMA content decreases the refractive
index difference between the non-polymerized and polymer-
ized samples. Table 1 shows the theoretical refractive indices
of different admixtures based on the molar refraction approx-
imation with lower and upper limits. The theoretical and
measured values are in good agreement.
The dependence of the extinction coefcients of differ-
ent admixtures as on curing time is summarized in Table 2.

Table 2 Extinction coefcients as a function of time for different BisGMA/TEGDMA admixtures

 (cm1 ) Curing time (s)

0 40 60 300 900 1800

50/50 3.3 0.5 3.4 0.4 3.3 0.5 0.7 0.1 0.4 0.1 0.5 0.1
70/30 3.3 0.1 3.4 0.6 3.4 0.6 1.0 0.5 0.6 0.3 0.8 0.3
99/1 2.7 0.5 2.6 0.4 2.5 0.4 0.8 0.3 0.4 0.1 0.5 0.2

Measurement error is expressed as standard deviation.

 d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 13241328
Fig. 2 Extinction coefcients of BisGMA/TEGDMA 50/50
and 99/1 admixtures as a function of the curing time. Error
bars indicate standard deviation.
Fig. 2 shows the dependence of the extinction coefcient of
the 70/30 BisGMA/TEGDMA admixture on curing time. Unlike
the index of refraction, the extinction coefcient remains con-
stant at the beginning of the curing process. However, from 60
to 900 s a decrease in the extinction coefcient occurs. Further
curing after 900 s does not have any signicant effect on the
materials extinction coefcient.
4. Discussion
The present study revealed that the index of refraction
increases with polymerization of the resin system. At the time
point of 40 s a plateau in the index of refraction was reached
for the resin mixtures containing substantial quantities of
TEGDMA resin, whereas the resin mixture predominantly of
BisGMA showed a slight ongoing increase in the index even
after longer curing times up to 300 s. Thus the highly viscous
BisGMA resin takes more time to polymerize by light activation
than those monomer mixtures which have been diluted with,
e.g., monomer of TEGDMA. A comparison between the theo-
retical and measured values shows good agreement despite
the difference between the wavelengths of the measured and
calculated values. The values of theoretical calculations differ
at most by 1% from the measured ones. In BisGMA/TEGDMA
admixtures with the 50/50 and 70/30 volume fractions, this dif-
ference can be explained by the wavelength dependence of the
refractive index. At higher volume fractions, 80/20 and 99/1,
the theoretical molar refraction approximation yields slightly
too high refractive index values. The extinction coefcients of
the resin mixtures decreased with curing time. After 60 s of
curing, the coefcient of extinction drops considerably up to
about 900 s.
The difference in the temporal behavior of the extinc-
tion coefcient and the refractive index can be explained by
exploring the fundamental reasons for these two phenomena.
Refractive index is basically related to the molecular proper-
ties (polarizability) and the density of the substance [15]. The
reorganization of the molecular structure during polymeriza-
1327
tion is, in many cases, a rapid process. According to the results,
polymerization increases the refractive index.
On the other hand, the absorption of light at 470 nm
depends mainly on the amount of photoinitiator (CQ). The
curing radicalizes the photoinitiator molecules, which then
bond with the monomer molecules in order to enable free rad-
ical chain polymerization [16]. Bonding with the monomers
reduces the amount of the photoinitiator that can absorb the
curing light and therefore the extinction coefcient at 470 nm
decreases during curing. The extinction coefcient decreases
until the extinction is dominated by the BisGMA/TEGDMA
mixture. To verify the reduction of CQ as a function of
the curing time the transmittance was monitored with a
UVvis recording spectrophotometer (Shimadzu Corp., UV-
2501PC). The transmittance of 2-mm thick slabs of 50/50
BisGMA/TEGDMA polymer admixture was measured with dif-
ferent curing times. From Fig. 3 it can be observed that the
absorption due to CQ decreases as a function of curing time.
This decrease is pronounced at longer curing times. The
authors suggest that this explains the difference in the tem-
poral behavior between the extinction coefcient and the
refractive index.
It needs to be emphasized that the present study deter-
mined optical properties of resins only. In many dental
applications the resins are used as a part of compos-
ite materials, where particulates or bers are used as
llers and structural reinforcements. The detailed optical
behavior of isotropic particulate ller composite resins and
iso/ortho/anisotropic ber-reinforced composite resins [17]
needs to be investigated further.
The results obtained in this work aid in the development of
novel and optimized curing methods for larger volume resins,
for instance in root canal applications, where light transmis-
sion to the apical part of the root is not adequate [18]. There
are also interests to develop novel single-step curing methods
for larger volume medical polymer composites [19]. If low-
shrinking polymer systems investigated here, or those based
on ring-opening polymerization [20] mature to clinical use,
the characterization of the optical properties described in the
present study could be of great importance.
Fig. 3 The transmission of BisGMA/TEGDMA admixture
with 50/50 volume fraction as a function of the wavelength
for different curing times.
1328 d e n t a l m a t e r i a l s 2 4 ( 2 0 0 8 ) 13241328

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